Advances in Addition-Cure Phenolic Resins

Prog. Polym. Sci. 29 (2004) 401498 www.elsevier.
com/locate/ppolysci
Advances in addition-cure phenolic resins

C.P. Reghunadhan Nair*
Propellant and Special Chemicals Group, Polymers and Special Chemicals Division, Vikram Sarabhai Space Centre, Thiruvananthapuram 695 022, India Received 15 January 2003; revised 12 December 2003; accepted 8 January 2004
Abstract Recent developments in the area of addition curable phenolic resins are reviewed. The article highlights the chemistry of addition-cure phenolic resins and discusses the different strategies involved in their molecular design. Structural modication through incorporation of thermally stable, addition curable groups on the novolac backbone is one strategy. The transformation of phenolic hydroxyl groups to addition curable functions forms an alternate approach. Cross-linking of novolac or its derivatives with a suitable curative also leads to addition-curable phenolic resin systems. This article examines the synthesis, characterization and curing of noted addition curable phenolic systems. Their thermal, physical and mechanical properties are discussed and the structure property correlations examined. In selected cases, the adhesive properties of the systems have been examined. The review includes discussions on the properties of the composites in relevant cases. The systems discussed here include mainly allyl- and maleimide-functional phenolics, epoxy phenolic, polybenzoxazine, bisoxazoline phenolic, acetylene-functional and propargyl ether phenolics and phenolic-triazine. The relative advantages and demerits of these systems are discussed and their application potentials are considered. q 2004 Elsevier Ltd. All rights reserved.
Keywords: Addition curable polymers; Phenolic resins; Novolac resins; Epoxyphenolic; Bismaleimides; Allyl phenolics; Xylok; Diallyl bisphenol; Bismaleimides; Maleimide-functional phenolics; Bisoxazolinephenolic; Polybenzoxazine; Propargyl ether phenolic; Acetyleneterminated polymers; Phenyl ethynyl polymers; Phenolic-triazine; High char-yielding polymers; Thermally stable polymers; Film adhesives; Polymer adhesives; Alder-ene reaction; Polymer matrix composites
Contents 1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1.1. Strategies for designing addition-cure phenolics . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2. Allyl-functional phenolics . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2.1. Allyl phenolic bismaleimide blend . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2.1.1. Allyl phenol maleimide reaction mechanism . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2.2. High performance polymers based on allyl phenol BMI systems. . . . . . . . . . . . . . . . . . . . . . . . 2.3. Adhesives based on allyl phenolics BMI . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3. Bisoxazoline phenolics . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3.1. Commercial PBOX phenolic systems. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3.2. Blends and composites of BISOX/Phenolic . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3.3. Structural modications of bisoxazoline phenolics . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
* Fax: 91-471-415236. E-mail address: [email protected] (C.P. Reghunadhan Nair). 0079-6700/03/$ - see front matter q 2004 Elsevier Ltd. All rights reserved. doi:10.1016/j.progpolymsci.2004.01.004
404 405 405 405 406 408 413 418 420 421 422
402
C.P. Reghunadhan Nair / Prog. Polym. Sci. 29 (2004) 401498
4. Polybenzoxazines (PBZ) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4.1. Features of polybenzoxazines . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4.2. Cure mechanism and cure kinetics . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4.3. Structure property relations . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4.4. Reactive blending of polybenzoxazines . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4.5. Non-reactive blends and composites of benzoxazine . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4.6. Degradation of polybenzoxazine . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4.6.1. Thermal stabilization and degradation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4.6.2. Chemical degradation of PBZ . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4.6.3. UV stability of PBZ . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5. Phenol epoxy systems . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5.1. Epoxy phenol cure kinetics . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5.2. Latent catalysis of epoxy phenol reaction. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5.3. Structure properties relations in epoxy phenol . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5.4. Flame resistant epoxy phenolic systems . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5.5. Miscellaneous curative for novolac . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6. Phenolic resins with phenyl maleimide functions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6.1. Maleimide phenolic resin cured with allyl phenolics . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6.2. Maleimide phenolic (PMF) epoxy blend. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7. Pendant phenol functional linear polymers. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7.1. Pendant phenol-functional thermoplastics . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7.2. Pendant phenol-functional addition-cure systems . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 8. Propargyl ether functional phenolics . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 8.1. Curing of propargyl ether resins . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 8.2. Structure property relation in propargyl phenolics . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 8.3. High molar-mass PN resins . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 8.4. Thermal degradation behavior . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 8.5. Propargyl ether resins based on oligomeric novolac . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 8.6. Propargyl novolac epoxy blend . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 9. Phenolic resins with terminal acetylene groups . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 9.1. Curing of EPAN resins. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 9.2. Thermal characteristics of EPAN resins . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 10. Phenolic resins with phenyl ethynyl groups . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 10.1. Phenyl ethynyl functional addition-curable phenolic resins. . . . . . . . . . . . . . . . . . . . . . . . . . . . . 10.1.1. Cure and thermal characteristics of PEPFN resins . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 10.2. Condensation addition cure phenyl ethynyl phenolic resins. . . . . . . . . . . . . . . . . . . . . . . . . . . . 11. Comparative thermal property of PMF, PN, EPAN and PEPFN resins. . . . . . . . . . . . . . . . . . . . . . . . . 12. Phenolic triazine resin (P T resins) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 12.1. Features of P T resins . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 12.2. Properties of P T systems . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 12.3. Structurally modied P T resins . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 12.4. P T/epoxy blends . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 12.5. Thermal degradation of P T resins. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 12.6. Applications of P T resins. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 13. Outlook . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Acknowledgements . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
422 422 424 425 428 431 435 435 437 437 437 437 440 441 447 451 451 455 456 460 460 462 464 465 466 468 469 471 472 474 475 475 477 477 478 479 480 480 481 484 487 489 490 490 490 491 491
403
Nomenclature allyl-functional novolac of bisphenol-A allyl phenolic epoxy allyl phenol novolac from DOPO reacted with terephthaldicarboxaldehyde and phenol B-a bisphenol A-based benzoxazine {bis(4-phenyl-3,4-dihydro-2H-1,3benzoxazinyl) isopropane} BER bispropargyl ether resins BHPP bis (3-hydroxyphenyl) phenyl phosphate BisA-N bisphenol A-novolac BME 4,40 -bismaleimidodiphenyl ether BMI bismaleimide BMIP bisphenol A-bismaleimide BMM 4,40 -bismaleimido diphenyl methane {4,40 - methylene bis (maleimido benzene)} BMS 4,40 -bismaleimidodiphenyl sulfone BPA bisphenol A BPBA bis propargyl ether bisphenol A BPh bisphthalonitrile BPK bis propargyl ether bisphenol ketone BPS bis propargyl ether bisphenol sulfone BZ benzoxazine CAI compression after impact CNE o-cresol novolac epoxy CNH cresol novolac hardener CTE coefcient of thermal expansion DABA 2,20 -diallyl bisphenol A DCPDP dicyclopentadienephenolic resin DDM diamino diphenylmethane DGEBA diglycidyl ether of bisphenol A {2,20 bis (4-glycidyloxy phenyl) propane} Dk dielectric constant DMA dynamic mechanical analysis DMF dimethyl formamide DMSO dimethyl sulfoxide DOPO 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide DOPO-MA melamine-modied Ar-DOPO-N DOPO-PF Ar-DOPO-N, blended with PF novolac DOPO-PN novolac from DOPO and 4-hydroxy benzaldehyde DPn degree of polymerization (number average) ABPF AE AP Ar-DOPO-N
differential thermal analysis ethynyl phenyl azo novolac ethynyl phenyl azo phenol novolac epoxy resin fourier transform infra red fourier transform mechanical spectroscopy technique GC/MS gas chromatography-mass spectrum fracture energy GIC GPC gel permeation chromatography HDT heat distortion temperature HPM 4-hydroxy phenyl maleimide IDT initial decomposition temperature ILSS inter laminar shear strength KIC the fracture toughness (plain-strain stress intensity factor) LOI limiting oxygen index LSS lap shear strength MDI 4,40 -diphenyl methane diisocyanate MMT montmorillonite clay MPN melamine phenol formaldehyde novolac NBR nitrile rubber ODOPB 2-(6-oxido-6H-dibenzo kc,eloxa-phophorin-6-yl)1,4-benzene diol ODOPM DOPO formaldehyde reaction product (2-(6-oxid-6H-dibenz kc,el k1,2l oxaphosphorin-6-yl)-methanol) ODOPM-MPN melamine phenol formaldehyde novolac (MPN)-modied ODOPM ODOPM-PN phenol formaldehyde novolac (PN)modied ODOPM OMMT organically modied montmorillonite clay OPN oligomeric propargyl novolac 1,3-PBOX 1,3-phenylene bisoxazoline PBOX poly(bisoxazoline) PBZ poly(benzoxazine) PC polycarbonate PCL poly(1-caprolactone) PCS poly(4-cyanato styrene) PCS-BD copolymers of 4-cyanato styrene with butadiene PCS-MMA copolymers of 4-cyanato styrene with MMA PDT peak decomposition temperature
DSC EPAN EPAP EPN FTIR FTMS
404
PEAR PEK PEPFN PEPFR PES PF phr PHRR PMAF PMF PMI PMR PN PS P-T Pth-PBZ PTMO PU PVP RT RTM SBSS SEM SIN
poly ether amide resin polyether ketone phenyl ethynyl phenol phenol formaldehyde novolac resin phenyl ethynyl phenol formaldehyde resole resin polyether sulfone phenol formaldehyde novolac resin parts per hundred parts of resin peak heat release rate phenolic resin from HPM, allylphenol and formaldehyde phenolic resin from HPM, phenol and formaldehyde N-phenyl maleimide polymerizable monomeric reactants propargyl novolac polyethersulfone phenolic-triazine phthalonitrile functional polybenzoxazines poly(tetramethylene oxide) polyurethane poly(N-vinyl-2-pyrrolidone) room temperature resin transfer molding short beam shear strength scanning electron microscopy simultaneous interpenetrating networks
T5 Te TEM Terp-Bz Tg TGA TGMDA THF Ti
Tm
TPP TPS TTT UD Va Vba VBP VP VRTM WLF
temperature at 5% weight-loss in TGA temperature of end of thermal phenomenon transmission electron microscopy terpene diphenol-based benzoxazine glass transition temperature thermo gravimetric analysis tetra glycidlyl methylene dianiline tetra hydro furan temperature of onset of thermal phenomenon (curing or decomposition) temperature of maximum of thermal phenomenon (curing or decomposition) triphenyl phosphine T-peel strength time temperature-transformation unidirectional benzoxazine from poly( p-vinyl phenol) benzoxazine from vinyl phenol butyl acrylate copolymer vinyl phenol butyl acrylate copolymer poly( p-vinyl phenol) vacuum resin transfer molding William Landel Ferry
1. Introduction Despite the emergence of several new classes of thermosets, high performance polymers and several other new generation materials that are superior in some respects, phenolic resins retain industrial and commercial interest, a century after its introduction. Phenolic resins are preferred in a wide range of applications, from commodity and construction materials to high technology aerospace industry. This recognition emerges from the fact that these resins have several desirable characteristics, such as superior mechanical strength, heat resistance and dimensional stability, as well as, high resistance
against various solvents, acids and water. They are inherently ame resistant, and evolve low smoke upon incineration. Although phenolics cannot be substitutes for epoxies and polyimides in many engineering areas, their composites still nd a major market in thermo-structural application in the aerospace industry due to good heat and ame resistance, excellent ablative properties and low cost. These key properties add to their market growth, and as a result of innovative research, new products and applications continue to emerge, demonstrating the versatility and the potential of phenol resins to cope with the ever-changing requirements and challenges of advanced technology [1 5].
405
Undisputedly, classical phenolic resins based on resole and novolac dominate the resin market. However, their acceptance as a universal material in many engineering areas is hampered by some of the inherent qualities derived from their special chemical structures. These resins cure at moderately high temperature by a condensation mechanism with the evolution of volatiles, which necessitates application of pressure during molding to form void-free components. The need for the use of catalyst for curing and the limited shelf life of resin at ambient conditions are also major shortcomings of these systems. When compared to many known thermally stable polymers, their thermo-oxidative stability is low. The rigid aromatic units tightly held by the short methylene linkages make the matrix brittle. In view of this, a new chemistry is needed to modify the cure of phenolic resins, in particular, a new method is needed to chain extend and/or to cross-link phenolic resins without production of volatiles and allow for extended shelf stability at ambient conditions for the formulated thermosets. In doing so, it is imperative that the modications do not impair the thermo-mechanical characteristics of the resultant system. The concept of addition cure phenolics gains signicance in this context. 1.1. Strategies for designing addition-cure phenolics Several approaches have been reported for modication of phenolic resins and their cure chemistry. Structural modication to confer addition-cure character has been one thrust area of research [6,7]. Addition-curable phenolic resins with improved thermal and pyrolysis characteristics will be the desirable resins in composites for thermo-structural applications [8]. Higher char-yield leads also to a better heat shielding. Such high char phenolics could be potential candidates as matrices in carbon/carbon composites too with obvious advantages [9]. The major strategies in designing addition-cure phenolics are: (i) Incorporation of thermally stable addition-curable groups on to novolac backbone (ii) Structural modication (transformation) involving phenolic hydroxyl groups (iii) Curing of novolac by suitable curatives through addition reactions of OH groups
(iv) Reactive blending of structurally modied phenolic resin with a functional reactant This article gives an account of recent research efforts in these directions for realizing addition curable phenolic resins.
2. Allyl-functional phenolics Allyl phenol formaldehyde novolac, synthesized by the allylation of novolac can cure thermally at 180 8C without the evolution of volatiles. On heating, the O-allyl derivative rearranges to the C-allyl polymer prior to cross-linking. The thermal curing of this resin takes place by polyaddition at allyl double bonds. The curing rate and cross-link density depend on the content of the reaction centers in the polymer molecule [10]. The allyl derivatives of phenols have been used for the manufacture of glass berreinforced plastics and moldings, casting or impregnating compositions of high heat resistance, mechanical strength and chemical resistance [11]. However, achieving complete allyl curing is difcult. Moreover, the cured matrix is not thermally stable due to the thermal fragility of the cross-links arising from polymerization of allyl groups. It has been observed that allyl phenyl groups generally require prolonged heating (nearly 6 h) at 250 8C for meaningful extent of curing, which risks degradation of other fragile groups in the network [12]. 2.1. Allyl phenolic bismaleimide blend While reducing the cure temperature, the thermal stability of the allyl phenolic novolac resins can be further improved by reactive blending with bismaleimide compounds (BMI). The reaction between allyl phenol (AP) and phenyl maleimide groups has been exploited to synthesize a variety of polymer systems with useful properties. In such reactive blends, further improvement in properties is possible by way of structural modication of either the BMI or the phenolic ring. The properties of the resultant matrix depend on the relative ratio of the two reactants, and the cure schedules.
406
2.1.1. Allyl phenol maleimide reaction mechanism Earlier studies by Enoki et al. [13] showed that the reaction between the two components proceeds via the Ene reaction. The unsaturated Ene adduct intermediate undergoes a further Diels-Alder type reaction with BMI to give the bis- and tris adducts. The intermediate step (Diels-Alder) is sometimes referred to as Wagner Jauregg reaction too [14]. The total reaction sequence is also referred to as Alder-ene reaction. At very high temperatures, a retro-DielsAlder reaction is also suggested. Investigation of Reyx et al. [15] through reaction of model compounds, (i.e. phenylmaleimide with AP) and identication of products conrmed the Enoki mechanism. The reaction sequences are shown in Scheme 1. A multitude of reactions occurs at different temperatures and reactant stoichiometries. All the three structures are possible, but their relative concentrations could depend on the stoichiometry. Ideally, a ratio 1:3
(allyl:maleimide) gives a maximum cross linking and enhanced thermal stability, but this could lead to brittle matrices. Lower maleimide-content ensures the Ene structure-dominated, tough matrix with good exural properties, but with reduced Tg and thermal capability. In most of the cases, a compromise of various properties is achieved at an allyl/BMI ratio of 1:2. The Ene reaction between maleimide and allyl groups has been separately investigated by Cunningham et al. [16]. Although an unambiguous mechanism has not been evolved, the generally accepted mechanism is along the lines of Reyx et al. However, others have proposed modied mechanisms, through investigation of the cure chemistry by various techniques. Thus, curing of BMI/2,20 -diallylbisphenol-A (DABA) system under different heat schedules has been investigated by fourier Transform Infra Red (FTIR), uorescence, and UV-reectance spectroscopy [17]. FTIR was used to quantify the extent of succinimide
Scheme 1. Reaction sequences for 2-allylphenol phenyl maleimide reaction (Alder-ene reaction) [6].
407
formation and to identify the cross-linking processes, which occurred during high temperature curing (250 260 8C). High-temperature curing processes were also identied by reection spectroscopy with a tungsten source. Various reaction pathways were discussed in terms of their consistency with the spectroscopic data. Another investigation on the mechanism and kinetics of cure of a two-component BMI formulation, composed of 4,40 -bis(maleimido) diphenyl methane (BMM) and DABA suggested a copolymerization of maleimide and allyl groups as the major reaction [18]. In this study, an in-situ real time study of the progress of reaction was conducted in the temperature range from 140 to 250 8C, using remote ber optic near-infrared spectroscopy. The principal reaction observed was an alternating copolymerization involving maleimide and allyl double bonds. Maleimide homopolymerization was detected only in the initial stages of reaction at temperatures above 200 8C. The extent of self-condensation (or etherication) of hydroxyl groups on the allyl component, which leads to the cross-linking was observed to vary with the reaction temperature. Yet another sequence is predicted for this reaction when catalyzed by triphenyl phosphine (TPP)[19]. Thus, the studies on model compounds, N-phenylmaleimide (PMI) and o-allylphenol (AP) showed that the products of the PMI/TPP system are oligomers and polymers of PMI, whereas the main product of the PMI/AP/TPP system is the PMI trimer, which had the ve-member ring
formed via the phosphonium ylide intermediate as shown in Scheme 2. In the BMI/TPP system, maleimides only polymerize above 175 8C. On the other hand, maleimides trimerize above 120 8C in the presence of DABA and TPP. The BMI polymerization was faster in the presence of DABA. Since the network structure differs in the presence of TPP, the polymer properties could depend on the cure conditions, the presence of catalysts, etc. In continued work, Shibahara et al. [20] established that the product also depends on the reactants molecular environment. Thus, while investigating the thermal reactions of PMI and AP (or DABA) using 13C NMR and GPC, they found that reactions of PMI and AP (1:1 and 3:1 adducts) proceeded through an Ene-reaction, and that sequential Diels-Alder reactions accompanied the polymer of PMI and AP. On the other hand, the products from PMI and DABA were the Ene-adduct and the polymer, but the Diels-Alder adduct could not be detected, in contrast to the PMI/AP system. This difference in reactivity for PMI-AP and PMI-DABA was attributed to steric repulsion of DABA. A slightly different mechanism, including the condensation of OH-groups at higher temperatures has been proposed by Morgan et al. for the curing reaction in BMI/allylphenol systems [21]. The glass-transition temperature was investigated as a function of curing conversion for a diaminodiphenylsulfone-modied DABA/BMI resin system at different temperature regimes, and modeled
Scheme 2. Formation of maleimide trimer from phenyl maleimide in presence of triphenyl phosphine.
408
2.2. High performance polymers based on allyl phenol BMI systems Commercial addition-cure formulations based on co-reaction of diallylphenols and BMIs are available. Thus, Matrimide-5292 of Ciba-Geigy typically contains DABA and BMM (Scheme 3). This is one of the leading matrix resins for carbon ber composite for advanced aerospace applications. The earlier formulations contained a lower concentration of BMI. As discussed earlier, the neat resin properties are composition-dependent. But in a narrow concentration band, the variation in properties are not signicant except for a moderately better thermomechanical prole at higher BMI load, as evident from the representative data given in Table 1 [23]. The thermal capability and mechanical performance of the cured resin also depends on the cure schedule. Low temperature cure produces apparently stronger and tougher systems, with a marginal penalty in thermal capabilities. Data in Table 2 substantiate this [24]. Under a given cure schedule, BMI enhances the thermal capability at the cost of toughness and exural strength. A compromise in properties is generally observed for an allyl:BMI ratio of 1:2. Suitably formulated, the resin system made up of 4,40 -bismaleimidodiphenyl methane, DABA and desirable catalysts can give a high Tg (, 315 8C) matrix, despite a post cure temperature of only 200 8C [25]. It is stable up to 450 8C, with a char-yield of , 30% at 700 8C. T-300 carbon laminates retained
Scheme 3. Components of Matrimide 5292.
using a modied DiBenedetto equation [22]. Although the relationship between the glass-transition temperature and conversion of the BMI system conforms to the DiBenedetto equation for conversion , 0.6 and at lower cure temperatures, the results deviated signicantly from the equation at higher cure temperatures; thus, it was an inadequate model for the system. FTIR analysis showed that the major cross linking reactions did not occur during cure of the modied BMI at and below 150 8C. However, as the cure temperature was increased, the cross linking reactions responsible for three-dimensional network structures became more dominant. At 190 8C, formation of succinimide rings occurred in the curing process. The higher cure temperatures induced a signicantly faster initial cross-linking rate. However, further cross linking was retarded because the increase in the cross-links sterically slowed further cross-linking activity.
Table 1 Neat resin properties of BMI/DABA of different molar ratio (cure schedule: 180 8C/1 h 200 8C/2 h 250 8C/6 h) [23] (Reprinted from 29th Int SAMPE Symp by permission, q1984 Society for the Advancement of Materials and Process Engineering) Property (MPa) BMI/DABA-1/1 RT Tensile strength Tensile modulus Elongation (%) Flexural strength Flexural modulus Compressive strength Compressive modulus HDT (8C) Tg (8C, DMA) GIC (J/m2) 85 4430 2.3 172 4207 21 2485 273 295 195 149 8C 53 2529 2.6 204 8C 41 2100 2.3 BMI/DABA-1.2/1 RT 97 4030 3 192 4140 220 2570 285 310 217 149 8C 72 2943 3.05 204 8C 74 2418 4.6 80 4243 2.3 160 4114 295 BMI/DABA 0.87/1 (RT)
C.P. Reghunadhan Nair / Prog. Polym. Sci. 29 (2004) 401498 Table 2 Properties of BMI/DABA system (cure schedule: 175 8C/3 h 230 8C/4 h) [24] (Reprinted from Advances in Polymer Science by permission, q1994 Springer-Verlag) Property BMI/DABA molar ratio 1.2/1 Flexural strength (MPa) Flexural modulus (GPa) Deection (%) KIC (MN/m1.5) GIC (J/m2) Tg (8C) 186 4.02 7.78 0.97 197 279 1.5/1 188 3.94 7.3 0.86 158 282 02/1 174 4.05 5.53 0.8 133 288 03/1 131 4.14 3.5 0.64 83 288
409
51% of short beam shear strength (SBSS) at 230 8C. The processibility of the blend can be enhanced by reactive diluents. Thus, a modied BMI resin system for resin transfer molding (RTM) was prepared using diallyl bisphenol-A ether and 1,4-diallyl phenyl ether as reactive diluents for BMI [26]. Further toughening of Matrimide has been achieved by incorporation of polyetherimide particulates and Kevlar-49-whisker [27]. Such systems are also characterized by enhanced glass transition temperatures. Silicone has been incorporated into the maleimide-modied allyl novolac by reaction with substituted siloxanes. These compositions have better heat- and moisture resistance and are useful for semiconductor applications [28]. The thermal stabilities of BMI DABA blends modied with high-performance amorphous thermoplastics such as bisphenol A (BPA) polysulfone (PS), polyether ketone (PEK), and polyether sulfone (PES) bearing a phthalidylidene group, etc. have been studied by differential scanning calorimetry (DSC) and scanning electron microscopy (SEM) [29]. The stability of thermoplastic components were compared with the area of the endothermic peak that appeared within the glass transition region for thermoplastic components in the cured blends aged at a temperature below Tg : The stability of thermoplastic was improved by the formation of semi-interpenetrating polymer networks. The stability of thermoplastic with higher Tg was more easily controlled. As for epoxies, the N-phenylmaleimide styrene copolymers are useful toughening agents for the BMI resin composed of BMM, DABA and triallyl isocyanurate [30]. The matrix structure was controlled by changing the equivalent ratio of the two
allyl components. Morphologies of the modied resins changed from particulate to co-continuous and to inverted phase structures, depending on the modiercontent. The optimum matrix structure contained about 20 wt% triallyl isocyanurate and 5 wt% of polymer additive wherein, the fracture toughness KIC for the modied resins increased 100% at a moderate loss of exural strength and with retention in exural modulus and the glass transition temperature. The Alder-ene reaction has been used to derive diverse high performance polymers. Thus, partially allylated novolac, when mixed with BMM and molded under pressure at high temperature gave products with high decomposition temperature (465 8C) [31]. By a similar strategy, a thermosetting resin system for resintransfer molding based on allyl novolac and BMI has been developed [32]. In this case, the novolac resin was allylated by conventional route and BMI was used as the curing agent and allyl phenyl ether, as the diluent. It was blended with BMM (in 1:1 ratio). On heating, the O-allyl derivative rearranges to the C-allyl derivative as shown in Scheme 4. This was followed by the Alderene reaction.
Scheme 4. Synthesis protocol and curing for allyl novolac bismaleimide system.
410
The viscosity temperature curve and the viscosity time curve were used to characterize the processing property of the resin system. The resin system had a long pot life at the injection temperature. The cured resin showed outstanding heat resistance and good exural properties. The exural strength of 122 MPa and corresponding modulus of 3.53 GPa conrm their good strength characteristics. The Tg was 288 8C. However, the system absorbed 4.5% water. The glass cloth composite fabricated using RTM technology showed a exural strength of 413 MPa which was retained to 90% and 65 at 200 and 300 8C, respectively. In a nearly identical strategy, aromatic hydrocarbon-modied maleimides have been used with allyl etheried-novolac to improve the exural modulus [33]. Condensation resin of aralkyl ether and phenol, i.e. polyaralkyl phenol (Xylok) is used commercially as a high heat resistant phenolic resin. Xylok is a desirable matrix resin for advanced composites [34]. This is primarily because of its excellent insulation, heat resistance and good processibility. The major disadvantage of Xylok is its low reactivity and the brittleness of the cured structure. One of the methods used to modify xylok, to improve its properties is by allylization to derive the allyl Xylok as per Scheme 5. Allyl xylok can be thermally polymerized through the unsaturated bonds in its structure, but it yields only an oligo polymer. In order to obtain highly cross linked structure, allyl xylok can be co-cured with BMIs, resulting in a class of high
performance matrix resin for advanced composites. Thus, BMI is a desirable comonomer for allyl xylok [35]. The copolymer of the BMM and allyl xylok exhibits excellent heat resistance (no mass-loss up to 490 500 8C) with good mechanical properties and hot-wet resistance. The heat distortion temperature (HDT) of the water-aged (for 10 h) copolymer is 280 8C and the polymer absorbs only 2.3% water. Although the properties are not commendably high, the excellent high temperature retention is worth mention. The good water-ageing resistance is also reected in the properties. The exural strength drops from 114 to 78 MPa at 250 8C. For wet conditions, the corresponding drop is from 92 to 55 MPa. For glass composites, the drop in exural strength is proportional, from 360 to 242 MPa. The Tg of the system is very high, almost close to the decomposition temperature. The Tg of 490 8C is the highest for a thermoset and drops only to 478 8C under wet conditions. The polymer starts to degrade rapidly at 490 8C. The glass-reinforced, compressionmolded material showed good thermal and mechanical properties and outstanding dielectric characteristics. Thus, the material is projected as a high performance insulator [36]. During curing, no by-products of low molecular weight are generated. Hence, the resulting cured structure is compact and has few defects. High performance blends of BMI DABA resulted on blending the BMM/DABA system with bismaleimidodiphenyl ether (BME), BPA BMI (BMIP),
Scheme 5. Synthesis of Allyl-xylok and curing with bismaleimide.
411
allyl phenolic epoxy (AE) and a thermoplasticmodied polyetherketone (PEK-C) [37]. The inuences of the various modifying components on the properties of BMI neat resin and BMI/T300 composites were investigated. Results indicated that the two BMI neat resin systems modied with AE and PEK-C, and BMIP, AE and PEK-C had outstanding impact strength (. 18 kJ/m2) and excellent heat resistance. BMI/T300 carbon composites corresponding to these modied BMI resin systems showed excellent toughness (CAI . 210 MPa), outstanding mechanical properties, good processibility and relatively high Tg : A copolymer of BMI, DABA and diphenylsilanediol was synthesized in a similar approach [38]. The copolymer could be cured around 200 8C, and the cured resins had good thermal stability. A higher curing temperature in the range 170 210 8C was favorable to obtain a more thermally stable resin. By reducing the content of diphenylsilanediol cyclo-homopolymer in the resin, thermal stability could be improved further. Allyl naphthols can replace allylphenols in Alder-ene adducts [39]. The simplest co-reactant prepared in this work was 7-allyloxy-2-naphthol, and satisfactory matrices were obtained with appropriate BMIs. However, the laminate coupons made by using this system had lower thermal stability in comparison to Matrimid 5292. The performance of this new chemistry was further tested by incorporating the naphthol/ maleimide Diels-Alder addition structure into two other co-reactants. The most successful of these compounds (i.e. the Diels-Alder adduct made from the diallyl ether 2,7-dihydroxynaphthalene and 4-hydroxyphenylmaleimide) produced a cured neat resin having Tg , 30 8C higher than that of a comparable system cured with the standard BMI co-reactant (BMM). The system also possessed marginally higher tensile strength and modulus. The fact that these laminate coupons had better thermal performance than the system using commercial co-reactant showed that the presence of the Diels-Alder adduct structure in the resin backbone was not detrimental to the normal performance of the Ene-cured BMIs. The Alder-ene polymers can be conferred good ablative properties by introducing boron into the molecular backbone of allyl compounds. Such systems manifest improved thermal resistance, without altering the mechanical strength [40]. Linear polymeric boron-allyl compounds were synthesized
from DABA, or its mixture with bisphenol-A (BPA) or 4,40 dihydroxy diphenyl sulfone, and boracic acid (Structures B to E). The condensation product of boracic acid and 2-allyl phenol (structure A) or boracic acid and DABA (structure B), reacted with formaldehyde (structure E and F, respectively) also served as a co-reactant for BMM. The different compositions are shown in Scheme 6. These allyl derivatives were blended with BMM in 2:3 weight ratio and heat cured. The mechanical properties showed marginal improvement for systems containing compounds A D, as did Tg and HDT. However, incorporation of boron gave signicant enhancement of the thermal stability for all cases. The more crosslinked systems based on compounds E and F showed enhanced Tg and thermal stability at the cost of the mechanical and impact strength. The Ti values increased by more than 60 8C and the char-yield shot up to about 56 60% (from 21% for the nonboron system). The relevant property data are compiled in Table 3. The tensile properties are comparable to the earlier reported vales for similar systems (refer Tables 1 and 2). However, the exural properties are inferior, including for the control composition. This may be a result of the different allyl/BMI ratio and the cure schedule. From the thermal characteristics, the authors concluded that the system might possess good ablative properties, but no true ablative evaluation was performed. Simultaneous interpenetrating networks (SIN), based on polyurethane allylnovolac have been reported [41]. The PU components were prepared by reacting 4,40 -diphenyl methane diisocyanate with poly(tetramethylene oxide) (PTMO) of different molecular weight ranges (UT series). The phenolic resin component was synthesized by substituting the hydroxy groups of the phenolic resin with the allyl groups. To prove that the alkene groups can be applied as a binding element between the networks to improve the network compatibility, trimethylol propane monoallyl ether was chosen as the PU chain extender in one series of the PU/allyl novolac resin SINs (TUT series). A detailed study of the thermal, mechanical, and dynamic properties and morphology revealed that the extent of phase mixing of the graft PU/allyl novolac resin SINs (TUT series SINs) was signicantly improved over that of UT series SINs. This result was consistent with the loss tangent shift in dynamic
412
Scheme 6. Synthesis strategy for Boron-containing allylphenol bismaleimide system [40] (Reprinted from Journal of Applied Polymer Science by permission, q1999 John Wiley and Sons). Table 3 Mechanical and thermal properties of boron-containing alder-ene polymers. Control system contains DABA/BMM in the ratio 0.8/1 [40] (Reprinted from Journal of Applied Polymer Science by permission, q1999 John Wiley and Sons) Property Tensile strength (MPa) Tensile modulus (GPa) Elongation (%) Flexural strength (MPa) Impact strength (kJ/m2) Tg (8C) Ti (8C) Char-yield (%) A 83.6 3.72 2.3 124 12.6 277 489 57 B 83.3 3.77 2.32 139 10.9 282 490 56 C 80.7 3.7 2.45 129 9.6 278 487 54 D 79.5 3.78 2.25 122 17.7 283 495 60 E 77.8 3.78 2.25 116 11.8 285 495 58 F 74.4 3.79 2.17 98 8.9 330 499 61 Control 73 3.61 2.2 112 13 274 426 21
413
mechanical analysis (DMA) measurements and with transmission electron microscope. The mechanical properties of the graft SINs (TUT series) were lower than those of the original SINs (UT series). In a related work, SINs based on poly(urethane epoxy)/ allyl novolac resins were prepared by cross-linking a urethane epoxy adduct with diamino diphenylmethane (DDM) and allyl novolac resin simultaneously [42]. A urethane epoxy adduct was synthesized by terminating the urethane prepolymer composed of 4,40 -diphenyl methane diisocyanate (MDI) and PTMO with epoxy. The thermal, mechanical and dynamical characteristics of these SINs correlated well with morphological observations from transmission electron microscopy (TEM). All these SINs exhibited a two-phase structure and the mechanical properties were correlated with the phase behavior. Further modication in the structure was effected by synthesizing polyurethane and phenolic resin via a maleimide-terminated PU/allyl nonyl novolac resin (ABCP) [43]. The polyurethane was again a product of MDI and PTMO. The composition, compatibility, mechanical and thermal properties of these inhomogeneous network polymers were investigated. The miscibility was improved very little, but the tensile strength had a clear improvement when the PUs soft segment, i.e. PTMO, was longer. This was attributed to the entanglement between the components. Attempts to improve the phase miscibility in a maleimide-terminated polyurethane/allyl nonyl novolac resin system by way of co-reaction with BMM did not meet with success [44]. In fact, a higher content of BMM promoted phase separation, although a lower BMM-content enhanced the tensile strength. 2.3. Adhesives based on allyl phenolics BMI The Alder-ene chemistry was used to derive high temperature phenolic adhesives, based on the reactive blend of an allyl-functional bisphenol-A novolac (ABPF) and BPA BMI (BMIP) [45]. ABPF was synthesized by reaction of DABA with formaldehyde under acidic conditions. The reaction was followed by GPC, and the synthesis conditions were optimized to produce soluble polymer of desirable molecular weight distribution. The polymers were characterized by FTIR, NMR and GPC. ABPF was reactively blended with BMIP and cured through the Alder-ene
reaction at high temperatures. The cure characteristics of ABPF BMIP blends were studied using DSC and DMA, which evidenced the multi-step cure reactions characteristic of the Alder-ene systems. The DSC thermograms in Fig. 1 substantiate this. The cure reaction showed two distinct exotherms in the temperature ranges 100 170 and 180 270 8C, respectively, and a less prominent exotherm initiated at about 280 8C and extending beyond 300 8C. The rst broad exotherm encompasses the Ene reaction, and the second unresolved one contains the Wagner Jauregg and nal Diels-Alder steps. DSC of the resin system already cured at 200 8C/3 h and 250 8C/2 h are presented in the same gure. DSC of the 200 8C/3 h cured system shows appreciable residual cure exotherm beyond 260 8C. Since this system can not contain any unreacted maleimide, the exotherm spreading from 260 8C can be assigned to the curing of residual unsaturated groups. The exotherm onset at 260 8C is triggered by curing of the vinyl phenyl groups (of probably the Ene-adduct), followed by the residual allyl groups. The DSC of the 250 8C/2 h-cured one also shows the presence of less signicant residual cure exotherm around 300 8C, assignable to the allylphenol polymerization. Except for these,
Fig. 1. DSC of bisphenol A bismaleimide(BMIP)-diallylbisphenol A novolac(ABPF) blend; (A) before cure; (B) after cure at 200 8C/3 h and (C) after cure at 250 8C/2 h [45] (Reprinted from Polymer International by permission, q2001 Society of Chemical Industry).
414
Fig. 2. Non-isothermal DMA of bisphenol A bismaleimide (BMIP)allylbisphenol A novolac (ABPF)/glass prepreg (heating rate: 5 8C/min, frequency 1 Hz, N2 atmosphere [45] (Reprinted from Polymer International by permission, q2001 Society of Chemical Industry).
the cure becomes practically completed at 250 8C, and at this temperature, the network could retain part of the unsaturated bonds derived from the initial reactions. The non-isothermal DMA of the glass prepreg (in Fig. 2) implied that the major cross linking process
is the Diels-Alder step occurring beyond 220 8C, since no considerable modulus build-up occurs prior to this temperature corresponding to the Ene-reaction. The isothermal DMA of ABPF BMIP system at three different temperatures in Fig. 3 show that the cure is accelerated at higher temperature, and the ultimate modulus is dependent on the temperature of cure. The cure is practically complete in about 90 min at 250 8C. However, a 6 h curing was performed to achieve maximum reaction at this temperature. This cure schedule also ensures complete polymerization of any residual allyl groups. The cure sequences are identical to those shown Scheme 1, and extrapolating the same chemistry, the cured structure of the resin can be depicted as in Scheme 7. The adhesive properties of the cured blend are given in Table 4. Although the adhesive properties of the system are only moderately good, it is remarkable that the properties are retained to greater than 100% at 150 8C. Moderate cross linking achieved through a 1:1 maleimide allyl phenol stoichiometry and a stepwise cure up to a maximum of 250 8C for 2 h was found to be very effective for the optimum LSS properties in this series. The stoichiometry of BMIP/ABPF was varied from 0.8:1.0 to 3.0:1.0 and the LSS at RT and at 150 8C were determined. The dependence of
Fig. 3. Isothermal DMA of bisphenol A bismaleimide (BMIP)-allylbisphenol A novolac (ABPF) blend, evaluated as glass prepreg, at different temperatures: (A) 160 8C, (B) 200 8C, (C) 250 8C (frequency 1 Hz, N2 atmosphere, heating rate 5 8C/min for the dynamic part) [45] (Reprinted from Polymer International by permission, q2001 Society of Chemical Industry).
415
Scheme 7. Likely Alder-ene reaction products from 1:1 Dallylbisphenolformaldehyde (ABPF)bismaleimide (BMIP) blend [46] (Reprinted from High Performance Polymers by permission, q2000 SAGE Publications).
adhesive properties on reactant stoichiometry is shown in Fig. 4. It was observed that the LSS properties optimized at a 1:1 ratio. The variation of relative retention of LSS at 150 8C shown in the same gure conrms the optimum value for this ratio. A BMI concentration lower than this stoichiometry leads to very low LSS at 150 8C, and also the lowest high temperature retention (about 90%) of the LSS due to the reduced number of cross-links in the system. An excess of allyl groups in such case leads to
more chances of Ene homopolymerization resulting in more linear structures than does the Diels-Alder cyclo-adduct. A stoichiometric excess of BMIP could lead to increased cross-linking reactions and the homopolymerization could result in rigid, brittle network structure, with decreased load-bearing capability. However, the higher cross linked system is conducive to an excellent retention of properties at 150 8C. Interestingly, the 1:1 combination also showed a good retention of the adhesive strength up
416
Table 4 Adhesive properties of cured BMIPABPF (1:1 stoichiometry) under different cure conditions [45] (Reprinted from Polymer International by permission, q2001 Society of Chemical Industry) Sl. no. Cure conditions (temperature/ time) (8C/h) 160/4 160/0.5 200/3 160/0.5 200/0.5 250/2 160/0.5 200/0.5 250/6 LSS at RT (MPa) LSS at 150 8C (MPa) 2.6 3.4 4.8 Retention of LSS at 150 8C (%) 137 121 117
1 2 3
1.9 2.8 4.1
133
Fig. 4. Dependence of adhesive properties on reactant stoichiometry for bisphenol A bismaleimide (BMIP)-diallylbisphenol A novolac (ABPF)system (a) at ambient, (b) at 150 8C, (c) percent retention at 150 8C [46] (Reprinted from High Performance Polymers by permission, q2000 SAGE Publications).
to 250 8C. The adhesive properties of this system were improved tremendously on matrix modication using polysulfone (PS) and polycarbonate (PC) [46]. The performance advantage was more in the case of PS, showing an optimum improvement at a 20% loading, as against PC exhibiting maximum properties at 10% loading. The related adhesive data are compiled in Table 5. The performance advantage of the additives is clear in Fig. 5, showing a comparison of the adhesive properties and thermo-adhesive proles of different systems. The properties decrease beyond 200 8C in the case of toughened systems, whereas the properties are retained for the neat resin well above 250 8C. The relatively better performance of a homogeneous blend resulting from PS is manifested as a signicant improvement in the properties at ambient conditions, but these decrease drastically at about 200 8C, in contrast to the PC-modied system. An SEM analysis of the modied formulations corroborated this relative difference as resulting from different morphological features in cases of PS and PC. A comparatively uniform distribution of the thermoplastic component leading to the co-existence of the resin-rich and additive-rich phases was found to enhance the toughness of the PS-system, whereas precipitation of larger particles in PC-modied system was less efcient for enhancing the adhesive properties. DMA corroborated the observations made in SEM. Existence of co-continuous phases of thermoplastic, resin matrix and thermoplastic-dissolved matrix in PS-modication and a clear phase separation in the case of PC-modied system, manifested independent glass transitions. The DMA for various systems are shown in Fig. 6. Both the additives decreased
Table 5 Adhesive properties of thermoplastic-modied BMIP-ABPF system (1:1 stoichiometry; cured at 160 8C/30 min 200 8C/30 min 250 8C/2 h) [46] (Reprinted from High Performance Polymers by permission, q2000 SAGE Publications) Properties Un-modied PES-content (phr) 10 LSS at RT (MPa) LSS at 150 8C (MPa) LSS at 200 8C (MPa) LSS at 250 8C (MPa) TPS at RT (kN/m) 4.1 4.8 5 5.2 Poor 13.9 11 7.1 4.6 0.32 20 19.3 16.5 11 6.4 0.38 30 14.8 13.7 10.7 5.5 0.4 PC-content (phr) 10 11.3 9.5 8.4 8 Poor 20 8.8 6.9 6.2 5.4 Poor 30 8.3 6.7 5.5 3.5 Poor
417
Table 6 Tg data for different BMIP-ABPF systems from DMA [46] (Reprinted from High Performance Polymers by permission, q2000 SAGE Publications) System BMIP/ ABPF molar ratio 01:01 02:01 03:01 01:01 01:01 Tg (1)a (8C) Tg (2)b (8C)
BMIPABPF BMIPABPF BMIPABPF BMIPABPF-PS20 BMIPABPF-PC20 Fig. 5. Adhesive Performance advantage of polysulfone (PS)- and polycarbonate (PC)- modied adduct of bisphenol A bismaleimide(BMIP)-diallylbisphenol A novolac(ABPF) at 1:1 maleimideallyl phenol/stoichiometry.
a b
335 ,380 ,380 190,260,300 150,210,320
355 ,380 ,390 190,260,345 150,210,350
Based on the deection point, tan d in curve. Corresponding to tan d peak temperature.
the modulus. The low temperature Tg is due to the phase-separated additives. The co-existing phase showed intermediate Tg : The transition zones of different phases and corresponding Tg values are given in Table 6. The unmodied systems manifested
Fig. 6. DMA of () bisphenol A bismaleimide (BMIP)-allylbisphenol A novolac (ABPF); (- - -) bisphenol A bismaleimide (BMIP)-diallylbisphenol A novolac (ABPF)-polysulfone-20(PS20); and ( -- --) bisphenol A bismaleimide (BMIP)-diallylbisphenol A novolac (ABPF)-polycarbonate-20 (PC-20), showing the different Tg regimes [46] (Reprinted from High Performance Polymers by permission, q2000 SAGE Publications).
high Tg ; of the order of 350 8C, which increased to 390 8C on enhancing the maleimide ratio. All these systems provided good adhesion up to 250 8C and can be used for moderate load bearing applications at high temperatures, as is required in certain aircraft and defense applications. The TGA of the blend of ABPF and BMIP with varying maleimide to AP ratio indicated that the thermal stability of the system was only marginally improved by an increase in BMI stoichiometry [47]. The effect of the BMI structure on the adhesive properties was also evaluated, using four different BMIs, namely, BMIP, BMM, BME and 4,40 -bismaleimido phenyl sulfone (BMS) [48]. The polar groups in BMIS and BMIE contributed to better adherend wetting and consequently better LSS at ambient. The hightemperature LSS retention was comparatively better for BMIP and BMS systems. The thermo-mechanical properties of the blend, implied from DMA, showed that BMM and BME systems with higher cross link density manifested higher Tg : Although the absolute values are not high, all systems exhibited remarkably high retention of LSS (.100%) at 250 8C. The data for different BMIs are given in Table 7. DABA, the precursor diphenol for ABPF was also reacted with BMIP stoichiometrically [48]. The LSS values at temperatures up to 250 8C for this system in comparison to those of its polymer analogue (i.e. ABPF) are presented in Fig. 7. At low temperatures,
418
Table 7 LSS properties (in MPa) of different BMI-ABPF systems (1:1 stoichiometry; cured at 160 8C/30 min 200 8C/30 min 250 8 C/2 h) [48] (Reprinted from Polymers and Polymer Composites by permission, q2003 Rapra Technology) System BMIP-ABPF BMM-ABPF BME-ABPF BMS-ABPF RT 4.1 4.2 5.4 5.9 150 8C 4.8 4.3 5.5 6.6 200 8C 5 4.3 5.5 7.1 250 8C 5.2 4.2 5.6 7.6
tune with their relative DMA behavior included in Fig. 6. The DABA-system showed a broader glass transition initiated below 200 8C, with a Tg maximum of , 300 8C tan dmax ; in contrast to the ABPF system showing a higher Tg of about 350 8C under identical cure conditions.
3. Bisoxazoline phenolics The unusual addition co-reaction of novolac phenolic resins with phenylene bisoxazoline has been explored to derive a new class of nonconventional phenolic thermosetting resin by Culbertson et al. [49]. The polymerization involves a tertiary phosphine-catalyzed reaction of bisoxazoline with a phenol-free novolac resin leading to an ether amide copolymer as shown in Scheme 8. The systems are suited for high performance composite applications [50]. The key features, which foretell the great usefulness of bisoxazoline phenolic resins in aerospace and other high performance application areas, include: No volatile bye products produced during curing Low cure exotherm, about 20% of epoxies and BMI Long term thermo-oxidative stability (10,000 h at 177 8C) Low cure shrinkage (, 1%) High neat resin modulus (. 500 MPa) High compression and shear strength for composites Excellent toughness (GIC is , 5 times greater than those of epoxies and BMI)
the LSS values for the DABA-based systems are better than those of the corresponding ABPF-based ones. This is attributed to a better wetting of the adherend by the low viscous, monomeric BMI-DABA blend in contrast to the polymer-based one. However, the thermo-adhesive prole is far superior for the polymer version. Thus, the LSS dropped signicantly above 150 8C for DABA, whereas it continuously increased for the ABPF-based system up to 250 8C (Fig. 7). The better high temperature performance of the polymeric (BMIP-ABPF) system is a consequence of the comparatively higher cross-link density leading to enhanced cohesive strength for the network. The thermo-adhesion proles of the two systems are in
Fig. 7. Comparative adhesive properties of diallylbisphenol-A (DABA)-bisphenol A bismaleimide (BMIP) and bisphenol A bismaleimide (BMIP)-diallylbisphenol A novolac (ABPF) systems at different temperatures.
Scheme 8. Addition polymerisation of bisoxazolinephenolic system.
419
Excellent adhesion to glass, reinforcing bers and particulates Long shelf life for resin and prepregs Low melt temperature and low viscosity for melt Low ammability and smoke release, meeting aircraft use regulations Low CTE (, 4 1025/8C) Easy prepreg formation as claimed by the inventors High Tg (170 295 8C) and high service temperature (275 8C) The usual cure cycle is 175 8C with a post cure at 225 8C. Composites are processable by RTM technique. The ber-reinforced copolymers possess the low smoke and heat release requirements of materials for aircraft interior applications [51]. Through selective use of catalysts, a very long shelf life for unrefrigerated prepregs at typical aerospace autoclave conditions (, 176 8C) is achievable. Reactive, low viscosity additives enhance the formation of prepregs with the resin (as claimed by the inventors). Based on this chemistry, several compositions with many interesting properties have been patented. Electrical, physical and mechanical properties of the neat resin suggest that these new thermosets could be useful in a variety of electrical applications. Further, their chemical, physical and mechanical properties, coupled with the ease of formulating tough, machineable materials (which can be highly lled with metals and other llers) conrm opportunities to use them in a wide variety of plastic material and/or mouldmaking applications. The glass transition temperature of the system can be widely tuned through variation in stoichiometry of the phenolic resin and the bisoxazoline. The Tg increases with the PBOX-content as shown in Fig. 8. The physical, thermal and mechanical properties are also composition-dependent. The variation in fracture toughness with composition is shown in Fig. 9, which includes the toughness range for aircraft grade commercial TGMDA/DDS systems for comparison. Toughness becomes optimized at a PBOX/Phenolic weight ratio of 40/60, and is much higher than those of commercial epoxy systems. Thus, successful bisoxazoline phenolic compositions contain about 60% by weight of novolac. Data in Table 8, on the comparative mechanical performance of typical aerospace resins show
Fig. 8. Dependence of Tg on PBOX/phenolic composition [49].
the superiority of PBOX phenolic over the epoxies [52]. The properties are even superior to those of the toughened BMI. The 40/60 PBOX/PF composition has better mechanical characteristics than the 60/40 composition. The mechanical data of composites of bisoxazoline phenolic indicate that these resin systems have excellent potential for use in a range of high
Fig. 9. Composition dependence of fracture property of PBOX/ Phenolic system in comparison to epoxy system (TGDMA/DDS: tetraglycidyl methylene diamine/diamiodiphenyl sulfone) [52].
420
Table 8 Comparative mechanical properties of neat PBOXphenolic and high performance epoxy and BMI [52] (Reprinted from 20th Int SAMPE Tech Conf by permission, q1988 Society for the Advancement of Materials and Process Engineering) Property 1,3-PBOX /phenolic (40/60) 193.7 5033 89.6 1.8 5137 236.5 4882 157 223 1,3-PBOX /phenolic (60/40) 172.4 4909 256 4789 TGMDA/DDS (untoughened) 91.7 3440 56.8 1.8 3737 201.3 1958 54 BMI, XU292/DDS (improved BMI) 184.8 4000 93.8 3 3889 210 2482 250
Flexural strength (MPa) Flexural modulus (MPa) Tensile strength (MPa ) Elongation at break (%) Tensile modulus (MPa) Compressive strength (MPa) Compressive modulus (MPa) Fracture energy (GIC ; J/m2)
performance applications, particularly when high modulus, good compressive strength and high interlaminar shear strength are demanded. The glass composite properties given in Table 9 show the superiority of these systems over the conventional resins [49]. The very small cure shrinkage (, 0.1%) and low CTE are believed to contribute greatly to the good physical properties and excellent thermal shock resistance of laminates. The shelf life of the prepregs can be tuned by selective use of catalysts. The carbon composite properties are either comparable or superior to the best-improved epoxy systems, as evident from the selected data given in Table 10. 3.1. Commercial PBOX phenolic systems Southwest Research Institute, USA has developed and patented bisoxazoline phenolic thermoset resins
Table 9 Mechanical properties of glass-cloth reinforced laminates compared to epoxy and phenolic systems [49] (Reprinted from 34th Int SAMPE Symp by permission, q1989 Society for the Advancement of Materials and Process Engineering) Property 1,3-PBOX/ phenolic (40/60) 758.5 31 451.6 28.3 76.5 Epoxy (Hexcel F-161) 606.8 24.8 489.5 24.1 Phenolic
that are tough and possessing low-ammability and high service temperature (176 8C), (named as PEARe, Poly Ether Amide Resin) and also their carbon ber- or berglass composites. The work is aimed at developing materials for a wide range of applications, including subsonic and supersonic aircrafts, ground and marine transportation, lightweight composite pipes, heat shields, and other high-strength, non-conductive materials for the construction, electrical, and oil industries [53]. PEARe is a lightweight, strong, economical and versatile
Table 10 Comparative mechanical properties of carbon composites of PBOX phenolic and high performance epoxy systems [52] (Reprinted from 20th Int SAMPE Tech Conf by permission, q1988 Society for the Advancement of Materials and Process Engineering) Property 1,3-PBOX/PF DOW71788.00 NAEMCO (40/60) epoxy (tough)/ RIGIDITEand AS-4 DDS and AS-4 5225 (improved EPOXY) and CELION 2069 115.1 89.6 1999 122 1682 132 1793 124.1 111.7 1724 129.6 1448 126.2
Flexural strength (MPa) Flexural modulus (GPa) Tensile strength (MPa) Tensile modulus (GPa) SBSS (MPa)
608.1 28.3 403.4
Flexural 1593 strength (MPa) Flexural 113.1 modulus (GPa) SBSS (MPa) 108.3 Tensile 1924 strength (MPa) Tensile 140 modulus (GPa) Compressive 1524 strength (MPa) Compressive 115.8 modulus (GPa)
421
composite matrix. This resin fuses a variety of signicant performance characteristics into a single material. Composites made with the PEAR resin system tends to experience longer wear resistance, longer life expectancy, ame resistance, and the ability to endure cyclic stress loading. Some critical product qualities of PEARe are: Heat and ame resistance Low toxicity when exposed to high levels of heat Excellent mechanical properties Electrical insulating properties Dimensional stability Relative ease of processing
Table 12 Properties of PEAR resin [54] Key properties Volatiles during cure Shrinkage during cure Viscosity Fracture Toughness GIC Curing exotherm (J/g) CTE Tg Range Specic gravity (neat resin) Neat resin strength (MPa) Tensile strength Compressive strength Flexural strength Neat resin modulus (MPa) Tensile modulus Compressive modulus Flexural modulus
0.0 100 cps 156 223 J/m2 78.0 42 1026 8/C 87 121 8C 1.25
90 237 194 5134 4879 5030
The manufacturer markets different varieties of PEAR resins, depending on their composition, solvent, etc. [54] (Refer to Table 11). Some of the properties of PEAR resins are given in Table 12 [54]. From the property data, it appears that the resin formulation is close to 40/60 PBOX phenolic composition.
Composite strength glass 57% resin 43% (MPa) Tensile strength 490 Flexural strength 758 Composite modulus (glass 57% resin 43% (GPa)) Tensile modulus 28.2 Flexural modulus 31 Composite short beam shear strength (glass 57% resin 43%) (MPa) Room temperaturedry 108 93 8C Hot-wet 91 Thermal cycles 0 50 (glass cloth composite) Cycles (MPa) Cycles (MPa) Flexural strength 784 779 93 8C Hot-wet 32.4 33.1 Total heat release (kW/m2) (FAA-OSU heat release calorimeter 35) In two minutes 65.3 Maximum heat release 67.6 Flammability (kW/m2) (NIST cone calorimeter) Maximum rate of heat 295.0 release
3.2. Blends and composites of BISOX/Phenolic As the phenolic resin market for aircraft interiors and mass transportation applications grows, re retardant standards in stringent applications must be met by improved formulations. One method to enhance ame resistance is to add siloxane to the resin. Addition and exfoliation of montmorillonite clay (MMT) is yet another approach. These two techniques have been adapted in concert for bisoxazoline phenolic system [55]. Thus, the co-reaction of an epoxy-terminated siloxane with
Table 11 Features of different polyether amide from bisoxazoline [54] PEARe product version Hot melt Solvent Low melt Manufacturing process Typical applications
RTM resin infusion Pre-preg lamination RTM
Aircraft and structural components Sports equipment, aircraft interiors Low stress applications, consumer products
a novolac phenolic/bisoxazoline reduced the peak heat release rate (PHRR) by 27% compared to a control. At 8% siloxane, PHRR dropped from 225 to 164 kW/m2 at a 75 kW/m2 heat ux. DMA testing showed a Tg of 220 8C for the 8% polysiloxanemodied material, compared to the Tg of 248 8C for the unmodied version. The clay (MMT) was then incorporated into a novolac resin using solvent fractionation techniques, and employing ethanol and toluene. Clear plaques were produced, and X-ray
422
diffraction (XRD) showed exfoliation due to loss of the clay peak at 19 A. 3.3. Structural modications of bisoxazoline phenolics Structurally modied bisoxazoline derivatives have led to new poly(ether ester amide) multiblock terpolymers and copolymers, which are hetero-phase materials, endowed with elastomer properties [56]. Aliphatic and aromatic alternating poly(ether amide) copolymers represent potential engineering materials. Binary and tertiary polyester/polyamide composites reinforced in situ are prepared by reactive blending in the melt. The chemical bonds formed between the separate phases via diblock copolymers improve the compatibility of blend components. Perfectly branched and hyper branched poly(ether amide)s based on bisoxazoline have also been reported [57]. The nucleophilic ring-opening addition reaction of phenol groups towards oxazoline units has been used for the preparation of hyperbranched poly(ether amide)s [58]. For this, the AB2 monomer, viz. 2-(3,5bishydroxyphenyl)-1,3-oxazoline, was synthesized and converted to a highly branched polymer in bulk or in solution at temperatures above 190 8C. The resulting hyperbranched polymers exhibit a degree of branching of 50%, as veried by high-resolution NMR spectroscopy, and are highly soluble in polar organic solvents with low solution viscosity. Their glass transition temperatures are in the region of 170 8C and degradation does not start below 300 8C. Melt rheology measurements revealed a predominantly elastic behavior with a relatively high viscosity at low frequency. A lower melt viscosity was achieved by end-group modication. The hyperbranched poly(ether amide)s serve as effective viscosity modiers for polyamide-6 matrix. New monomers for formulating thermosetting composites, based on tetraphenyl-substituted bisoxazoline monomers were synthesized via the direct reaction of 2-(diphenylmethyl)oxazoline with bromoalkyls, using tert-butyllithium [59]. These bisoxazolines have different melting points with varied molecular chain exibility. They functioned well as cross linkers when heated with phenolic resins or poly(acrylic acid), providing a path to new thermosetting materials with controlled glass transition temperature. Six new
ether-linked bisoxazolines were synthesized via reaction of p-hydroxyphenyl-2-oxazoline with dihalides [60]. These bisoxazolines were used as chain extenders or cross linkers for resins, monomers or polymers containing various acidic groups, including phenolics, via step-growth reactions. Thus, a novolac and a bisphenol-A oligomer resin, as well as poly( p-hydroxy styrene) were chain extended and cross linked to produce thermosets with high glass transition temperatures. The new bisoxazolines were also polymerized with diphenols to generate linear or branched oligomers and polymers. These new, etherlinked bisoxazolines are claimed to be potential high performance thermosets.
4. Polybenzoxazines (PBZ) Another interesting addition-cure phenolic system is based on oxazine-modied phenolic resin that undergoes a ring-opening polymerization to give polybenzoxazine, which is effectively a poly(aminophenol). The precursors are formed from phenol and formaldehyde in the presence of amines. The choice for phenol and amine permits design exibility and polymer property tailoring. The as-synthesized mixture consists of monomer, and oligomers that contain phenolic groups. For practical applications, the mixture is good enough, but for controlled structure and properties, the monomer is freed of the oligomers. The ring-opening polymerization can be catalyzed by acidic catalysts that permits a wide cure temperature. In the presence of acidic catalysts (e.g. phenols), the cure temperature window can be reduced from 160 220 8C to about 130 170 8C (i.e. a decrease of 30 50 8C). The synthesis and polymerization of BZ are depicted in Scheme 9. 4.1. Features of polybenzoxazines These new materials, belonging to the additioncure phenolics family were developed to combine the thermal properties and ame retardance of phenolics and the mechanical performance and molecular design exibility of advanced epoxy systems [61]. The polybenzoxazines overcome several shortcomings of conventional novolac and resole-type
423
Scheme 9. General protocol for the synthesis and polymerisation of benzoxazine based on bisphenol A.
phenolic resins, while retaining their benets. PBZ resins are expected to replace traditional phenolics, polyesters, vinyl esters, epoxies, BMI, cyanate esters and polyimides in many respects. The molecular structure of PBZ offers superb design exibility that allows properties of the cured material to be controlled for specic requirements of a wide variety of individual requirements. The physical and mechanical properties of these new polybenzoxazines are shown to compare very favorably with those of conventional phenolic and epoxy resins. The resin permits development of new applications by utilizing some of their unique features such as [62,63]: Near zero volumetric change upon polymerization Low water absorption Tg much higher than cure temperature Fast mechanical property build-up as a function of degree of polymerization High char-yield Low CTE
Low viscosity Excellent electrical properties Table 13 compares the properties of PBZ with those of the state-of-the-art matrices. The relative advantages of PBZ are obvious. They present a resin system with the highest tensile properties, and Tg can be boosted to as much as 340 8C through proper choice of the precursor phenol. This new family of phenolic resin features a wide range of mechanical and physical properties that can be tailored to various needs. DMA reveals that these candidate resins for composite applications possess high moduli and glass transition temperatures, at low cross-link densities. Long-term immersion studies indicate that these materials have a low rate of water absorption and low saturation content. Impact, tensile, and exural properties are also good. Results of the dielectric analysis on these polybenzoxazines demonstrate their suitability for electrical applications [64]. BZs are cured usually in the temperature window of 160 220 8C. The polymers exhibit Tg in the range
Table 13 Comparative properties of various high performance polymers Property Density (g/cc) Max use temperature (8C) Tensile strength (MPa) Tensile modulus (GPa) Elongation (%) Dielectric constant (1 MHz) Cure temperature (8C) Cure shrinkage (%) TGA onset (8C) Tg (8C) GIC (J/m2) KIC (MPa m1/2) Epoxy 1.21.25 180 90120 3.13.8 34.3 3.84.5 RT180 .3 260340 150220 54100 0.6 Phenolics 1.241.32 200 2445 03/05 0.3 04/10 150190 0.002 300360 170 Toughened BMI 1.21.3 ,200 5090 3.54.5 3 3.43.7 220300 0.007 360400 230380 160250 0.85 Bisoxphen (40:60) 1.3 250 91 4.65.1 1.8 175225 ,1 370390 160295 157223 Cyanate ester 1.11.35 150200 70130 3.13.4 02/04 2.73.0 180250 ,3 400420 250270 P T resin 1.25 300 350 42 4.1 2 3.1 177 316 ,3 410 450 300 400 PBZ 1.19 130280 100125 3.84.5 2.32.9 33.5 160220 ,0 380400 170340 168 0/94
424
160 340 8C depending on the structure, and have higher thermal stability. The high TGA decomposition onset temperature (for dihydroxy benzophenone aniline system, it is , 400 8C) is attributed to the very strong intramolecular H-bonding between phenolic OH and the Mannich bridge. Char-yield as high as 82% has been claimed. Their composites are comparable to polyimides and other high performance polymers, but are easily processable [65]. The ring-opening polymerization of these new materials occurs with either near-zero shrinkage or even with a slight expansion upon cure. It is proposed that the volumetric expansion of the BZ resin is mostly due to the consequence of molecular packing inuenced by inter- and intramolecular hydrogen bonding. The role of hydrogen bonding on the volumetric expansion has been studied by systematically changing the primary amine used in the BZ monomer synthesis. In comparison to the other known expanding monomers and spiro ortho compounds, this resin has been shown to have a high potential for structural/engineering applications [66]. Polybenzoxazines have the lowest heat release during combustion and is therefore, more ame resistant, surpassing that of phenolics and polyetherimides, the current aerospace matrices of choice. Table 14 gives the heat out put for three low-heat-release, aerospace grade polymers. PBZ possess the lowest heat release characteristics. 4.2. Cure mechanism and cure kinetics Polymerization of BZ with a free ortho position can occur through a ring-opening reaction. No volatile by-products are evolved and no strong catalyst is required for the reaction [67]. The reaction site of the ring-opening polymerization in monofunctional aromatic amine-based BZs has been investigated through
Table 14 Comparative heat release for various polymer systems [66] Polymer Peak heat release rate (W/g) 200 100 30 Total heat release (kJ/g) 10 7.5 2.5
Polyetherimide Phenolic resin PBZ
a systematic manipulation of the monomer chemistry [68]. Thus, selective protection or activation of sites on the arylamine ring towards electrophilic aromatic substitution has allowed a series of materials to be developed, which contain varying amounts of phenolic Mannich base bridges, arylamine Mannich base bridges, and methylene bridges. Electron-donating alkyl substituent groups at one or both the meta positions on the arylamine ring facilitate ring-opening/ degradation at lower temperatures. This opening of rings in a step other than the polymerization reaction greatly increases the numbers of methylene linkages. Conrmation of the reaction sites was obtained via 1H and 13C NMR spectroscopy of the oligomeric species. The reaction pathways on the curing reaction of 3-aryl substituted benzoxazine was investigated for the model reaction of 3,4-dihydro-6,8-dimethyl-3-phenyl-2H-1,3-benzoxazine with 2,4-xylenol [69]. The reaction was carried out at 140 8C for 5 h. N,N-Bis (2-hydroxy-3,5-dimethylbenzyl) phenylamine and N-(2-hydroxy-3,5-dimethylbenzyl) phenylamine were isolated as the main products at an early stage. The reaction of the rst compound by the thermal treatment was studied by proton-NMR spectroscopy. This result indicates that this compound produces several inter- and intramolecular rearrangement products. Based on these data, some possible reaction pathways were proposed. In the presence of p-toluene sulfonic acid monohydrate, 3,30 [4,4 0 -methylenediphenyl]bis(3,4-dihydro-6,8-dimethyl-2H-1,3-benzoxazine) was isolated as one of the intermediates. The polymerization generally manifests autocatalysis. The ring-opening polymerization of BZ was monitored by rheological analysis utilizing both conventional isochronic and a new multi frequency approach that can observe the critical gel [70]. The activation energies were calculated for the process. The methylamine-based Bz has higher activation energy for the gelation process than the aniline-based one. The cure kinetics of BZ precursor has been analyzed by torsional braid analysis [71], and gelation and glass transition during curing were studied. Two specic glass transitions were obtained at the curing temperature of 220 8C. The time temperature-transformation spectra were also generated. BZ is also cationically polymerizable [72]. Electrochemical polymerization of PBZ in acetonitrile/alkaline aqueous solution has also been reported [73].
425
The resultant polymer showed good heat-resistance properties. 4.3. Structure property relations The physical, mechanical and thermal properties of polybenzoxazines are primarily decided by the nature of the diphenol and the amine. The system derived from 4,40 -dihydroxy benzophenone and aniline provides a combination of high thermal stability (5% weight loss at . 400 8C) and high Tg (340 8C). Table 15 typically illustrates the structure property relation for three different BZs [61]. It is seen that the thermal capability for dihydroxy benzophenone-based system is achieved at the cost of mechanical performance. The impact property is good for PBZ derived from aliphatic amine. Similar to BZs, naphthoxazines were obtained from hydroxy naphthalene with aniline and formaldehyde [74]. The polynaphthoxazine also showed a Tg higher than the cure temperature. Thermal properties in terms of the weight loss after isothermal ageing in static air, the decomposition temperature from thermogravimetric analysis, and the change of dynamic storage moduli at high temperatures also conrmed their superior thermal characteristics. The dependence of thermal stability and mechanical properties on the nature of the amine were also examined. Thus, the thermal and mechanical properties of polybenzoxazine thermoset networks containing varying amounts of phenolic Mannich
Table 15 Structure-property relation for polybenzoxazines [61] Properties Bis benzoxazine formed from BPA methyl amine BPA aniline Dihydroxy benzophenone aniline 6.2 .6 2.3 1.250 340
Tensile strength (MPa) Tensile modulus (GPa) Strain at break (%) Impact strength (J/m) Polymer density Tg (8C)
103 3.8 2.6 31 1.122 180
126 4.5 2.9 18 1.195 170
bridges, arylamine Mannich bridges, and methylene bridges were investigated [75]. In materials based on, m-toluidine and 3,5-xylidine, the onset of thermal degradation is delayed until around 350 8C with no signicant effect on the nal char-yield. Materials with additional amounts of arylamine Mannich bridges and methylene bridges show improved mechanical properties, including higher cross link densities and rubbery plateau moduli. Regulation of the viscosity of a difunctional BZ resin is achieved by addition of a monofunctional BZ monomer or a difunctional epoxy monomer as reactive diluents to further improve processibility [76]. The glassy state properties, such as stiffness at room temperature, are unaffected by the incorporation of the monofunctional BZs. The thermal stability of the monofunctionalmodied polybenzoxazine is not signicantly affected below 200 8C. Properties sensitive to network structure, however, are affected. The incorporation of the monofunctional BZ reduces cross link density and produces a looser network structure, while the difunctional epoxy increases cross link density and leads to a more connected network structure. The relatively low cross-link density of BZ has been overcome by synthesizing pendant BZ functional vinyl polymer by reacting poly(4-vinylphenol) (VP) with formalin and aniline [77]. The pendant phenol polymer was obtained by homopolymerization of vinyl phenol (VP) or its copolymerization with butyl acrylate (VBP). The corresponding BZs (Va and VBa, respectively) were reacted with bisphenol A epoxy (DGEBA) and o-cresol novolac epoxy (CNE). The curing reaction proceeded rapidly at higher temperatures without a curing accelerator. The reaction induction time or cure time of the molten mixture from VP-based BZ and epoxy resin was found to decrease, in comparison to those of conventional BPA-based BZ and epoxy resin. The cured resins from VP-based BZ and epoxy resin showed higher Tg ; mechanical properties, electrical insulation, and water resistance compared to the one from VP and epoxy resin (phenol epoxy reaction) using imidazole as the catalyst. In the case of CNE, the net gain in Tg was not substantial. The improvement in exural properties was also marginal. BZ epoxy co-cure is described in detail in Section 4.4. The properties of the cured resin are complied in Table 16. The electrical requirements
426
Table 16 Properties of pendant phenol- and benzoxazine-functional linear polymers cured with different epoxies [77] (Reprinted from Journal of Applied Polymer Science by permission, q2001 John Wiley and Sons) Resin system* Tg (8C) KIC (MPa m1/2) Water absorption (%) 0.32 0.54 0.5 1.39 0.11 0.16 0.16 0.28 Flexural strength (MPa) 77 70 71 69 Flexural modulus (GPa) 7.8 6.9 6.6 5.1
Va/DGEBA VBa/DGEBA VP/DGEBA VBP/DGEBA Va/CNE VBa/CNE VP/CNE VBP/CNE
174 143 165 118 209 177 209 160
0.63 0.6 0.64 0.6
of new printed wire boards are beyond the capabilities of epoxies. The dielectric constant Dk (3 3.5) and dissipation factor (0.006 0.012) of selected and structurally modied PBZ systems
are inferior only to cyanate esters and they nd application in printed wire boards [78]. Whereas selection of suitable precursors can lead to high char-yielding PBZ, this can also be achieved
Table 17 Thermal properties of various acetylene functional PBZ [80] (Reprinted from 43rd Int SAMPE Symp by permission, q1988 Society for the Advancement of Materials and Process Engineering) Monomer structure T5 (8C) 462 470 489 415 478 458 494 440 Char yield % (800 8C) 73 78 79 75 80 74 71 78
390
32
380
76
488
81
427
by the incorporation of additional curing sites such as acetylene on the BZ backbone. The synthesis is achieved using amino phenyl acetylene in place of amine. They are polymerized in the range 190 200 8C. DMA analyses showed a Tg of the order of 329 368 8C, much higher than those of the nonacetylene BZs [79]. The high thermal stability of this class of polybenzoxazines is a combined result of the independent polymerization of both the terminal acetylene groups and the BZ rings. The thermal capability is a combined effect of the acetylene and BZ as these properties are dependant also on the backbone structure. The structure of various acetylene functional polymer and their thermal properties are compiled in Table 17 [80]. The high char-yield achieved for this class of materials is in the range 71 81% by weight at 800 8C in a nitrogen atmosphere, and 30% by weight at 700 8C in air, as determined by TGA. The increase in
char-yield is very signicant. Temperature at 5% weight loss T5 increases from 390 8C to as high as 490 8C for the acetylene-functional polymers. Temperature at 10% weight loss T10 is in the range 520 600 8C. Blending BZs with the acetylene-functional BZ resulted in improved char-yield of the former [79, 81]. Mechanistic investigations revealed that the acetylene group polymerizes to form short chains of polyenes, almost simultaneously with the ring-opening polymerization of BZ [81]. In fact the thermal stability depends on the atmosphere of curing. Thus, polymerization in air conferred better thermal stability and char-yield than the polymerization done in an inert atmosphere. Both the ring-opening polymerization and the acetylene polyene formation are faster in air. The syntheses of two typical acetylene-containing polymers (i) with terminal acetylene and (ii) with phenyl acetylene groups are shown in Scheme 10 [81]. The phenyl ethynyl benzoxazine (structure ii)
Scheme 10. Synthesis protocol for benzoxazines containing (i) terminal acetylene (ii) phenyl ethynyl groups [81] (Reprinted from Polymer by permission, q1999 Elsevier Science).
428
C.P. Reghunadhan Nair / Prog. Polym. Sci. 29 (2004) 401498 Table 18 Comparative thermal performance of various phthalonitrile polymers [84] Polymer N2 T10 Char-yield (%) 800 8C 80 65 70 Air T10 Char-yield (%) 600 8C 75 10 15
required very high cure temperature (i.e. 350 8C) for cure completion, typical of phenyl ethynyl group polymerization. Another strategy to improve Tg and thermal stability is by uorination of BZ. Thus, a uorinated polybenzoxazine was synthesized by the ring-opening polymerization of hexauoroisopropylidene-containing BZ monomer. Substantial development of Tg occurred at low degrees of conversion. The thermal stability also improved upon uorination [82]. Fluorinated PBZ with uorine groups on the amine (viz. 3,4-dihydro-3-pentauorophenyl-2H-1,3-benzoxazine) was obtained in high yield from pentauoroaniline [83]. This monomer, synthesized by a non-conventional route is a potential precursor for a polybenzoxazine in electronic applications in view of its low Dk , low ammability, low refractive index, low coefcient of friction and high glass transition temperature. PBZ with phthalonitrile groups manifested good thermal characteristics [84]. The phthalonitrile-functional polybenzoxazines (Pth-PBZ, structure in Scheme 11) showed good char retention up to 80% at 800 8C. In air, the char-yield is up to 70% at 600 8C with T5 in the range 380 420 8C. Tg is in the range 275 300 8C. Unlike conventional phthalonitrile polymers, these systems require a relatively lower cure temperature, of the order of 250 8C. The unreacted nitrile groups react further during degradation accounting for the high char residue. The polymers are classied as ame resistant. The superior thermal stability is evident from the comparative thermal properties of different phthalonitrile-based polymer
Pth-PBZ Pth-polyimidea Pth-diamineb

a b
596 550 500
450 510 500
Phthalonitrilepolyimide. Phthalonitrile cured by diamine (2%).
given in Table 18. The gain in char-yield in air is substantial. Dendrictic macromolecules containing BZ moieties have also been synthesized [85]. The dendritic building blocks were made by coupling reactions via a convergent approach. The BZs were synthesized by various combinations of amines and phenols permitting design exibility by using derivatives of phenol, primary amine and aldehyde. Dendrimers containing several different BZ moieties were synthesized up to generation 2. As the generation number increased, the curing temperature decreased gradually. 4.4. Reactive blending of polybenzoxazines Despite high modulus and Tg ; polybenzoxazines have surprisingly low cross-link density in comparison to other thermosets. Hydrogen-bonding is adequate to induce rigidity and constrain the mobility in the glassy state. The reactive blending with epoxy resins allows the network to achieve higher crosslinking. The co-reaction proceeds via the ring-opening polymerization of BZ followed, by reaction of the generated phenol with the epoxy, probably catalyzed by the amine group. The proposed reaction sequences can be found in Scheme 12. Epoxy ring-opening by the generated amine is totally not ruled out. Copolymerization leads to a signicant increase in the glass transition temperature [86]. Reaction of DGEBA with BPA-based benzoxazine (B-a) increased the Tg of the latter from about 143 to about 153 8C for an epoxy-content of 35%. Further increase in epoxy decreases Tg to below that of pure PBZ. This behavior is shown in Fig. 10. The copolymer exhibits strain at breakage that is up to
Scheme 11. Structure of phthalonitrile-functional benzoxazine [84] (Reprinted from Polymer by permission, q2000 Elsevier Science).
429
Scheme 12. General expected reaction sequence for curing of benzoxazine and epoxy.
twice the strain for pure BZ and a exural strength signicantly improved with minimal sacrice in modulus. The exural strength increased from 125 to 170 MPa on enhancing the epoxy-content to 50%. Interestingly, the increase is almost linear to the epoxy-content as shown in Fig. 11. The modulus decreased from 4.4 to 3.4 GPa, translating to an increase in strain at break from 3 to 6.3%. A corresponding decrease occurred in the storage modulus determined by DMA. By understanding the structural changes induced by variations of epoxy-content and their effect on material properties, network can be tailored to specic performance requirements. Thermally stable systems resulted on
using BPA based BZ as a hardener of the epoxy resin [87]. The curing reaction proceeded without any accelerator. The molding compound showed good thermal stability under 150 8C, which corresponded to the injection molding temperature. Above 150 8C, the curing reaction proceeded rapidly. The cured epoxy resin showed good heat resistance, water resistance, electrical insulation, and mechanical properties compared with the epoxy resin cured by the bisphenol-A type novolac. PBZ EPOXY system has been projected as a high performance matrix for several applications [88]. These systems are processable by traditional techniques such as prepreg, RTM and VRTM etc. for composite fabrication. The system, not requiring any refrigeration, is stable at ambient conditions indenitely. Suitably formulated, their Tg
Fig. 10. Dependence of Tg on composition for diglycidyl ether of bisphenol A (DGEBA)/ {bis(4-phenyl-3,4-dihydro-2H-1,3-benzoxazinyl) isopropane} (B-a) blend [86] (Reprinted from Polymer with permission, q1996 Elsevier Science).
Fig. 11. Relative increase in exural strength with epoxy-content for polybenzoxazine-epoxy blend [86].
430
Table 19 Mechanical properties of neat castings of PBZ, PBZ epoxy and a control epoxy [88] (Reprinted from 46th Int SAMPE Symp by permission, q2001 Society for the Advancement of Materials and Process Engineering) Properties PBZa RT Tensile strength (MPa) Tensile modulus (MPa) Elongation (%) Flexural strength (MPa) Flexural modulus (MPa) Compress strength (MPa) Compress modulus (MPa) KIC (MPa m1/2) GIC (J/m2) Tg (8C)
a b
PBZZepoxy Wet, RT 31 5016 1.5 103 4844 150 8C 21 1290 3 44 1538 RT 52 4319 1.6 115 4430 232 3243 0.65 83 219 Wet, RT 45 4513 1.1 84 4610 150 8C 52 2788 2.4 89 3015
Epoxyb RT 52 3995 1.4 142 3712 279 1939 0.55 71 223 Wet, RT 30 3491 1 61 3457 150 8C 37 2401 2.2 77 2518
31 5334 1.2 132 4602 228 3505 0.94 168 171
Undisclosed structure. TGMDA DDS.
can be boosted to , 200 8C, and they possess excellent mechanical properties and low moisture absorption. The mechanical properties of these systems in comparison to pure BZ and a standard epoxy can be found in Table 19. The blend shows improved mechanical performance at ambient. The trend is maintained in the wet and high temperature conditions. However, in this case, the fracture properties are adversely affected although Tg was enhanced. BZ epoxy blend with superior heat- and water resistance and electrical insulation resulted when a terpene diphenol-based benzoxazine (Terp-Bz) was cured by an epoxy (o-cresol novolac epoxy) quantitatively above 180 8C [89]. The properties were superior to bisphenol-A-based benzoxazine (B-a) or bisphenol-novolac (BisA-N) system cured in the presence of the same epoxy. The gain in properties, is however only marginal (about 10% increase in exural strength). A ternary mixture of BZ, epoxy, and phenolic novolac resins provided low melt viscosity resins and void-free specimens with minimal processing step [90,91]. The material properties were highly dependent on the composition of the monomers in the mixture. A Tg of 170 8C and considerable thermal stability can be obtained from these systems. Phenolic novolac resin acts mainly as an initiator for these ternary systems, while low melt viscosity, exibility and improved cross link density of the materials were attributed to the epoxy fraction.
Polybenzoxazine imparts thermal curability, mechanical properties as well as low water uptake to the ternary systems. The authors claim the materials as promising candidates for application as underlling encapsulation and other highly lled systems. The gelation behavior of this low melt viscosity ternary blend was investigated by Fourier Transform Mechanical Spectroscopy technique (FTMS) in order to study the effect of epoxy diluent on the rheological property development before and after the gel points [92]. The gel times range from 5 to 30 min at 140 8C to less than 5 min at 180 8C for all tested ternary system compositions. The gelation of the ternary mixture showed Arrhenius-type behavior, permitting prediction of the gel time. BZ can be used for functionalization of other polymeric systems as a means of cross linking. Thus, polysiloxanes are ctionalized with these groups and their adhesion properties in glass ber-reinforced composites are improved [93]. BPA-based BZ can be cured by bisoxazoline in the presence of triphenylphosphine as a catalyst at 170 8C [94]. The blend is processable by melt impregnation, RTM etc. The phenolic hydroxyl groups generated by the ringopening reaction of the BZ ring react with the oxazoline ring at 200 8C as shown in Scheme 13. The cure can be completed in less than 30 min at this temperature as evident from DMA. The system ows easily at 100 140 8C, and has good thermal stability. The melt viscosity of the molding compound
431
Scheme 13. Co-reaction between benzoxazine and bisoxazoline [95] (Reprinted from Journal of Applied Polymer Science by permission, q2001 John Wiley and Sons).
is around 0.1 1.0 Pa s at 140 8C, even after 1.5 h, but increases rapidly at 180 8C. The cured resin showed good heat resistance (Tg , 195 8C), water resistance (0.28% absorption), electrical insulation (volume resistivity of 3.5 1016 ohm cm), and mechanical properties (KIC , 0.93 MPa m1/2), that are only marginally superior to cured resin from BPA-type novolac and bisoxazoline. On the other hand, when BPA-based benzoxazine (B-a) containing oligomers (oligo-B-a) was cured with bisoxazoline, the cure time and temperature could be lowered, compared with those from pure B-a and bisoxazoline [95]. Above 160 8C, the curing reaction of oligo-B-a with bisoxazoline (1,3-PBOX) proceeded more rapidly than that of B-a with bisoxazoline. The cured resin from oligo-B-a and bisoxazoline showed better heat resistance (Tg - 232 8C) and water resistance (0.23% absorption), than the cured resin from B-a and bisoxazoline. However, the fracture toughness showed a reverse trend (KIC -0.75 against 0.93 MPa m1/2 for the latter). In another study, two poly functional BZ monomers, viz. 8,80 -bis (3,4-dihydro-3-phenyl-2H-1,3-benzoxazine) and 6,60 -bis(2,3-dihydro-3-phenyl-4H-1, 3-benzoxazinyl) ketone, were co-cured in an autoclave [96]. These two polybenzoxazines showed mechanical and thermal properties similar to or better than BMIs and some polyimides. They also showed very high char-yield after carbonization in a nitrogen atmosphere. Thermally stable blends result when phenyl nitrile functional BZs are blended with nitrile systems and cured [97]. Ortho-, meta-, and paraphenylnitrile-functional BZs were polymerized at different compositions with phthalonitrile-functional monomers, providing copolybenzoxazines of high
thermal stability and easy processibility. The copolymer char-yield increased from 59 to 77 wt% and Tg from 180 to 294 8C with only 30 mol% of phthalonitrile-functional monomer. 4.5. Non-reactive blends and composites of benzoxazine PBZ is amenable for matrix modication by llers, reinforcements and polymer blends. The thermal properties of physical blends containing BZ monomer and polycarbonate (PC) were studied by non-isothermal DSC, TGA and FTIR [98]. The ring-opening reaction and subsequent polymerization reaction of the BZ were inhibited signicantly by the presence of polycarbonate. The glass-transition temperature of the resulting blends decreased as the concentration of polycarbonate increased and deviated markedly from the Fox equation. An earlier degradation event appeared in the blend with 11 and 33 wt% of PC. Intermolecular hydrogen bonding between PC and cured polybenzoxazine appeared after 1 h of isothermal curing at 180 8C, and continued throughout the entire curing process. Subsequent studies conrmed a possible cross-reaction between PC and the ringopened BZ that led to PC-grafted and PC-cross linked PBZ [99]. The chain fragmentation in PC and polybenzoxazine blend upon thermal polymerization was investigated by size exclusion chromatography. Molecular weight reduction of PC via trans esterication between the hydroxyl groups of ring-opened BZ and the carbonate groups from PC was observed. In addition, excess heat of reaction compared to the expected value was detected from DSC and was assigned to the exotherm associated with the exchange
432
Scheme 14. Proposed reaction between polycarbonate and polybenzoxazine [99] (Reprinted from Journal of Applied Polymer Science by permission, q2002 John Wiley and Sons).
reaction. The proposed PBZ-PC interaction leading to grafts and cross links is shown in Scheme 14. Improved systems are reported to result due to synergism on melt blending BZ resins with poly(1caprolactone) (PCL) [100]. The PCL-content was varied in the range 0 15 wt%. The Tg s of the BZ blends were found to be slightly lower than that of neat polybenzoxazine resin. The blends showed improved mechanical properties, including higher cross link densities, rubbery plateau moduli, and exural strengths compared to pure polybenzoxazine. Unlike the previous case of PC-modication, the thermal stability at the mid-temperature range was enhanced, evident from the delayed onset of decomposition temperature and the disappearance of the rst degradation event. However, at higher PCLloading, only one Tg resulted, and the Tg value of the resulting blend appeared to be higher in the blend with a greater amount of PCL [101]. Phase separation occurred when a BZ monomer (B-a) was blended with soluble poly(imide siloxane)s [102]. The soluble poly(imide siloxane)s with and without pendent phenolic groups (structures PISi OH and PISi, respectively, in Scheme 15) were prepared from the reaction of 2,20 -bis(3,4-dicarboxylphenyl)hexauoropropane dianhydride with a,v-bis(aminopropyl) dimethylsiloxane oligomer (PDMS; molecular
Scheme 15. Poly (imidesiloxane) additives for polybenzoxazine matrix modication. Poly(imidesiloxane)s with pendent phenolic groups (PISiOH) and without pendent phenolic groups(PISi) [102], (Reprinted from Journal of Polymer Science Polymer Chemistry Edition by permission, q2001 John Wiley and Sons).
433
Scheme 16. Synthesis of poly(urethane benzoxazine)[103] (Reprinted from Journal of Polymer Science Polymer Chemistry Edition by permission, q2000 John Wiley and Sons).
weight 5000) and 3,30 -dihydroxybenzidine or 4,40 diaminodiphenyl ether. In the presence of poly(imide siloxane)s, the cure onset shifted from 200 240 to 130 140 8C. Viscoelastic measurements of the cured blends containing poly(imide siloxane) with OH functionality (i.e. PISi OH) showed two glass-transition temperatures, one at 2 55 8C and another at around 250 300 8C, indicating phase separation between PDMS and the combined phase consisting of polyimide and polybenzoxazine components, due to the formation of ABcross linked polymer. For the blends containing PISi, however, in addition to the Tg due to PDMS, two Tg s were observed in high-temperature ranges, 230 260 and 300 350 8C, indicating further phase separation between the polyimide and PBa components due to the formation of semi-interpenetrating networks. In both cases, Tg increased with increasing poly(imide siloxane)-content. Thus, the Tg of PBa increased from 160 to about 300 8C on enhancing the polyimide siloxane-content to 20% in the case of PiSi OH. For PISi, the Tg increase was to about 2258. As the siloxane-content increased, tensile strength and modulus decreased implying an improved toughness caused by the addition of poly(imide siloxane). The thermal stability of PBa also was enhanced by the addition of poly(imide siloxane)[102]. Urethane benzoxazine copolymer lms were prepared by blending a monofunctional BZ monomer, viz.3-phenyl-3,4-dihydro-2H-1,3-benzoxazine (Pa), and polyurethane (PU) prepolymer that was synthesized from 2,4-tolylene diisocyanate and polyethylene adipate polyol (Mw , 1000) in 2:1 molar ratio, followed by casting as lms and thermal curing at 190 8C [103]. Their synthesis is depicted in Scheme 16.
The poly(urethane benzoxazine) lms exhibited only one glass transition temperature, indicating good miscibility between PU and polybenzoxazine (Pba) due to the in-situ copolymerization of B-a and PU prepolymers. The Tg of the polyurethane was enhanced with increased Pba-content. Films containing less than 50% of Pa had the characteristics of an elastomer, with an elongation at break of more than 200%. These elastic lms exhibited good resilience with excellent reinstating behavior. Films containing more than 60% of Pa had the characteristics of a plastic. Up to 15% Pba, the lms were elastomeric with tensile strength of the order of 2 6 MPa. The value shot up to the range 280 MPa when the Pa-content exceeded 15%. The variations in tensile strength and elongation for different copolymers illustrating their evolution from elastomer to plastic nature, are shown in
Fig. 12. Variation of mechanical properties with polybenzoxazinecontent for benzoxazine-modied PU lm [103].
434
Fig. 12. Poly(urethane benzoxazine) lms showed excellent resistance to solvents such as THF, DMF, NMP and DMSO [104]. Amine-terminated butadiene acrylonitrile copolymer (ATBN) and CTBN were introduced to polybenzoxazine by modication of the monomer prior to curing. On a comparative scale, ATBN is more effective than CTBN in improving the fracture toughness of PBZ [105]. This was attributed to the better distribution of rubber particles in an ATBNmodied matrix than for the CTBN-modied one. DMA conrmed the existence of two networks in the ATBN-modied matrix [106]. The BZ resin permits compounding with a variety of additives, including nanoparticles such as montmorillonite, to make nanocomposites [107,108]. Thus, polybenzoxazine clay hybrid composites were prepared from a BZ precursor based on BPA and aniline or bis (3-phenyl-3,4-dihydro-2H-1,3-benzoxazinyl) isopropane, (B-a, structure in Scheme 9) and surfacetreated montmorillonite. The dispersity of organically modied montmorillonite (OMMT) at the molecular level in the polybenzoxazine matrix was conrmed by XRD. The Tg of the hybrid ` material was enhanced vis-a-vis the base polymer.
The reinforcement effect of OMMT was reected in the enhanced high temperature storage modulus of the composite. The additive also delayed the thermal decomposition of the matrix in the high temperature regime. The isothermal degradation studies indicated good thermal stabilization. This was attributed to the formation of OMMT nano-barriers minimizing the permeability of volatile degradation products in the material. Several types of polybenzoxazine/clay hybrid nanocomposites have been prepared from OMMT and mono- or bifunctional benzoxazine {3-phenyl-3,4-dihydro-2H-1,3-benzoxazine (Pa) or bis(3-phenyl-3,4-dihydro-2H-1,3-benzoxazinyl) isopropane (B-a), respectively} [109]. OMMT was prepared by a cation exchange of MMT with ammonium salts of amines such as tyramine, phenylethylamine, aminolauric acid, and dodecyl amine, with the structures given in Scheme 17. Strong hydrogen-bonding existed between PBZ and poly(N-vinyl-2-pyrrolidone) (PVP) on blending the two polymers, via interaction between OH group of phenol and the carbonyl groups of PVP. This caused a positive deviation in the Tg -versus composition curve for the two systems. A Tg maximum was observed at around 50/50 composition of the two
Scheme 17. Structures of benzoxazine monomers and organic modiers for montmorillonite [109] (Reprinted from Polymer by permission, q2002 Elsevier Science).
435
Fig. 13. Dependence of Tg on blend composition for polybenzoxazine/poly(N-vinyl-2-pyrrolidone)system [110] (Reprinted from Polymer with permission, q2003 Elsevier Science).
components as seen in Fig. 13. The Tg -composition curve conformed to the Kiwi equation, accounting for specic polymer polymer interaction. These interactions were corroborated by FTIR investigations [110]. Polybenzoxazine/clay nanocomposites were prepared by both melt method and solvent methods. XRD measurements of the nano composites showed that the blending method and the kind of solvent play crucial roles in the dispersion of OMMT in the polybenzoxazine matrix. The inclusion of any type of OMMT signicantly lowered the curing exotherm of BZs. The hybrid nanocomposites exhibited higher Tg ; higher modulus and enhanced thermal stability. The effect of clay was more signicant at around 2 5 wt% loading. The blending also reduced the exothermicity of curing signicantly. An immiscible polymer clay nanocomposite has been synthesized, consisting of dispersed layers of OMMT in a polybenzoxazine matrix, as shown by thermogravimetry, wide-angle
X-ray diffraction (WAXD), and TEM [111]. Protonated amines showed high ion-exchangeability. The spacing of the silicate layers was strongly dependent on the size or molecular weight of the amine derivative and the solvent type. Binary solvents (5% methanol in toluene) exhibited superior ability to swell OMMT. WAXD results revealed that the silicate layer expansion of all polybenzoxazine-OMMT nanocomposites prepared from either melt or solution methods were similar, with about a 48 A increment. This was correlated with TEM results that showed the aggregation of silicate layers, indicating that all prepared OMMT are immiscible with the polymer matrix. The compatibility between amine modifying agents and BZ dictated the characteristics of the nanocomposites. The curing reaction in the synthesis of polybenzoxazine montmorillonite (MMT) nanocomposites shows autocatalytic characteristics for fairly good conversion range [112]. Inclusion of boron nitride, on the other hand, results in highly conducting polybenzoxazine composites [113]. The reduced heat of reaction and increased exothermic peak temperature indicated that the boron nitride surface is inhibiting the BZ polymerization reaction [114]. Incorporation of Kenaf ber in a polybenzoxazine resin matrix to form a unidirectional reinforced composite resulted in systems with enhanced exural property [115]. Compounding by calcium carbonate leads to good particulate-lled PBZ composite [116]. 4.6. Degradation of polybenzoxazine 4.6.1. Thermal stabilization and degradation Polybenzoxazines are thermo-oxidatively stable. This is exemplied by the superposition of the thermograms of the cured resin in air and N2 [61]. It has been shown that the thermal stability of polybenzoxazines is substantially improved further by reactive amines. Various diphenols are found to have some effect on the thermal stability of this series of polybenzoxazines. Nitrogen-containing phenolic resins are also non-ammable polymers [117]. A study on their thermal decomposition revealed that PBZ decompose by loss of amine fragments [118]. Hence, one strategy for thermal stabilization is to introduce cross-linking sites on the amine moieties. Thus, propargylation was an effective means for thermal stabilization.
436
The introduction of ethynyl [79 81,119] and nitrile [84,97] groups in the backbone has been fruitful for conferring thermal stability. It has been seen that thermally stable phenol precursor such as naphthols also ensures thermal stability for the resultant PBZ [74]. The structural modications and compounding conducive to enhanced resistance to thermal degradations of PBZ have been discussed at different points in the preceding sections. Ishida et al identied the decomposition product of aromatic amine based polybenzoxazines through TGA and GC-MS techniques [120]. Several degradation products were identied, derived from the degradation of the polymer and the recombination of the degradation products. Benzene derivatives, amines,
phenolic compounds and Mannich base emerge directly from the polymer. Benzofuran is derived from further degradation of phenols. Biphenyl compounds are obtained from recombination of phenyl radicals after the loss of substituents form benzene, amine and phenol derivatives. Isoquinoline and phenathridine derivatives result from Mannich base by loss of OH groups and dehydrogenation. The overall degradation pattern is shown in Scheme 18. This team also investigated the thermal decomposition processes of a model compound containing a Mannich bridge and a series of polybenzoxazine model dimer, with moreor-less similar observations [121]. In this case, the 2,4dimethylphenol-based BZ dimers degraded into smaller and highly volatile compounds, leaving no char at
Scheme 18. Degradation pattern for polybenzoxazine [120] (Reprinted from Polymer by permission, q2002 Elsevier Science).
437
the end of degradation. The p-cresol-based BZ dimers also degraded into smaller and highly volatile products. Some of these are able to undergo cross linking and aromatization processes and form char. The major decomposition products for modied, p-cresol-based dimers are amines and ester compounds. 4.6.2. Chemical degradation of PBZ As the network contains basic amine groups, the stability of polybenzoxazines in acid medium is doubtful. The chemical stability of typical polybenzoxazines based on bisphenol-A and primary amines in a carboxylic acid solution has been studied [122]. It was found that the Mannich base is stable. It is proposed that the nature of the primary amine is responsible for the interactions between the carboxylic acid and the Mannich-base model dimers. As a result, the chemical stability of polybenzoxazines may also be related to the nature of the amines, which, in turn, inuence the strength of the hydrogen-bonded network structure that develops upon cure. While aniline-based BZ was stable in acidic medium, that based on methylamine disintegrated into small fragments. The strong salt formation between the more basic Mannich bases from the former disrupts the hydrogen-bonding network and triggers the degradation. The rapid degradation of certain BZs in acid medium was attributed to macroscopic stress cracking. 4.6.3. UV stability of PBZ The UV stability of PBZ has also been investigated [123]. Carbonyl-containing species were formed when B-a resin was exposed to ultraviolet radiation (l . 290 nm) in ambient air at room temperature. The isopropylidene linkage was the reactive site of cleavage and oxidation, resulting in the formation of a 2,6-disubstituted benzoquinone. Interestingly, the Mannich bridge was neither cleaved nor oxidized. A comparative UV exposure study has been performed on polybenzoxazines containing the same amine (methylamine), but with phenolic units possessing various substituents on the para-positions of the phenyl rings [124]. B-a is shown to have the highest degree of substituted benzoquinone formation followed by those polymers derived from hydroquinone, 4,40 -(hexauoroisopropylidene) diphenol, 4,40 -thiodiphenol, 4,4 0 -dihydroxybenzophenone, p-cresol
and phenol. The nature of the para-position in phenolic substituents was found to have an impact on the oxidation process affecting the degrees of substituted benzoquinone formation. Some secondary reactions were also found to occur as a result of photooxidation.
5. Phenol epoxy systems Curing of epoxy with novolac type phenolic resin, making use of the OH epoxy reaction, appears to be the simplest way to design addition-cure phenolic system. Although less preferred, polyphenols are used as curative for epoxies, since the addition-curing results in void-free products which are comparatively tougher due to the formation of exible ether network [125 128]. Phenol epoxy thermosets are preferred in void-free composite structures. The interest in these systems has been revived further by the need for voidfree, low moisture absorbing matrices with low dielectric properties for various electronic applications. The phenol epoxy reaction is less facile than amine-epoxy reaction, and is usually performed in the presence of catalysts such as triphenyl phosphine (TPP). The choice of phenolic resin and the epoxy allows for a wide design exibility and property tailoring. 5.1. Epoxy phenol cure kinetics Since the cure kinetics control the morphology and properties of the nal polymer, they have been the focus of research. Various researchers propose different cure models and various hypotheses to explain the observations. A few studies are presented here. Thus, the cure kinetics and Tg of the products have been investigated for the phenol epoxy system, where the phenols bear cyclopentadiene and xylok moieties [129]. Investigation of the cure kinetics and relationships between the glass transition temperature and conversion of biphenyl epoxy resin (4,40 -diglycidyloxy-3,30 ,5,50 -tetramethyl biphenyl) with these phenolic hardeners were performed by differential scanning calorimeter, using an isothermal approach over the temperature range 120 150 8C. The results indicated that the curing reaction of formulations using xylok and dicyclopentadiene type phenolic
438
resins (DCPDP) as hardeners proceeds through a rstorder kinetic mechanism {Eq. (1)}, whereas the curing reaction of formulations using novolac as a hardener goes through an autocatalytic kinetic mechanism {Eq. (2)}, da=dt k1 1 2 a da=dt k1 k2 a 1 2 a
m n
describe the kinetics over the entire conversion range as in Eq. (5), da=dt {k01 k02 am 1 2 an B} {1=1 expCa 2 ac }
1 2
Differences of curing reaction with change of the hardener in biphenyl epoxy resin systems were explained with the relationship between Tg and the reaction conversion, using the DiBenedetto equation [130] as, Tg Tgo Tga 2 Tgo lx=1 2 1 2 lx 3
where, Tgo and Tga are the glass transition temperatures of the monomer and the fully cured network, respectively, and l is an adjustable parameter. In an analogous study, the cure kinetics of a biphenyl epoxy (4,4-diglycidyloxy-3,30 , 5,50 -tetramethyl biphenyl)-xylok resin system with four different catalysts was performed by a differential scanning calorimeter using an isothermal approach [131]. The curing reaction of the formulations using TPP and 1-benzyl-2-methylimidazole as catalysts proceeded through a rst order kinetic mechanism, whereas that of the formulations using diazabicycloundecene and tetraphenyl phosphonium tetraphenyl borate proceeded by an autocatalytic kinetic mechanism. The effects of concentration of TPP as catalyst on the curing of biphenyl epoxy and phenol novolac resin system was also investigated. All kinetic parameters were deduced from the isothermal DSC analyses. A kinetic model with a diffusion term was invoked to describe the reaction for the entire conversion range [132]. Through the analyses of the cure kinetics and the relationship between Tg and conversion, it was concluded that TPP affects only the kinetics and not the nal cross link density. The modied kinetic model takes the form: da=dt k01 k02 am 1 2 an B 4
where k01 and k02 are the absolute rate constants for the normal and auto catalytic reactions, and [B] is the catalyst concentration. Although this equation described the kinetics at any given concentration of TPP, the authors introduced a diffusion term to
where C is a material constant, ac is the critical concentration beyond which the diffusion comes in to effect and is temperature-dependent. The modied, diffusion-corrected model clearly dened the kinetics at all conversions and catalyst concentrations. The cure kinetics of off-stoichiometric biphenyl epoxy (4,4-diglycidyloxy-3,30 ,5,50 -tetramethyl biphenyl)dicyclopentadiene phenolic resin system by DSC using an isothermal approach was investigated [133]. To describe the curing reaction after the vitrication, controlled by a diffusion factor, a semiempirical relationship was used. A one-to-one relationship, which is independent of the cure temperature between the Tg and the fractional conversion, was interpreted using the DiBenedetto equation. A Time Temperature-Transformation (TTT) isothermal cure diagram has been established at each equivalent weight ratio using the kinetic model coupled with the diffusion factor and the DiBenedetto equation. A study on similar lines of the cure kinetics of the above biphenyl epoxy reacted with a dicyclopentadiene type phenolic resin was done with four different kinds of catalysts [134]. The relative performance of the four catalysts and their kinetics were identical to those in the previous study [131]. The kinetics of reactions of certain phenol epoxy ternary systems has also interested the researchers. Thus, the kinetics of cure of bisphenol-A diglycidyl ether, bisphenol-A, and a sulphanilamide was investigated using HPLC [135]. The inuence of tetrabutyl phosphonium tetrauoroborate as a catalyst for the epoxy phenol reaction was studied. For the same initial composition, polymers differing by the crosslink point distribution and the chain length between cross-links were synthesized. Different solid-state behavior is expected in these two categories of networks. The phenol-epoxy reaction kinetics has been described in detail by Biernath and Soanne [136]. The kinetics of triphenyl phosphine-catalyzed thermal cure of the reactive blend of DABA and epoxy novolac (EPN) was investigated using DSC [137]. TPP catalyzed the phenol-epoxy reaction of
C.P. Reghunadhan Nair / Prog. Polym. Sci. 29 (2004) 401498 Table 20 Cure temperatures and kinetic parameters for the TPP-catalyzed cure of DABA-EPN [137] TPP (wt%) 0.5 1 2 3 E (kJ/mol) 68.3 79.7 79.4 74.5 A (s21) 1026 2.7 145 306 89.8 En (kJ/mol) for A 1.36 108 80.4 79.5 76.9 75.7 k100 (s21) 103 0.75 1.01 2.31 3.36
439
the dual cure system. The kinetic parameters for this step were estimated by the variable heating rate method of Kissinger. The activation energy E and pre-exponential factor A depended on the catalyst concentration. Although the variation in activation energy with increase in catalyst concentration did not follow a regular trend, the associated change in A implied a systematic increase in the rate constant. The apparent activation energies normalized to a xed A value En decreased with increasing catalyst concentration. The catalysis effect was evident in the computed rate constant k100 at 100 8C. The activation parameters were used to predict the cure prole of the resin under given conditions of temperature and catalyst concentration. Table 20 compiles the cure parameters and the kinetic constants. Fig. 14 shows the cure proles at different catalyst concentration.
Fig. 14. Time-conversion proles for epoxy novolac/diallylbisphenol A blend at varying concentration (wt%) of triphenyl phosphine. Heating rate 10 8C/min, [137].
At these cure conditions, the allyl group remains unreacted. This method can be used to synthesize allyl functional phenoxy resins. A rst order kinetics has also been observed for esteried novolac-epoxy cure. The resultant cured matrix is more moisture resistant [138]. The structure property correlation of phosphine-containing catalysts in phenol epoxy reaction has been separately investigated [139]. The relationships of melting behavior and chemical structure were discussed using the heat of formation calculated by a semiempirical method. Two schemes are proposed for the reactions with epoxy and phenol compounds: a complex formation scheme, and an ionic scheme. The reaction rate of epoxy and phenol compounds decreased on introducing electron-withdrawing substituents such as chlorine in the basic catalyst (TPP). The curing kinetics of epoxy phenol novolac compounds in the presence of a tertiary amine was studied by isothermal calorimetry and rotation viscometry [140]. The curing kinetics and mechanism, structural organization on the chemical, topological, and supramolecular levels, relaxation properties, rupture mechanism, and physico-mechanical properties of the resulting polymer were studied, as inuenced by the concentration of the tertiary amine. The reaction kinetics with diffusion controlled mechanism, as well as the volumetric change upon curing, of a cresol novolac epoxy/o-cresol formaldehyde novolac hardener system were studied by Tai [141]. Simple equations to model the change in linear coefcients of thermal expansion with conversion were derived. The true degree of conversion of this cross-linking epoxy system was obtained on the basis of the heat of reaction of monomeric monofunctional model compounds. The reaction was then modeled as one of a shifting order; autocatalytic followed by diffusion controlled. The reaction in the diffusion-controlled region was modeled by an nth order kinetic equation, with its rate constant described by a WLF-type equation. The experimental linear coefcients of thermal expansion above and below the glass transition temperature decreased linearly with the degree of conversion, in agreement with the derived equations. Yoon on the other hand, considered an active complex-formation for the cure kinetic model of biphenyl-type epoxy/phenol novolac resin system [142]. Investigation of the cure kinetics of a biphenyl epoxy phenol resin system with different kinds of
440
latent catalysts including encapsulated TPP was performed by DSC using an isothermal approach [143]. A combination of DSC and dynamic rheological measurements has been employed to study the chemo-rheological behavior of an epoxy novolac molding compound [144]. A procedure aiming at the phenomenological description of cure kinetics was developed. An empirical Arrhenius-type expression was adopted for the description of the dependence of the complex viscosity on temperature, frequency and conversion by allowing the pre-exponential factor and the ow activation energy to depend on frequency and conversion. At low conversions (, 5%), the system behaved approximately as a thermoplastic material. At higher conversions, the rheological behavior of the system was dominated by the extent of cure reaction. Similarly, the chemo-rheological study of biphenyl-type epoxy/phenol novolac system was performed at different isothermal curing temperatures [145]. A modied WLF equation was used to predict the chemo-viscosity during isothermal curing reaction. The glass transition temperature change due to curing reaction measured by DSC could be expressed as a function of conversion. From the measurements of isothermal viscosity, C1 and C2 terms in WLF equation were found to have an Arrhenius-type dependence on temperature. Using these relations in conjunction with the modied WLF equation, a good agreement between predicted and experimental viscosity has been claimed by the authors. Like TPP, imidazole is another preferred catalyst for the phenol-epoxy reaction. Thus, the cure reaction between DGEBA and BPA in the presence of the imidazole catalyst has been studied [146]. Two initiation reactions were proposed. One is based on the ionic complex formation between the epoxy and the pyridine-type nitrogen of imidazole, and the other on the ionic complex of BPA and imidazole. The subsequent propagation steps were composed of three steps, viz. the epoxy phenol reaction, the acid base reaction and the epoxide and the alkoxide. A generalized kinetic model was developed, which satisfactorily dened the kinetics in a wide range of imidazole and BPA concentrations. The kinetic model was further validated through prediction of the structural properties including epoxide conversion, molecular weight, sol gel fraction, branch points, loop density of the gel part by Monte Carlo
simulation, and verication of the properties through experimentation [147]. 5.2. Latent catalysis of epoxy phenol reaction The latent catalysis in thermoset curing has many implications in polymer processing. Latent catalysts are inert under normal conditions, but show activity at appropriate external stimulation, such as heating. Development of efcient latent catalysis is important for enhancement of both storage stability and handling of thermosetting resins, because they can simplify the curing operation to achieve one-pot synthesis systems. This aspect of phenolic epoxy curing has also interested many researchers, as evident from the large number of reports available in this eld. However, in the following discussion, only a few notable works will be mentioned. Thus, Park et al. [148] investigated the cure kinetics of the DGEBA/novolac blend system of different phenolic contents, initiated by a cationic latent thermal catalyst viz. N-benzylpyrazinium hexauoroantimonate (BPH), by means of the analysis of isothermal experiments using a DSC. Latent properties were investigated by measuring the conversion as a function of curing temperature. The results indicated that the BPH has good latent thermal initiator properties. The cure reaction of the blend system using BPH as a curing agent was strongly dependent on the cure temperature, and proceeded through an autocatalytic kinetic mechanism that was accelerated by the hydroxyl group produced through the reaction between DGEBA and BPH. It was concluded that at a specic conversion region, once vitrication took place, the cure reaction of the epoxy/phenol novolac/ BPH blend system became a diffusion-controlled cure reaction, rather an autocatalytic reaction. In a related study, the team investigated the viscoelastic properties and gelation in epoxy/phenol-novolac blend system initiated with BPH as a latent cationic thermal initiator [149]. Latent behavior was investigated by measuring the conversion as a function of curing temperature using traditional curing agents, such as ethylene diamine (EDA) and nadic methyl anhydride (NMA) in comparison to BPH. The gelation of epoxy/ phenol novolac blend system (as deduced from the time of modulus crossover and hence apparent) was dependent on frequency and cure temperature.
441
The activation energy for cross linking (Ec) from rheological analysis increased within the composition range 20 40 wt% novolac resin. The 40 wt% novolac to epoxy resin showed the highest value in the blend system, due to the three-dimensional cross-linking that can take place between hydroxyl groups (within the phenol resin or epoxides) and the epoxy resin. Sulfonium salts are the most common latent catalysts, with a latency that emerges from the thermal dissociation of the carbon sulfur bond to afford alkyl cations [150]. Other onium salts such as iodonium, ammonium, pyridinium and phosphonium salts have also been developed with considerable substituent and counter ions. Latent catalysis by quaternary ammonium borates [151] possessing good latency and storage stability, and by (triphenylphosphinemethylene) boranes [152] has also been disclosed. The latter study made use of the thermo reversibility of the bond formation between the ylide and boranes for the latent catalysis for polyaddition of phenol to epoxy. The catalytic activity could be controlled by introduction of substituents [153]. It was found that among many substituents, an acyl group on
the ylide is more effective in enhancing catalysis. Based on the substituent effect, the authors concluded that the ease of B C bond cleavage of the alkyl borane and the Lewis acidity of the phosphonium ion are critical in deciding the latent nature and the catalytic activity. The dissociation and catalysis are depicted in Scheme 19 [153]. An alternate mode for latent catalysis in phenolic epoxy matrix compositions is by embedding the catalyst in the matrix [154]. Thus, tough, ame retardant matrices for ber-reinforced composites have been realized. The strategy of embedding the initiators for matrix cure provides a means for ensuring stability (i.e. no reaction) of the phenolic epoxy matrix resins up to 140 8C while the matrix is applied to the ber preforms. Then, it is possible to effect a rapid reaction of the composites at the cure temperature of 180 200 8C. The cure times can be signicantly reduced since high initiator levels can be employed with this approach. Reaction kinetics were investigated by DSC to predict cure times of the system. Initiators such as tris(2,4,6-trimethoxyphenyl)phosphine encapsulated in thermoplastic polyimide ber sizing yielded promising results. The composite toughness and fatigue properties of these ame-retardant composites were excellent, and comparable to systems without embedding the initiator in the ber sizing. The toughness was comparable to that of toughened epoxies, and fatigue to that of vinyl ester composites, unlike general ame-retardant epoxies. The latent catalysis by encapsulated TPP in phenol epoxy has been discussed above [143]. 5.3. Structure properties relations in epoxy phenol The structure-property relationships of epoxy phenolic networks are quite well understood. Tysberg et al. [128,155] developed a series of phenol epoxy networks and evaluated the structural and composition dependencies of the various properties. The epoxy-phenol equivalent ratio was varied from 1:1 to 1:7.2. Generally, Tg decreased as the phenol-content increased. A moderately high Tg (, 150 8C) was obtained for the bisphenol-A- and tetrabromo bisphenol-A- based diepoxies. A siloxane diol-based epoxy decreased the Tg tremendously (to 87 109 8C). However, the phenol-content increased the ame retardance signicantly. Brominated-epoxy
Scheme 19. Mechanism of latent catalysis by (triphenyl phosphinemethylene) boranes in phenolepoxy reaction [153] (Reprinted from Macromolecules by permission, q2002 American Chemical Society).
442
and siloxane-epoxy exhibited better ame resistance. The latter manifested the lowest heat release and smoke toxicity. The fracture toughness in terms of the plain-strain stress intensity factor KIC indicated an increased resistance to crack propagation. A maximum KIC of 0.85 MPa m1/2 was observed for the ratio 1:3 for DGEBA. The properties of composites also showed a remarkable improvement over the DDScured control material. Network densities were explored by measuring the moduli in the rubbery regions, and these experimental values were compared with those predicted from stoichiometry [156]. A phenolic hardener with an average functionality of 7.3 was used in compositions ranging from 50 to 80%. The Tg s decreased, and toughness increased as the phenolic novolac-content in the network was increased. Both results were correlated to a decrease in network densities along this series. An analysis of the co-operativity of the networks suggested a crossover in properties from two competing factors, viz. the network density and intermolecular forces (hydrogen bonding). Measured fracture toughness values exceeded those of typical untoughened epoxy networks, and far exceeded that for commercial phenolic networks. In addition, an increase in the novolac-content improved the ame retardance rather dramatically. Thus, by controlling the novolac-content to reach an appropriate phenol to epoxy ratio, a void-free system with both favorable mechanical properties and ame retardance could be achieved. The carbon composites-composites properties given in Table 21 imply formation of strong composites. Mesogenic epoxy phenol systems could be realized by reaction of a biphenol with a variety of catechol novolacs [156]. In the epoxy resin cured with catechol novolac, which has a small substituent, such
as methyl group, the glass-rubber transition almost disappeared and a characteristic pattern, such as a Schlieren texture was clearly observed with a crossed polarized optical microscope. On the other hand, the epoxy resin cured with catechol novolacs that contained large substituents, such as phenyl groups, showed a well-dened glass rubber transition. These results showed that the motion of the network chains is highly suppressed in the former system, because of the orientation of mesogenic groups in the cured resins. In the latter system, however, the orientation of the mesogenic groups seems to be prevented by the large substituents. Networks containing both exible segments and rigid structures were synthesized on the basis of bisphenol-A novolac and diglycidylether of butanediol using imidazole as an accelerator [157]. A stoichiometric ratio between epoxy groups and phenolic groups of the novolacs led to networks with methylene bridges as network junctions. In contrast to this, the same reaction with bisphenol-A led to completely soluble products. The glass transition temperature of this soluble material was considerably lower than that of the networks. Increasing the content of methylene bridges in the novolacs led to an increased Tg of the networks, and to a decrease of the specic heat Cp at the glass transition. Furthermore, epoxy excess led to networks with rubber-like properties. It was concluded that intramolecular hydrogen bonding between phenolic hydroxyl groups considerably inuenced the reactivity of the novolac with the epoxy group. The exibility of the cured epoxy resin can be improved by introducing specic moieties in the matrix. Tricyclodecane is one such moiety [158]. This group was introduced by way of curing epoxy resin
Table 21 Flexural strength of carbon bre composite of epoxy phenolic system [155] (Reprinted from Polymer by permission, q2000 Elsevier Science) Novolac/epoxy (wt/wt) 08 Flexural strength (MPa) 1389 2051 2020 1808 08 Flexural modulus (GPa) 159 156 162 174 908 Flexural strength (MPa) 29 63 66 39 908 Flexural modulus (GPa) 8.9 12.1 11.3 11.1 Warp exural strength (MPa) 28 strands 442 436 567 379 Warp exural strength (MPa) 16 strands 367 351 372 261
Epoxy/DDSa 50/50 70/30 80/20

a
Control without phenol.
443
Table 22 The properties of the epoxy resins cured by two types of nonylphenol/cyclopentadiene formaldehyde adduct (NP/CPD) with PF resin co-curative [158] (Reprinted from Journal of Applied Polymer Science by permission, q1999 John Wiley and Sons) Composition Weight ratio Tensile strength (MPa) 45.3 7.3 21.7 30.3 8.3 32.6 36.6 Elongation (%) 5.2 1.6 2.6 3.5 1.5 3.8 4.9 Flexural strength (MPa) 98.6 13.3 36.5 64.4 17.4 55.6 73.6 Flexural modulus (MPa)
PF/DGEBA A/PF/DGEBA A/PF/DGEBA A/PF/DGEBA B/PF/DGEBA B/PF/DGEBA B/PF/DGEBA
36/64 33/16.5/50.5 23/23/54 14/28/58 33/16.5/50.5 23/23/54 14/28/58
2903 2826 3085 2928 2726 2859 2932
A NP/CPD (2:1), B NP/CPD (3:2), PF Novolac (see Scheme 19).
with nonylphenol(NP)/dicyclopentadiene(CPD) formaldehyde adducts, along with other commercially available curing agents such as Jeffamine D-400 and a novolac. The effect of these tricyclodecane groups on the properties of the cured epoxy resins is evident from typical data in Table 22. The presence of the exible NP/CPD groups impaired the mechanical performance of the PF-cured epoxy resin, whereas in combination with Jeffamine D-400, the properties were practically independent of the composition. The low cross-linking caused by the NP/CPD moieties could be the reason for this observation. In the presence of Jeffamine D-400 (at the place of PF), all mechanical properties improved. An associated
increase in elongation (almost two-fold) implies that the impact properties are signicantly improved in the presence of Jeffamine D-400. The proposed composition and structure of the modied novolacs are shown in Scheme 20. Epoxyphenol systems with markedly improved fracture toughness (KIC 1:32 MPa m1/2), higher Tg ; lower moisture absorption, and higher thermal decomposition temperature result when the epoxy resin contains a 4,40 biphenylene moiety (Bis-EBP) in the backbone and cured with a novolac [159]. This is achieved without sacricing the mechanical properties signicantly. The improved thermal characteristics, despite a lower cross link density are attributed to the restricted movement
Scheme 20. Different nonyl phenol/cyclopentadieneepoxy compositions. A and B represent the cyclopentadiene nonyl phenol copolymer in different rations [158] (Reprinted from Journal of Applied Polymer Science by permission, q1999 John Wiley and Sons).
444
Scheme 21. General synthesis protocol and structure of epoxy resins containing pyrene, anthrylene and tetramethyl phenylene moieties [160] (Reprinted from Journal of Applied Polymer Science by permission, q2000 John Wiley and Sons).
445
caused by the stiff 4,40 - biphenylene unit. The moisture absorption was reduced to 1.39% form about 2% for the control material. The gain in Tg was substantial (154 8C for Bis-EP and 172 8C for Bis-EBP in comparison to 142 8C for the control). The thermal stability of phenolepoxy systems can be enhanced by incorporation of certain specic moieties in the backbone. Thus, incorporation of pyrene in the backbone of an epoxy enhanced the thermal properties of a novolac-cured system in comparison with epoxy resins having an anthrylene or tetramethyl phenylene moieties [160]. The pyrene-based system showed a marginally higher glass transition temperature, lower coefcient of linear thermal expansion, lower moisture absorption (1.28%), and higher anaerobic char-yield at 700 8C. It is not known how these marginal gains in physical parameters affect the mechanical performances, in view of the rigid backbone structures. Scheme 21 shows the structure of various epoxy systems, and the common synthesis protocol adopted for their syntheses. Epoxy phenol systems meant for electronic applications must meet certain stringent requirements in electrical performance. One way to achieve this is by siloxane modication of such systems. Thus, vinyl siloxane (VS)-modied cresol novolac epoxy (CNE) cured by cresol novolac hardener (CNH) resins results in improved performance for electronic applications [161]. The VS-modied CNE/CNH compound possessed a lower Youngs modulus, a lower linear coefcient of thermal expansion (LCTE), and a higher strain at break than its unmodied counterpart. The combination of lower mechanical moduli and lower LCTE resulted in a 33% reduction in thermal stress caused by thermal mismatch. The incorporation of VS incurred a 25% reduction in the equilibrium moisture uptake and a 16% reduction in the coefcient of diffusion for the system. The reaction kinetics were studied for both components, to determine the conditions required for simultaneous cross linking in a designed synthesis procedure. The Tg of CNE/CNH resins could be effectively controlled through careful adjustment of a triphenylphosphine dosage [162]. Behavior characteristic of a diffusion-controlled reaction were observed. The incorporation of VS incurred a 35% reduction in the equilibrium moisture uptake and a 20% reduction in the coefcient of diffusion for the modied resin. This modied resin
could help alleviate the popcorn problems in integrated circuit packages, which result from hygrothermal stresses. Another process has been described to incorporate stable dispersed polysiloxane particles into a PF-aralkyl novolac epoxy resin, used as an ingredient in the encapsulant formulation to withstand the thermal stress [163]. The siliconization was done by hydrosilylation of allyl functional aralkyl epoxy (as per Scheme 22), with curing by novolac (PF), catalyzed by TPP. The Tg of the cured system was unaltered by incorporation of siloxane (Tg 163 8C). In this case, a sea-island structure (islands of silicone rubber dispersed in a sea of an epoxy resin) was observed in the cured rubber-modied epoxy networks via SEM. The dispersed silicone rubbermodied aralkyl novolac epoxy resin effectively reduced the stress of cured epoxy molding compounds by reducing the exural modulus and the CTE. Electronic devices encapsulated with the dispersed silicone rubber-modied epoxy molding compounds exhibited excellent resistance to the thermal shock cycling test, resulting in an extended use life for the devices. Whereas the control exhibited about 90% failure at around 3000 cycles, the modied one showed only 45% failure. The internal stress of the encapsulant is signicantly lowered by siliconization. The molding composition containing about 17.5% cresol novolac 9% phenolic hardener and about 68.5% silica ller (control) was modied with 3% of siloxane-modied aralkyl group. Their comparative properties are given in Table 23. Phenol epoxy based adhesives with high strength and high heat resistance have been developed for a novel iron-core printed circuit board with high mechanical strength and high heat radiation capability [164]. A reticular pattern was formed on the surface of an adhesive resin composed of nitrile rubber (NBR), phenolic resin, and epoxy resin. This pattern was formed as a result of phase separation of the epoxy resin or phenolic resin from the NBR. Using a highmolecular-weight epoxy resin led to high adhesive strength and high heat resistance, without phase separation. Reactive blends of 2,2 0 -diallyl bisphenol A (DABA) and a novolac epoxy resin (EPN) were investigated for their cure behavior, and rheological, physical, mechanical and thermal properties [12]. Cure characterization done by DSC and DMA
446
Scheme 22. Synthesis protocol for dispersed silicone rubber modied aralkyl epoxy system [163] (Reprinted from European Polym Journal by permission, q2001 Elsevier Science).
C.P. Reghunadhan Nair / Prog. Polym. Sci. 29 (2004) 401498 Table 23 Properties of siloxane-modied epoxyphenol moulding compound [163] (Reprinted from European Polymer Journal by permission, q2001 Elsevier Science) Property Control epoxy Siloxanemodied epoxy 163 1.8 1025 7.5 1025 128.1 10.7 192.6 0.29
447
Tg (8C) CTE (,Tg ) CTE (.Tg ) Flexural strength (MPa ) Flexural modulus (GPa) Thermal stress parameter (kPa K21) Moisture absorption (%)
164 2 1025 7.3 1025 131.3 12.8 256 0.32
conrmed the dual curing through a sequential phenol-epoxy reaction and allyl polymerization as shown in Fig. 15. The cure sequences are shown in Scheme 23. The former reaction was catalyzed by triphenyl phosphine (TPP). By the regulation of cure conditions, the phenol epoxy reaction could be completed while the allyl polymerization was limited to 40%. The mechanical properties of the neat systems with varying composition of EPN and DABA (Table 24) showed that an increase of epoxy concentration in
the blend led to an improvement in the tensile strength and exural strength of the neat castings. The exural strength and interlaminar shear strength of the glass laminate also showed an improvement with an increase in EPN concentration. Although the crosslink density of the neat casting was enhanced by epoxy-concentration, this did not result in any signicant variations in Tg of the cured matrix, which was in the range 78 82 8C. Complete polymerization of the allyl groups resulted in an increase in Tg (from 76 to 92 8C) and thermal stability, with a minor deterioration in the mechanical properties of the neat system, but a considerable increase in the mechanical properties of their glass composites. The Tg of the composite was signicantly higher than that of the neat resin. The comparative data of the 40 and 100% cured systems are given in Table 25. The increased ILSS at 100% allyl cure points to the consolidation of the interphase by enhanced crosslinking. A similar trend in ILSS and exural strength conrm the possible failure of the composite at the interphase. This improved interphase strength accounts for the enhanced composite properties, despite the fact that the resin becomes more brittle on effecting 100% allyl polymerization. Distribution of the OH groups in the phenolic curative could dictate the thermal mechanical characteristics signicantly. Thus, a weak glass transition corresponding to a rubbery modulus was observed for a biphenol type epoxy cured by catechol type novolac, whereas the glass transition was clearly manifested for phenol novolac. The suppression of the Brownian movement in catechol-cured systems due to the orientation of the biphenyl group (aided by H-bonding) accounted also for a better high temperature tensile and bond strength in this case [165]. 5.4. Flame resistant epoxy phenolic systems Although epoxy phenolic systems are inherently ame resistant at high phenol-content, for certain stringent applications, this property requires further amelioration. This can be achieved by way of incorporation of specic elements such as phosphorous, Si, etc. in the network. Different strategies are adopted for their syntheses. Thus, a novel phosphoruscontaining novolac (DOPO-PN) from 9,10-dihydro9-oxa-10-phosphaphenanthrene-10-oxide (DOPO)
Fig. 15. Non-isothermal DMA and DSC of the epoxy novolac/diallylbisphenol A blend, heating rate 10 8C/min [12] (Reprinted from Polymers and Polymer Composites by permission, q2003 Rapra Technology).
448
Scheme 23. Cure sequences for diallyl bisphenol A (DABA)-Epoxy novolac (EPN) system [12] (Reprinted from Polymers & Polymer Composites by permission, q2003 Rapra Technology). Table 24 Properties of DABAEPN neat resin and composites (40% allyl curing) [12] (Reprinted from Polymers and Polymer Composites by permission, q2003 Rapra Technology) DABA/EPN equivalent ratio Neat moulding Flexural strength (MPa) 01:00.8 01:00.9 01:01.0 01:01.1 01:01.2 77 91 113 106 116 Tensile strength (MPa) 81 105 118 131 130 Elongation (%) 3.5 3 3.6 4 3.6 Tg (8C) 77 81 79 78 82 Mc (g/mol) 58 41 19 17 26 Glass laminate LSS (MPa) 30 29 34 Flexural strength (MPa) 361 369 438
and 4-hydroxy benzaldehyde was obtained via a simple addition reaction, per Scheme 24 [166]. The DOPO-PN novolac with multi-phenol groups in the molecular chain was used as a polyfunctional curing agent for epoxies. Curing occurred over a broad temperature range, from 160 to 275 8C. The activation energies of the DOPO PN curing reactions with epoxies were in the range 76 85 kJ/mol from DSC evaluation. High Tg (above 160 8C) and good thermal stability (Ti above 300 8C) were observed for the DOPO-PN/CNE200 (o-cresol novolac epoxy)-based resins. However, increasing DOPO decreased Tg : High char-yields and high limiting oxygen index (LOI) values implied good ame retardance for DOPO-PN-cured epoxy resins. The LOI values of the epoxy resins increased from 21 to 36 on enhancing
the P-content from 0 to 5%. DOPO led to decreased thermal stability although the char-content showed a proportional increase from 20 to 40% in one case,
Table 25 Effect of extent of allyl curing on properties of neat molding and composite (1:1 composition) [12] (Reprinted from Polymers and Polymer Composites by permission, q2003 Rapra Technology) Property 40% Allyl cured Neat Tensile strength (MPa) Elongation (%) Flexural strength (MPa) Tg (8C) ILSS (MPa) 118 3.6 113 79 Composite 369 86 29 100% Allyl cured Neat 77 3.3 110 91 Composite 458 107 32
449
Scheme 24. Synthesis of P-containing novolac (DOPO-PN) from 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO) and 4-hydroxy benzaldehyde [166], (Reprinted from Polymer by permission, q2001 Elsevier Science).
and from 35 to 45% in another. In a related work, Liu [167] synthesized DOPO-based aralkyl novolac by reaction of DOPO with terephthaldicarboxaldehyde and phenol. The resultant product (Ar-DOPO-N, see Scheme 25), blended with PF novolac (referred as DOPO PF) and melamine-modied novolac
(referred as DOPO MA) were used as curative for o-cresol formaldehyde novolac epoxy. The cured system possessed moderately high Tg (159 177 8C) and thermal stability (Ti . 320 8C). High char-yields and good ame resistance (LOI 26 32.5) were also observed. On replacing PF novolac with melaminemodied PF novolac, the Tg enhanced further to 160 186 8C. A phosphorous nitrogen synergism is believed to be the reason for the enhanced ame resistance in this case. An almost linear relationship was observed between LOI and phosphorous-content. In this case, the LOI increased to 28 33.3, despite a decreased char-yield in air caused by the melamine. The reverse trends in LOI and char-yields imply a possible vapor-phase action of the ame-retardant elements. The linear relationship between LOI and Pcontent and inverse relationship between LOI and char-yield, substantiating the above hypothesis is demonstrated in Fig. 16. Another approach for ame retardance was based on DOPO-formaldehyde reaction products. Thus, DOPO was reacted with formaldehyde to produce a reactive 2-(6-oxid-6H-dibenz kc,el k1,2l oxaphosphorin-6-yl)-methanol (ODOPM). Subsequently, novel ame-retardant curing agents for epoxy resins,
Scheme 25. Synthesis of P-containing aralkyl novolac (Ar-DOPO-N) from reaction of DOPO with terephthaldicarboxaldehyde and phenol [167]. (Reprinted from Journal of Polymer Science Polymer Chemistry Edition by permission, q2002 John Wiley and Sons).
450
Fig. 16. Variation of LOI and char-content with P-content for ame retardant epoxy-phenol polymer with two curatives. DOPO-MA: Melamine-modied Ar-DOPO-N; DOPO-PF: Ar-DOPO-N blended with PF novolac; Ar-DOPO-N: Novolac from DOPO reacted with terephthaldicarboxaldehyde and phenol [167].
viz. ODOPM-PN and ODOPM-MPN were prepared from phenol formaldehyde novolac (PN), melaminephenol formaldehyde novolac (MPN) and ODOPM, respectively. The compounds ODOPM PN and ODOPM MPN were used as ame-retardant hardener for o-cresol formaldehyde novolac epoxy (CNE) resin for electronic applications [168]. The phosphorus nitrogen synergistic effect on ame retardance, combined with the rigid structure of ODOPM resulted in better ame retardance, higher Tg
and thermal stability for the phosphorus-nitrogen containing epoxy resin system in comparison to the regular phosphorus-containing ame-retardant epoxy resin. The UL 94-VO rating could be achieved with a phosphorus-content as low as 0.81 with 2.36% nitrogen for the ODOPM-MPN cured epoxy resin system. No fume and toxic gas emission was observed. The same team investigated the physical and ame retardant properties of o-cresol formaldehyde novolac resin cured in the presence of 2-(6Oxido-6H-dibenzokc,eloxa-phophorin-6-yl)1,4-benzene diol (ODOPB) and bis (3-hydroxyphenyl) phenyl phosphate (BHPP, structures in Scheme 26) [169]. The rigid cyclic structure of ODOPB caused an enhanced Tg for the resultant cured material. The phosphorous-containing epoxy exhibited higher Tg ; thermal stability and ame resistance when compared to the state-of-the-art ame-retardant formulations based on tetrabromobisphenol-A-based epoxies. In this case, the UL-94VO rating was achieved with a P-content as low as 1.1%. The ODOPB-epoxy system gave Tg values in the range 183 187 8C, whereas the BHPP only gave Tg in the range 125 155 8C. The modulus, thermal stability and char-yield were also higher for the ODOPB-cured resins. Flame-retardant phenol epoxy systems have been realized through synergism of phosphorous/silicon and nitrogen/silicon also. This was achieved by curing silicon-containing epoxy resins with DOPO PN-based and melaminebased phenolic resins [170]. The silicon-containing epoxies resulted on reacting diphenylsilandiol with
Scheme 26. Synthesis of P-containing phenolic curatives 2-(6-oxido-6H-dibenzokc,eloxa-phophorin-6-yl)1,4-benzene diol (ODOPB) and Bis (3-hydroxyphenyl) phenyl phosphate (BHPP) for epoxy resin [169] (Reprinted from Journal of Polymer Science Polymer Chemistry Edition by permission, q2002 John Wiley and Sons).
451
epoxy resins based on bisphenol-A and o-cresol novolac in the presence of tin (II) chloride. Silicon, in synergism with phosphorous, conferred signicant ame retardance to the systems. LOI values of the order of 49 could be achieved at a phosphorous level of 4.71%. However, the Tg values were reduced when compared to the DOPO PF and DOPO MA systems described above. 5.5. Miscellaneous curative for novolac Void-free thermosets have been prepared from novolac, cured by bisphthalonitrile (BPh) compounds. A BPh proportion of 15 20 wt% led to tough, high Tg and extremely ame-resistant networks [171]. The polymer properties depend on reactant ratios. The Tg increased from 120 8C to about 210 8C on enhancing the BPh-content from 5 to 25 wt%. TGA indicated a slow degradation in air, beginning at about 500 8C and extending to 750 800 8C. The char residue at 700 8C is
60 80%, which is signicantly higher when compared to the conventional thermosets including epoxy novolac. The degradation is non-thermo-oxidative in nature. The system possessed good fracture toughness (KIC , 0.8 MPa m1/2). Investigation of the cure mechanism using model compounds indicated formation of diiminoisoindoline structure. Based on the study, a product structure as depicted in Scheme 27 was proposed, although the authors admit that this is inconclusive.
6. Phenolic resins with phenyl maleimide functions Novel phenolic novolac resins, bearing maleimide groups (PMF resin) and capable of undergoing cure principally through addition polymerization of these groups were synthesized by polymerizing a mixture of phenol and N-(4-hydroxy phenyl) maleimide (HPM) with formaldehyde in the presence of an acid catalyst
Scheme 27. Possible reaction product of bisphthalonitrile and novolac [171] (Reprinted from Polymer by permission, q2002 Elsevier Science).
452
Scheme 28. Synthesis and curing of phenolmaleimidophenol formaldehyde (PMF) resin from hydroxy phenyl maleimide (HPM), phenol and formaldehyde [172] (Reprinted from Journal of Applied Polymer Science by permission, q2000 John Wiley and Sons).
[172]. The synthesis is shown in Scheme 28. The maleimide-content was varied by regulation of the stoichiometry in the feed. The resins were characterized by chemical, spectral and thermal analyses. DSC and DMA revealed an unexpected two-stage curing for these systems. The DSC of PMF resin of different maleimide-content shows identical two-stage curing as seen in Fig. 17. Whereas the cure at 225 275 8C was attributable to the addition polymerization reaction of maleimide groups, the exotherm at around 150 170 8C was ascribed to the condensation reaction of methylol groups formed in minor quantities on the phenyl ring of HPM. 13C NMR exhibited a signal at 65 ppm due to CH2 OH groups. Polymerization studies on non-hydroxy functional, N-phenyl maleimide (with formaldehyde) revealed that the phenyl groups of these molecules are activated towards electrophilic substitution reaction by the protonated methylol intermediates (formed during the acid catalyzed reaction of phenol and formaldehyde). The methylol groups are formed by activation of the alkyl substituted HPM molecule towards the protonated formaldehyde molecule. The proposed reaction pathways are depicted in Scheme 29. It was also revealed that the presence of the phenolic group on N-phenyl maleimides was not imperative for its copolymerization with phenol and formaldehyde. The cure characterization of the PMF
resin by DMA conrmed a two-stage cure. Although DSC implied a prominence for the methylol condensation, DMA showed that the contribution of this step in the total cross-linking process is negligible, although helpful in causing an early gelation for the system. The methylol substitution amounted to about 6%. The isothermal DMA of the system (Fig. 18) showed a minor increase in storage modulus at
Fig. 17. DSC of various phenolmaleimidophenolformaldehyde (PMF) resins in N2. The number denotes the composition of the polymer in terms of the maleimidophenol-content. Heating rate 10 8C/min [210].
453
Scheme 29. Proposed reaction paths for formation of phenolmaleimidophenolformaldehyde polymer [172] (Reprinted from Journal of Polymer Science Polymer Chemistry Edition by permission, q2000 John Wiley and Sons).
the initial stage due to this reaction. The DMA also conrmed the dominance of maleimide polymerization over methylol condensation in the network build-up process. The curing is practically complete in about 2 h at 250 8C. The kinetics of both the cure reactions substantiated the proposed cure mechanism for each stage
[173]. Although the initial decomposition temperature (IDT) of the cured resin was not signicantly improved, enhancing the cross-link density through HPM improved the thermal stability of the material at higher temperature regime. The anaerobic char-yield also increased proportional to the maleimide-content. Isothermal pyrolysis and analysis of the char
Fig. 18. Isothermal DMA of phenolmaleimidophenol-formaldehyde (PMF-29) at 250 8C. Heating rate for dynamic part, 10 8C/min. Frequency 1 Hz [173]. (Reprinted from Journal of Applied Polymer Science by permission, q2001 John Wiley and Sons).
454
Table 26 Mechanical properties of laminate composites of PMF using silica reinforcement, effect of composition and cure temperature [173] (Reprinted from Journal of Applied Polymer Science by permission, q2001 John Wiley and Sons) Resina ILSS (MPa) 08 Compressive strength (MPa) 250 8C 17 23 24 22 34 19 200 8C 39 74 55 250 8C 104 202 160 150 290 150 Flexural strength (MPa) 200 8C 84 147 166 250 8C 178 190 170 200 190 30 30 30 31 30 Resin-content (wt%)
200 8C PMF-19 PMF-23 PMF-29 PMF-35 PMF-29/glass Resole

a
11 16 18
Number signies the extent of phenyl maleimide-content (wt%) in PMF resin.
conrmed that the pyrolysis occurs by the loss of hydrocarbon and nitrogenous products. The resin served as effective matrices in silica- and glass fabricreinforced composites. Table 26 compiles the properties of the composites derived form PMF resins of varying maleimide-content and cured at two different temperatures. The resins cured at 200 8C naturally possessed inferior mechanical properties due to incomplete maleimide polymerization. On the contrary, higher cross-linking led to brittle failure. The mechanical properties were optimum for moderately cross-linked resins, wherein the composite failure was
found to occur through a combination of ber debonding and resin fracture. On a comparative scale, the properties were better than those of resole (resole cured at 150 180 8C). Changing the reinforcement from silica to glass resulted in a composite with improved strength. In related work, aminophenols were allowed to react with maleic and phthalic anhydrides, producing high yields of the corresponding N-(hydroxyphenyl) maleamic and phthalamic acids. Formaldehyde was allowed to react with these products in the presence of an acid catalyst. The resulting product was dehydrated
Scheme 30. Synthesis of isoimide- and imide-containing phenolic resin [174] (Reprinted from Journal of Polymer Science Polymer Chemistry Edition by permission, q2000 John Wiley and Sons).
455
Scheme 31. Cured structure of blend of phenolmaleimidophenolformaldehyde (PMF) and Phenolallylphenol formaldehyde (PAF) [175] (Reprinted from Journal of Applied Polymer Science by permission, q2001 John Wiley and Sons).
to the corresponding maleisoimide- and phthalisoimide-containing novel phenol formaldehyde resins (Novolac-like). On treatment with a sodium carbonate solution or on prolonged heating at 50 8C the resins suffered rearrangement to the corresponding phenolformaldehyde resins with pendant maleimides [174]. This rearrangement was accompanied by an increase in the softening point of the polymers. No other polymer properties were reported. A typical synthesis protocol is shown in Scheme 30. 6.1. Maleimide phenolic resin cured with allyl phenolics The thermal curing of the PMF system through polymerization of maleimide group resulted in comparatively brittle matrices. As a result, the mechanical properties of the resultant composites did not improve signicantly over the conventional phenolic resins. Hence, the concept of BMI toughening by way of reactive blending with allyl compounds (discussed in Section 2.1) was extrapolated to the PMF system. Thus, new addition-cure phenolic resin systems were developed, based on the co-reaction of maleimide-functional phenolic resin (PMF) with an allyl-functional novolac (PAF) in varying proportions [175]. The PAF resin was derived from 2-allyl phenol, phenol and formaldehyde. The Alder-ene cure sequences to form a cross-linked network system were evidenced from the cure characterization studies by DSC and DMA. Extrapolating the cure sequences, the network structure of a 1:3 blend can be depicted as in Scheme 31 for this system. Increasing allyl phenol content in the reactive blend decreased the cross linking in the cured matrix, leading to enhanced toughness and improved the resin-dominant
mechanical properties of the resultant silica laminates. The mechanical properties of the composites of the blend of different compositions are compiled in Table 27. Under the cure conditions employed, the properties are optimum at an allyl/maleimide ratio of 1:3. Changing the reinforcement from silica to glass resulted in further amelioration of the resin-reinforcement interaction, but the resin-dominant properties of the composite remained unaltered. However, the presence of AP diminished the thermal stability. The cured polymers showed Tg in the range 170 190 8C. In an analogous strategy, a one-component, self-cross linkable polymer was synthesized by reacting a mixture of phenol, HPM and 2-allyl phenol with formaldehyde (PMAF) where, the allylphenol/maleimide ratio was maintained as 1:3. When compared to the two-component system of similar composition, this system showed inferior composite properties [175] (data in Table 27). The structures of PMAF resin and the likely structure of its cured product are shown in Scheme 32.
Table 27 Mechanical Properties of Silica Laminate of PMF-29, blended with PAF resin [175] (Reprinted from Journal of Applied Polymer by permission, q2001 John Wiley and Sons) Blend Allyl/maleimide ratio (equivalent) 01:01 01:02 01:03 01:04 01:05 00:01 01:03 ILSS (MPa) Flexural strength (MPa) 203 209 202 204 176 168 165 08 Compressive strength (MPa)
MAP1 MAP2 MAP3 MAP4 MAP5 PMF PMAF
23.5 25 23 29 23.5 24 20
253 222 210 251 192 157 171
456
Scheme 32. Structure of one-component phenolallyl phenolmaleimidophenolformaldehyde polymer (PMAF) and its cured product.
6.2. Maleimide phenolic (PMF) epoxy blend The majority of phenolic-based adhesive formulations makes use of the condensation cure of resole resins, which necessitates the application of high pressure during the adhesive bonding to form void-free glue lines. The limited shelf life of the resole-based adhesives at ambient temperature is another shortcoming of phenolics. Addition curable phenolicsbased systems could be better suited for adhesive applications than conventional phenolics. Thus, the maleimide-functional novolac phenolic resin (PMF) was cured with epoxy resin (EPN). It was evaluated for the adhesive properties such as lap shear strength (LSS) and T-peel strength (TPS) using aluminum adherends, both in the thermally self-cured state as well as co-cured with epoxy resins [176]. The adhesive properties of the self-cured resin, although inferior at ambient temperature, improved at high temperature (150 8C) and the properties were found to depend on the extent of maleimide curing. Table 28 lists the adhesive properties of a typical PMF resin cured under different conditions. The extent of maleimide curing was estimated from studies on thermal polymerization of the model compound, HPM. Although the adhesive strength is not high, it is interesting that it increases at high temperature due to softening of the rigid matrix. The high temperature strength is also proportional to the maleimide cross-linking (see Table 28). However, on co-curing PMF with the EPN epoxy resin through the phenol-epoxy reaction and subsequent maleimide polymerization, the adhesive properties improved signicantly. The adhesive properties showed a strong dependence on the nature of the epoxy resin used, stoichiometry of the reactants, the concentration of imide groups in the phenolic resin and the extent of
polymerization of the maleimide groups. The cure sequences are shown in Scheme 33. The dependence of the LSS at RT, 150 and 175 8C as well as the TPS at RT on the epoxy phenolic stoichiometry for the PMF-29/ EPN system is shown in Fig. 19. The adhesive strength (both LSS and T-peel) becomes optimized at a 1:1 equivalent of the two components. The LSS at 150 and 175 8C as well as the retention of the LSS at these temperatures also become optimized at this stoichiometry. This shows the dominance of the epoxyphenol reaction in deciding the adhesive characteristics of the system. The 1:1 stoichiometry ensures maximum cross-linking through the phenolepoxy reaction. A maximum extent of phenolepoxy cure is desirable to promote better adhesion and better retention at higher temperature. An excess of EPN leaves unreacted epoxy groups, leading to matrix plasticization, and diminution of properties. Although their absolute values were lower, the phenol-rich systems exhibited better high-temperature retention of properties thanks to the presence of thermally stable imidophenol groups in the network. Typical adhesive values of PMF resins with varying
Table 28 Effects of cure temperature and maleimide polymerisation on LSS of self-cured PMF-29. (initial cure: 170 8C/30 min; ultimate-cure: 30 min) [176] (Reprinted from Journal of Applied Polymer Science by permission, q1999 John Wiley and Sons) Post-cure temperature (8C) Extent of maleimide polymerisation (%) 37 75 89 LSS at RT (MPa) LSS at 150 8C (MPa) Retention of LSS at 150 8C (%)
200 225 250
2.1 4.1 4.6
3.5 6.8 9.1
167 166 198
457
Scheme 33. Cure sequences of phenolmaleimidophenolformaldehydeepoxy novolac blend [176] (Reprinted from Journal of Applied Polymer Science by permission, q1999 John Wiley and Sons).
maleimide-content and measured at varying temperatures are given in Table 29. The maleimide is polymerized only to a minor extent (37%) under these conditions, whereas the phenol-epoxy reaction is complete. In comparison to the conventional novolac (PF), the imide novolac (PMF) contributed to improved adhesion and better adhesive property retention at higher temperature when cured with EPN. Good bonding resulted for PMF-29 with moderate maleimide-content. In fact, for the PMF/EPN system, the high temperature adhesion was directly proportional to the extent of maleimide polymerization, which was controlled by the cure temperature and time. Fig. 20 shows the direct relationship between high temperature (150 8C) retention of adhesion strength and the extent of maleimide curing. The TPS (at RT) tends to increase with maleimide-content, but the brittleness of the system at higher maleimide-loading deteriorates the strength. The comparative thermo-adhesive proles of the PMF-epoxy and PF-epoxy, showing
Fig. 19. Effect of phenol/epoxy stoichiometry on Lap shear strength and T-peel strength of phenolmaleimidophenolformaldehyde (PMF-29)/epoxy novolac (EPN) system (B) LSS at RT; (X) LSS at 150 8C; (O) LSS at 175 8C; (V) TPS at RT [176] (Reprinted from Journal of Applied Polymer Science by permission, q1999 John Wiley and Sons).
458
Table 29 Adhesive properties of various PMF resins reacted with EPN (1:1 stoichiometry, cure: 170 8C/30 min and 200 8C/30 min.; phenol-epoxy reaction is complete and extent of maleimide cure is 37%) [176] (Reprinted from Journal of Applied Polymer Science by permission, q1999 John Wiley and Sons) System LSS at RT (MPa) LSS at 150 8C (MPa) Retention of LSS at 150 8C (%) LSS at 175 8C (MPa) Retention of LSS at 175 8C (%) 20 18 47 35 T-peel at ambient (kN/m)
PF/EPN PMF-19/EPN PMF-29/EPN PMF-42/EPN
15.5 15.3 17 11.3
7.2 5.6 14.3 8.2
47 37 84 73
3.1 2.8 8 3.9
0.4 0.43 0.56 0.08
the superiority of the former are shown in Fig. 21. The absolute adhesion values and the thermal resistance are good for the former. Complimentary DMA studies led to the conclusion that the superior thermo-adhesive prole of the PMF/EPN system is contributed by secondary attraction forces induced by the polar imide groups. The partial polymerization of the imide helps consolidate these secondary forces of attraction both within the resin system and at the bonding interphase. The enhanced bonding characteristics of the PMF EPN system was manifested in a better short beam shear strength (SBSS) of the carbon-UD composite based on PMF/EPN (85.5 MPa) as against that of PF/EPN (68.5 MPa). The study also implied that the completion of epoxy phenolic
reaction and moderate cross-linking through the maleimide polymerization are conducive for achieving optimum adhesive properties. Although the adhesive properties of PMF/EPN blends were good, attempts were made to improve it further by blending with elastomeric modiers, viz. a liquid carboxyl-terminated butadiene acrylonitrile (CTBN-L), a solid carboxyl-terminated butadiene acrylonitrile (CTBN-S), epoxidized hydroxyl-terminated polybutadiene (EHTPB) and epoxidized butyl acrylate acrylonitrile polymer (EPOBAN) [177]. The adhesive properties were found to depend on the nature and concentration of the elastomers as well as on the nature of the thermoset matrix being modied.
Fig. 20. Retention of lap shear strength (at 150 8C) and T-peel strength at RT and their relationship to the extent of maleimide polymerisation for phenol maleimidophenol formaldehyde (PMF-29)/epoxy novolac (EPN) system. (B) Maleimide polymerisation; (X) LSS retention at 150 8C; (P) T-peel at RT.
Fig. 21. Comparative thermo-adhesion prole for (B) phenol maleimidophenolformaldehyde (PMF-29)/epoxy novolac (EPN) and (X) phenolformaldehyde (PF)/EPN systems [176] (Reprinted from Journal of Applied Polymer Science by permission, q1999 John Wiley and Sons).
459
Table 30 Effect of CTBN-S on the adhesive properties of PMF-29 and PMF29/EPN systems [177] (Reprinted from Journal of Applied Polymer Science by permission, q1999 John Wiley and Sons) Concentration of the additive (phr) Self-cured PMF PMF/EPN
LSS (MPa)
TPS at RT (kN/m)
LSS (MPa) RT 150 8C 14.3 10.6 9.4 7.8 6.5
TPS at RT (kN/m)
RT 0 10 15 20 30 2.1 5.3 8.0 11.3 14.3
150 8C 3.5 5.2 4.5 4.3 3.9 0.01 0.43 0.64 0.70 1.00
17.0 18.5 20.0 20.0 20.0
0.56 1.20 1.70 2.00 2.00
Fig. 22. Effect of carboxyl terminated polybutadiene (CTBN) on the adhesive characteristics of phenolmaleimidophenolformaldehyde(PMF) and PMF/epoxy novolac blend; CTBN-S: solid, CTBN-L: liquid [177] (Reprinted from Journal of Applied Polymer Science by permission, q1999 John Wiley and Sons).
Fig. 23. Effect of carboxyl terminated polybutadiene (CTBN) on the high temperature adhesion of phenolmaleimidophenolformaldehyde (PMF) and PMF/epoxy novolac systems. S CTBN-Solid, L CTBN-Liquid [177] (Reprinted from Journal of Applied Polymer Science by permission, q1999 John Wiley and Sons).
The adhesive properties at ambient temperature of the self-cured, brittle PMF resin were dramatically improved by the inclusion of the elastomers, the increase being substantial in the case of high molecular weight CTBN. Typical results are shown in Fig. 22. However, contrary to expectation, the adhesive properties of the epoxy PMF system were only marginally improved by the high molecular weight CTBN, while the other elastomers were nearly ineffective. For both the self-cured and epoxy-cured PMF systems, the inclusion of these elastomers generally decreased the high temperature adhesive properties, evidenced also from their dynamic mechanical spectra. This trend is evident from the LSS values at 150 8C in case of CTBN-modied matrices shown in Fig. 23. The decrease is sharper with CTBN-L. The presence of phase-separated elastomer particles in the modied systems was evident in the SEM analyses. The adhesive properties of the elastomermodied systems are given in Tables 30 and 31. CTBN-L was not effective in enhancing the properties, whereas high molecular weight CTBN-S was very effective for both LSS and TPS. The relative increase was more pronounced for the PMF self-cured system rather than the PMF-EPN system. The epoxy-containing EHTPB and EPOBAN were capable of improving the properties, but only to an insignicant extent. For a given composition, the decrease in high temperature property was sharper for CTBN-L than for CTBN-S, due to the reduced compatibility of the former in the matrix. Similarly, between EPOBAN and EHTPB,
460
Table 31 LSS (in MPa) of PMF-29 and PMF-29/EPN system modied by EHTPB and EPOBAN [177] (Reprinted from Journal of Applied Polymer Science by permission, q1999 John Wiley and Sons) Concentration of the additive (phr) EHTPB Self-cured PMF RT 150 8C 0 10 15 20 30 2.1 3.5 4.6 5.4 5.8 3.5 2.2 1.8 1.7 0.8 PMF/EPN RT 150 8C 17 16 14.7 13.2 12.9 14.3 6.3 5.3 3.6 2.5 EPOBAN Self-cured PMF RT 150 8C 2.1 2.2 3.3 3.5 2.6 2.4 PMF/EPN RT 150 8C 17 15.4 16.6 14.3 4.9 5.3
the former was comparatively better in retaining the LSS at high temperature; possibly due to its additional cross linking through the cyclization reaction of the nitrile groups under the cure conditions. A DMA study of the elastomer-modied PMF/EPN system showed that the absolute values of E0 are reduced with the inclusion of these elastomers, whereas the temperature for the maximum tand remain almost unaffected (Fig. 24). SEM analysis showed the single-phase morphology for the unmodied PMF and PMF/EPN systems and a phase-separated morphology for the elastomer-modied materials. The size and state of
the precipitated secondary phase depend on the molecular weight as well as the chemical reactivity of the added elastomer. For the CTBN-S modied systems, the dispersed phase was co-continuous and this morphology led to the maximum improvement in adhesive properties. For the CTBN-L-, EHTPB- and EPOBAN-modied PMF/EPN systems, the dispersed phase was non-uniform with a wide distribution of particle sizes. These particles were too large to be effective in improving the toughness of the system, and hence reduced the adhesive properties. The elastomers were, by and large, very effective in enhancing the peel strength of the adhesives. 7. Pendant phenol functional linear polymers 7.1. Pendant phenol-functional thermoplastics Linear vinyl polymers with pendant phenolic groups were realized by free radical copolymerization of N-(4-hydroxy phenyl) maleimide (HPM) with
Table 32 Composition, molecular and mechanical characteristics of BNM polymers (BuA/AN weight ratio 2) [178] (Reprinted from Journal of Adhesion Science and Technology by permission, q2001 Koninklijke Brill NV) Polymer HPM Mn Poly Tensile Elonga- Softening reference (wt%) 1024 disper- strength tion (%) temperasity (MPa ) ture (8C) index BNM-1 BNM-2 BNM-3 BNM-4 5.1 7.4 9.5 13.6 5.69 5.78 5.2 5.52 1.83 1.74 1.88 1.74 20 21.5 24.5 300 225 23 ,28 ,28 40 45
Fig. 24. DMA spectra of the elastomer-modied phenolmaleimidophenol formaldehyde (PMF-29)/epoxy novolac blends(EPN) cured in presence of epoxididsed hydroxy terminated polybutadiene (EHTPB),Liquid carboxyl terminated butadieneacrylonitrile polymer (CTBN-L), Solid carboxyl terminated butadiene acrylonitrile polymer (CTBN-S) and epoxidised butylacrylate acrylonitrile polymer (EPOBAN)[177] (Reprinted from Journal of Applied Polymer Science by permission, q1999 John Wiley and Sons).
461
Scheme 34. Butyl acrylateacrylonitrilemaleimidophenol (BNM) polymers and their thermosetting derivatives, A-triazine; B-propargyl ether; C-epoxy.
butyl acrylate (BuA) and acrylonitrile (AN) and were characterized [178]. These thermoplastics (BNM) could form good lms, with mechanical and adhesive properties dependent on the maleimido phenolcontent in the chain, as given in Table 32. The structure of the terpolymers can be found in Scheme 34. The polymer lms could be directly served as thermoplastic adhesives and their adhesive properties were studied in detail. LSS were determined at ambient temperature, 50 8C and at 196 8C, whereas T-peel strength (TPS) and at wise-tensile strength (FTS) were determined at ambient temperature. Enhancing the HPM-content increased Tg ; the tensile strength and modulus of the lms, but decreased their elongation. Nominal increase in phenol-content was found conducive to improving the adhesive properties of the lms. At higher concentrations of phenol, the lm properties showed a decreasing trend due to the embrittlement caused by the rigid maleimide groups. Whereas the adhesive property at 50 8C increased linearly with HPMcontent, due to increased Tg ; a reverse trend was observed for the property measured at 2 196 8C due to dominance of embrittlement effect. This trend is
demonstrated in Fig. 25. The reduced ow characteristics of the high HPM-loaded systems led to diminished tensile strength properties evaluated using at-wise bonded aluminium honeycomb adherends. The T-peel was also optimum for BNM-3, whereas FTS was good for BNM-2. The dependence of TPS and FTS on maleimido-phenol-content of the lm adhesives are presented in Fig. 26. On the contrary, enhanced HPM concentration promoted the adhesive properties for vulcanization bonding of NBR to aluminium. This is evident from the data presented in Table 33. The failure mode is also indicated. High maleimide-content promotes bonding to the extent that failure is induced in the rubber substrate for BNM-3 and BNM-4 in the peel mode. Addition of silica ller marginally improved the LSS for metal metal system, but was detrimental for metal rubber bonding. A reverse trend was observed for the carbon-lled BNM system, with the diminished performance for metal metal and enhanced performance for metal rubber systems attributed to the weakening of the interphase in the former, and to a possible reinforcement of the rubber phase by carbon in the latter. The llers generally
462
C.P. Reghunadhan Nair / Prog. Polym. Sci. 29 (2004) 401498 Table 33 Aluminium-to-NBR vulcanization bonding properties of BNM polymers (AF: cohesive failure in the adhesive; IF: adhesive rubber interface failure; RF: cohesive failure in the rubber) [178] (Reprinted from Journal of Adhesion Science and Technology by permission, q2001 Koninklijke, Brill NV) Adhesive property LSS at ambient temperature (MPa) Nature of failure TPS at ambient tempearture (kN/m) Nature of failure BNM-1 BNM-2 BNM-3 BNM-4 0.26 AF 2.8 AF 0.37 IF 4.1 IF 0.39 IF 5.0 RF 0.45 IF 5.0 RF
Fig. 25. Evolution in lap shear strength at different temperatures of butyl acrylate acrylonitrile maleimidophenol (BNM) polymers on hydroxy phenyl maleimide (HPM)-content[178] (Reprinted from Journal of Adhesion Science and Technology by permission, q2001 Koninklijke Brill NV).
the ow properties of the resin, and thereby adversely affected the at-wise bonded tensile strength in both cases. A compromise between reinforcement and ow property is reached at about 20 wt% of the ller loading, where the adhesive property is maximum. In general, the optimum LSS and T-peel properties were obtained for BNM-3 and FTS properties for BNM-2. 7.2. Pendant phenol-functional addition-cure systems The adhesives properties and their temperature retention could be improved further on transforming these lm adhesives to addition-curable phenolic thermoset lms by reactive blending with an epoxy
improved the temperature capability of the adhesives. This is shown in Fig. 27, which compares the adhesion strength at 50 8C for BNM-3 lled with silica and carbon. The retention is calculated based on the strength at ambient temperature. The llers impaired
Fig. 26. Dependence of T-peel strength (TPS) and at-wise tensile strength (FTS) on hydroxy phenyl maleimide-content for thermoplastic lm adhesive [178] (Reprinted from Journal of Adhesion Science and Technology by permission, q2001 Koninklijke Brill NV).
Fig. 27. Effect of ller on adhesive (metal-metal) properties of butyl acrylateacrylonitrilemaleimidophenol (BNM-3) thermoplastic at ambient and at 50 8C [178] (Reprinted from Journal of Adhesion Science and Technology by permission, q2001 Koninklijke Brill NV).
463
Fig. 28. Lap shear strength (LSS) at 25, 50 and 2196 8C for epoxy-cured butyl acrylateacrylonitrile maleimidophenol (EpBNM) polymers as a function of Hydroxy phenyl maleimide (HPM)-content in the polymer [179] (Reprinted from Journal of Adhesion Science and Technology by permission, q2001 Koninklijke Brill NV).
resin. Alternatively transformation of the phenolic OH groups to propargyl ether, cyanate etc and subsequent curing also provided thermosets [179]. On cross-linking through reaction with a diepoxide, the mechanical and adhesive properties of the lm adhesive (Ep-BNM) improved signicantly. In this case, the properties increased with the concentration of imido phenol and its cross-linking. However, high imide-content and higher cross-linking were detrimental for the low temperature adhesive properties
Table 34 Aluminium-to-NBR vulcanisation bonding properties of Ep-BNM polymers (AF: adhesive failure; IF: adhesiverubber interface failure; RF: rubber failure) [179] (Reprinted from Journal of Adhesion Science and Technology by permission, q2001 Koninklijke, Brill NV) Adhesive property LSS at 25 8C (MPa) Type of failure Peel strength at 25 8C (kN/m) Type of failure Ep-BNM-1 Ep-BNM-2 Ep-BNM-3 EpBNM-4 0.3 AF 2.8 AF 0.33 AF 4.2 IF 0.53 RF 5.1 RF 0.52 RF 5.0 RF
(at 196 8C), although the retention at high temperature was improved. Values of the LSS at different temperatures determined with Ep-BNM polymers (epoxy-cured BNM-3) using aluminium substrates are shown in Fig. 28, showing that the trend is the same for the LSS at 25, 50 and 2 196 8C. The initially observed adhesive performance advantage is lost at higher HPM-content. However, the effect is less pronounced for the LSS at 2 196 8C. As observed with thermoplastic BNM polymers [178], the increase in the LSS with HPM-content for the Ep-BNM polymers is attributed to the increased cohesive strength induced by the polar hydroxy- and maleimide moieties. Beyond 9.5% of HPM, the polymer becomes rather brittle, leading to inferior strength. In comparison with the corresponding thermoplastic BNM polymers, Ep-BNM polymers exhibit higher LSS values at 25 and 50 8C, but inferior properties at 2 196 8C. The LSS and peel strength values of the different Ep-BNM adhesives bonded aluminum-to-NBR joint are given in Table 34. Both LSS and peel values increase with increase in HPM-content and the failure mode changes from cohesive failure in adhesive (AF) to adhesive-rubber interface failure (IF), and nally to cohesive failure in the rubber (RF) with polymers having more than 7.4% HPM. Similar results were obtained with the thermoplastic BNM polymers where the LSS varied from 0.26 to 0.45 MPa and peel strength varied from 2.8 to 5.0 kN/m. The effect of introducing cross-links into the BNM polymer was much less pronounced for the case of metal-to-rubber bonding. Designing a one-component, self-curing type thermoset (through phenol epoxy reaction) based on an acrylic polymer bearing both epoxy and phenol groups (i.e. Gly BNM) and was not very effective in providing good adhesive properties. Cross-linking the BNM polymers after chemical reaction of the phenol group through propargylation improved the adhesive properties at RT to a comparable extent with that of epoxy cross-linked resin (Ep-BNM). The propargyl BNM polymer exhibited good LSS values at 25 8C, only slightly inferior to that of the Ep-BNM polymer; however, the LSS properties at 50 8C were very poor and nearly the same as with BNM. This could be due to incomplete thermal curing of propargyl groups under these cure conditions. Neither was chemical transformation of
464
Table 35 Adhesive properties of modied BNM polymers compared to the unmodied thermoplastic polymer (IF: adhesiverubber interface failure; RF: rubber failure) [179] (Reprinted from Journal of Adhesion Science and Technology by permission, q2001 Koninklijke, Brill NV) Adhesive property BNM-3 Ep-BNM-3 Gly-BNM Propargyl BNM Cyanate BNM
Metal-to-metal LSS at 25 8C, (MPa) LSS at 508C, (MPa) Retention of LSS at 508C (%) TPS at 25 8C (kN/m) Aluminium-to-NBR LSS at 25 8C( MPa) Type of failure TPS at 25 8C (kN/m) Type of failure
17.5 6.9 39 1.70 0.39 IF 5.0 RF
20.2 14.5 72 1.40 0.53 RF 5.1 RF
8.5 6.0 70 0.25 0.39 IF 4.0 IF
18.0 6.0 33 0.30 0.42 IF 4.3 IF
8.0 2.8 35 0.30 0.42 IF 3.8 IF
the phenol to cyanate groups, and its subsequent curing to polycyanurate very effective in improving adhesive properties. The lowest LSS values were exhibited by the cyanate BNM polymer. All the cross-linking reactions impaired the peel strength of the lm adhesive. Metal-to-NBR joint strength was found to be nearly the same as that for BNM-3 for all the modied polymers, indicating that the cross-links introduced did not appreciably affect the strength. Except Ep-BNM, all other polymers resulted in an adhesive rubber interfacial failure of the metal-torubber joints, probably due to the weaker interactions
of the propargyl and cyanate ester groups with NBR, in comparison to the epoxy. The various chemical structures have been included in Scheme 34. The adhesive properties of the thermosetting BNM polymers are given in Table 35. The dominance of epoxy curing in imparting the adhesive properties is clear. 8. Propargyl ether functional phenolics Although less commercially exploited, propargyl ether-functional phenolic resins were developed as a potential hydrophobic substitute for epoxies in
Scheme 35. Synthesis and curing of propargyl novolac (PN) resins [197] (Reprinted from Polymer International by permission, q2001 Society of Chemical Industry).
465
advanced composites, electronics, adhesives and coatings. The majority of thermosets, such as epoxy, BMI, etc. absorb moisture up to 5%, resulting in low hot/wet physico-chemical properties. For advanced applications, the required hot/wet performances for many composites are to exceed temperatures of about 230 8C. Hydrophilicity can lead to easy matrix delamination too. Obviously, the high Dk of absorbed water is detrimental for electronic applications of such polymers. Propargyl ether resins can address some of these problems. The structural similarity of propargyl ether to epoxy resins is useful for their preparation, processing and development of thermally stable polymers [180]. Derived from a phenolic backbone, resins based on propargyl ether possess some of the basic features of the parent polymer. Thus, propargyl phenolics can offer a compromise matrix between epoxy and phenolics. Propargyl ether resins are formed easily from the phenolic precursor by the Williamsons reaction with the propargyl halide. The synthesis of propargyl novolac (PN) is shown in Scheme 35. The various cure mechanisms are also depicted in the above scheme. More than PN resins, the synthesis and curing of bispropargyl ether resins (BER) have been quite well described in literature [181 183]. The latter is formed from the corresponding bisphenol. 8.1. Curing of propargyl ether resins The curing of propargyl ether resins proceeds by Claisen rearrangement followed by addition polymerization of the resultant chromene. This has been conrmed by studies on model propargyl ethers [184]. The structural dependence on cure kinetics of bis propargyl ether resins (BER) has been investigated [185]. Thus, bis propargyl ethers of bisphenol-A, (BPBA), bisphenol ketone (BPK) and bisphenol sulfone (BPS) were synthesized and characterized. These monomers were thermally polymerized to the corresponding poly(bischromenes). The cure behavior, as monitored by DSC, depended on the structure of the monomer. The non-isothermal kinetic analysis of the cure reaction using four integral methods revealed that the presence of an electron-withdrawing group did not favor the cyclization reaction leading to formation of chromene, which precedes the polymerization, and in agreement with the proposed
polymerization mechanism. Thus, the cure temperature and activation energy for the reaction increased in the order BPBA , BPK , BPS. The cure prole under isothermal and non-isothermal conditions could be simulated from the kinetic parameters. Typical isothermal cure predictions at varying temperatures are shown in Fig. 29, along with an experimental cure prole at one temperature for comparison with the prediction. The substituent group bridging the two phenyl rings also inuenced the thermal stability of the resultant polymers. Thus, sulfone and ketone-containing polymers were more stable than the isopropylidene-containing material. Kinetic analysis of thermal decomposition of the major step involving the chromene moieties revealed a two-stage degradation mechanism. The computed activation energies implied that the initiation of the degradation reaction was disfavored by the electron-withdrawing nature of the bridge unit, probably through destabilization of the intermediate radical. This made such polymers more thermally stable. The possible typical mechanism for initiation of thermal degradation of the crosslinked chromene is shown in Scheme 36, for polymer of BPBA. The decomposition is proposed to initiate at the crowded carbon, giving rise to benzyl type free radicals, with a stability that is decreased by the presence of electron-withdrawing substituents on the phenyl ring. The same scheme depicts the structure of BER, and its likely cured structure. In the presence of a catalyst, the polymerization mechanism is different, as are the properties of the resultant polymers. Certain catalysts are found to favor the linear polymerization of the acetylene groups. Thus, polymerization of nitrophenyl propargyl ethers with tungsten- and molybdenum-based metathesis catalyst systems (MoOCl4/Me4Sn and MoCl5/EtAlCl2) gave soluble linear high-molecular-weight poly(nitrophenyl propargyl ether) (Mw , 4 105) [186]. The expected cyclotrimerization is favored when the system is heated in the presence of the catalysts, such as cyclopentyl cobalt dicarbonyl [181]. In other cases, a mixture of cyclotrimerization, chromene formation and linear polymerization occur. Consequently, the thermal stability of polymer is strongly dependent on the mode of polymerization The Claisen rearrangement and the subsequent polymerization are so exothermic (, 1.200 kJ/g for PN resin) that curing has to be done
466
Fig. 29. Isothermal time-conversion prole prediction for bispropargyl ether of bisphenolA (BPBA) at various temperatures. (B) experimental data at 245 8C [185] (Reprinted from Polymer by permission, q1999 Elsevier Science).
the B-staged material to the nal network is below 1%. The B-staged BER systems have excellent tack and drape and are easily processable. The isothermal stability of propargyl ether resins is comparable to that of acetylene terminated resins [187]. Final curing of propargyl resin is done at high temperature (typical case 208 8C/4 h). Post curing is carried out at 260 8C; Tg is about 300 8C, and post curing boosts it to 360 8C. This value is high when compared with other thermosets. BER thermosets only absorb 0.3 0.4% moisture. Typical tensile properties of BER resin are as follows: tensile strength 103 MPa, modulus 4.55 GPa and elongation 1.9%. Flexural strength and modulus are 105 MPa and 4.33 GPa, respectively. These are higher than values for other thermosets. 8.2. Structure property relation in propargyl phenolics Propargyl ether resins of cyclopentadiene phenol has been synthesized, but no property data are given [180]. The mechanical strength of the bispropargyl ether resin of diphenols are almost double those of their corresponding acetylene-terminated analogues [180], but with identical isothermal stability [187]. Propargyl etheried and glycidyl etherifed novolac treated with a siloxane and modied with amino silane, zinc stearate and carbon black provided molding compositions with good mechanical strength and moderately good thermal capability. The exural strength amounted to 173 MPa with a exural modulus of 12.5 GPa. About 35% strength retention was observed at 260 8C. The polymer possessed a Tg of 243 8C, excellent moisture resistance and good solder crack resistance [188]. The adhesive strength of phenol formaldehyde resin increased on modication with propargyl glycidyl ether. The adhesive strength increased to 45.8 kg/cm2, heat resistance by 50 8C, and Brinell hardness to 33 kg/mm2 [189]. Thermosetting resins with good dimensional stability and heat resistance are obtained by mixing propargyl-etheried resin with resole [190]. Resin compositions with good workability and curability for laminates, heat- and moisture resistances and low Dk are obtained using propargyl-etheried phenolic resin-based formulations [191]. A siloxane-modied, heat- and moisture-resistant phenolic resin composition for
under controlled conditions, with a slow phase. B-staging of the resin is possible at 185 8C. Processing of the B-staged resins helps avoid the otherwise excessive cure shrinkage (1012%). The shrinkage of
Scheme 36. Proposed mechanism for curing of BER and initiation of thermal degradation of poly(bischromenes).
467
sealing semiconductor devices has been obtained by blending propargyl etheried novolac with amineterminated polysiloxane [192]. Novel ester imide prepolymers terminated by 3(4-aminophenoxy)-propane-1-yne as a thermally curable group were synthesized [193]. The cured resins showed excellent mechanical and thermal properties, i.e. exural strength of 269 370 MPa, Tg of 225 269 8C, moisture absorption of 0.20 0.78%, and Dk of 3.0 3.2. Glass-cloth-reinforced composites from propargyl ether-terminated ester imide prepolymers demonstrated excellent mechanical, chemical, and electrical properties [194]. The storage stability of the varnish of the prepolymer was also good. The initial exural strength was well maintained even after 1000 h at 200, 220 and 240 8C. Glass-cloth-reinforced composites prepared from prepolymers of blends of propargylether-terminated ester imide and a BMI
demonstrated that the Tg of the composite is directly related to the weight ratio of BMI [195]. The composites demonstrated excellent initial mechanical properties. The chemical and electrical properties under severe long-ageing conditions were also good. Novel BZ monomers containing arylpropargyl ether have also been reported [196]. On curing, thermally stable polybenzoxazines resulted. One monomer is a monofunctional BZ, i.e. 4-propargyloxyphenyl-3,4dihydro-2H-1,3-benzoxazine (P-appe), and the other is a bifunctional BZ, bis(4-propargyloxyphenyl-3,4dihydro-2H-1,3-benzoxazinyl)isopropane (B-appe). The synthesis protocol and structures of these monomers and the resultant polymers are given in Scheme 37. The cure behavior of the P-appe and B-appe monomers and the properties of the resulting polymers were studied in comparison with
Scheme 37. Synthesis and curing of propargyl ether-functional benzoxazines [196]. (Reprinted from Macromolecules by permission, q2001 American Chemical Society).
468
Table 36 Cure characteristics and related kinetic parameters of novolac-propargyl ethers [197] (Reprinted from Polymer International by permission, q2001, Society of Chemical Industry) Polymer reference Extent of propargylation (mol%) DSC cure parameters DH Kinetic parameters
Ti (8C) PN 18 PN 45 PN 54 PN 82
a
Tm (8C) 243 245 249 249
Te (8C) 330 335 320 320
J/g 244 630 683 1086
kJ/mola 27.5 77.5 86.5 148.9
E (kJ/mol) 85.4 103.9 109.1 118.6
A 1026 (s21) 3100 2500 8.8 10.7
18 45 54 82
165 173 174 175
Ti ; cure onset temperature, Tm ; maximum, Te ; cure end temperature in DSC. Per repeat unit.
4-phenyl-3,4-dihydro-2H-1,3-benzoxazine (P-a) and bis(4-phenyl-3,4-dihydro-2H-1,3-benzoxazinyl)isopropane (B-a) as typical BZ monomers without propargyl groups. The DSC cure of both P-appe and B-appe showed a single exotherm corresponding to the ring-opening polymerization of oxazine ring and cross-linking of aryl propargyl ether group, at almost the same temperature range as for P-a and B-a. The Tg values of polybenzoxazines derived from propargyl-containing monomers, PP-appe and PB-appe, were higher by , 100 and 140 8C, respectively, than for typical polybenzoxazines without propargyl groups. The storage moduli of Polymers of P-appe and B-appe were maintained constant up to a higher temperature in comparison to polymers of P-a and B-a. In other words, propargylation led to enhanced thermal stability of these structurally modied polybenzoxazines. The T5% for poly(B-a) shot up from 342 to 362 8C for poly(B-appe) and the increase in corresponding char-yield was from 44 to 66%. 8.3. High molar-mass PN resins PN resins, bearing varying extent of propargyl ether groups were synthesized from high molecular weight novolac and propargyl bromide [197]. The cure was followed via DSC in the temperature range 165 330 8C. The activation parameters for cure determined by the integral method of Coats-Redfern are compiled in Table 36. The activation energy for curing the propargyl novolac was substantially higher than that for model bispropargyl ether compounds and increased marginally with the degree of functionalization.
The heat of curing increased proportional to the degree of substitution. These were cured in the temperature range 180 220 8C under isothermal condition. The cure prole, extrapolated from non-isothermal DSC kinetics studies was in league with the results from DMA studies. The cure completion was ascertained from the complete disappearance of the xC H group absorption at 3272 cm21 in FTIR. The mechanical properties of the silica laminate of the resins of varying propargyl-content revealed good consolidation of the interphase, evident from the initial gain in both interlaminar shear strength (ILSS) and exural strength with increase in the degree of propargylation. However, the benet of the better resin-reinforcement interaction was not retained on cross linking the resin further, whereon the composite failed by a combination of ber debonding and brittle
Table 37 Mechanical properties of UD composites and laminates of PN resins (glass reinforcement) [197] (Reprinted from Polymer International by permission, q2001, Society of Chemical Industry) Polymer reference* Mechanical properties of laminates SBSS of UD (MPa) composite (MPa) ILSS (MPa) Flexural Compressive strength strength (08) (MPa) (MPa) 35 37 51 34 20 22 23 20 18 38 169 220 167 143 136 562 248 258 262
PN-18 PN-45 PN-54 PN-82 PN-82/silica PN-82/carbon
469
fracture of the matrix. The properties of the composites are given in Table 37. The mechanical properties of the composites were not very good. Changing the reinforcement to carbon enhanced the properties, but were still lower than the industrial standards. This was attributed to the fact that the PN resins used possessed high molecular weight, powdery in nature, whose ber wetting capabilities might not be very good. 8.4. Thermal degradation behavior PN resins possess good thermal stability. The thermograms of the resins with different degree of propargylation along with that of cured resole are shown in Fig. 30. TGA showed apparently single step decomposition starting above 380 8C and ending at around 640 8C for the cured PN resins. The decomposition parameters obtained from TGA thermograms are compiled in Table 38 [198]. The thermal stability of the PN resins with respect to IDT Ti and char residue at high temperature is signicantly higher than that of conventional resole systems. Whereas resole starts to decompose below 300 8C, the decomposition is triggered only at 380 8C for the PN resins. This advantage in thermal stability must be a consequence
Table 38 Thermal decomposition characteristics of PN resins (TGA) [198] (Reprinted from Journal of Macrolecular Sciences Pure and Applied Chemistry by permission, q2003 Marcel Dekker) Polymer reference Resole PN-18 PN-45 PN-54 PN-82 TI (8C) Tm (8C) Te (8C) Char at 600 8C (%) 68 74.3 72.6 70.3 68.1
320 390 385 380 405
380 510 450 360 350
650 640 640 650 650
Fig. 30. Thermograms of propargyl novolac polymers of different propargyl-content in N2. Heating rate 10 8C/min. The number denoted the extent of propargylation on the novolac [198] (Reprinted from Journal of Macromolecular Science Pure and Applied Chemistry by permission, q2003 Marcel Dekker).
of the protection of the OH groups by etherication that reduces the susceptibility of the methylene protons for degradation. It was found that even minor degree of propargylation was conducive for boosting the Ti values by about 70 8C. Although decomposition is initiated only at higher temperature, the degradation is found to be quite rapid for all the systems. Despite the increased cross-link density with enhanced extent of propargylation, TGA manifested nearly identical Ti values. Contrary to expectation, the degradation becomes rapid and the char-yield decreased with further increase in propargyl-content and cross-link density. The rapidity is clearly manifested in the systematic drift of the Tm to lower temperature as the degree of propargylation increases (Table 38). This unexpected behavior can be ascribed to two reasons. As the propargyl-content increases, the cured polymer possesses more aliphatic groups. The enhanced cross linking achieved through the aliphatic groups may not be conducive for increasing the thermal stability, as these links are thermally fragile. Moreover, the PN polymers synthesized at different extent of propargyl etherication is likely to possess varying substitution pattern, as shown in Scheme 38. At low degree of substitution, the propargyl etherication should occur preferentially at the least steric hindered terminal phenol groups and the ortho para substituted ones (Structure A). Then, the priority of substitution is in the ortho ortho methylene substituted phenols (Structure B) and the least preference should be for the 2,4,6-tris methylene substituted phenyl molecules (Structure C, which acts as branching position on the novolac backbone). The thermal reactions of phenyl propargyl ether groups
470
Scheme 38. Likely substitution pattern in propargyl novolac polymers at different degree of propargylation [198] (Reprinted from Journal of Macromolecular Science, Pure and Applied Chemistry by permission, q2003 Marcel Dekker.
of different substitution pattern have been studied [199 201]. The same mechanism can be extended to propargyl novolac polymers. The type (A) propargyl ether can rearrange to the chromene prior to polymerization giving rise to comparatively thermally stable cyclic structure. Type B giving the cyclic ketone, and type C giving the polyene, are thermally fragile entities. The curing reactions of various propargyl groups are included in Scheme 35. The
cross-links generated by thermally fragile groups (by structures resulting from B and C type substitutions) undergo easy thermal degradation. Evidence for the formation of the ketone structure (from Type B structure) was obtained in the FTIR spectrum with a broad absorption around 1740 cm21. This could account for the rapid thermal degradation and lower char-yield for the high-propargylated PN systems. Thus, the thermal stability is found to be good only at
471
8.5. Propargyl ether resins based on oligomeric novolac PN resins based on low molar mass, oligomeric novolac (Mn , 300 600) provided tacky, owing resins (OPN resins) with viscosity in the range 2000 6000 mPa s [202]. The propargylation was limited to about 85% as this was shown to result in good thermal stability. A GPC analyses conrmed that the resin possess oligomers other than monomeric phenyl propargyl. The identical distribution pattern for both the precursor novolac and the propargyl ether indicated a uniform propargylation for all molar mass species. The GPC pattern for the precursor and the PN resin shown in Fig. 31 conrm this. The viscosity of the resin decreased signicantly on raising the temperature as shown in Fig. 32. The temperature coefcient of viscosity b was obtained as 10. These resins are suitable for solvent-free impregnation. The resin cures at 200 220 8C, evident from the DMA of the resin. The non-isothermal DMA spectrum (shown in Fig. 33) was used to evaluate the gel time and cure time. The resin properties are given in Table 39. The time for stagnation of storage modulus G0 or complex viscosity hp is indicative of the cure time, and this decreases with increase in temperature as shown in Fig. 34. The gel time is obtained from the cross point of G0 and the loss
Fig. 31. GPC pattern for ( ) novolac and () oligomeric propargyl novolac (OPN) resins [202].
medium cross-linking. It may be remarked that these addition curable PN re sins loose only , 2% mass on curing, whereas resole looses 22 26% mass at the initial stages of curing. In short, the overall char residue of PN resins is superior to that of resole when a comparison is done based on virgin resins.
Fig. 32. Variation of viscosity with temperature for oligomeric propargyl novolac polymer [202].
Fig. 33. Non-isothermal DMA of PN resin in air. Heating rate 5 8C/min. Parallel plate rheometry, controlled stress at 100 Pa. 4 Hz. [202].
472
Table 39 Typical thermal and physical properties of oligomeric PN resins [202] Sp gravity Extent of propargylation GPC molar mass Cure initiation Cure completion DH of curing h at 50 8C Temperature coefcient of hb 1.16 g/cc 85% Mn 600; Mp 2500; Mw =Mn 5 170 8C ( ex: DSC) 300 8C 1.2 kJ/g 3 Pa s 10
modulus G0 ; as typically shown for one case in Fig. 35. Since the cross-point is frequency-dependent, the gel points are only apparent. The gel time and cure times at different temperatures, determined by rheometry are given in Fig. 36. Both decrease with increase in temperature. The glass laminate showed improved mechanical performance. The resin has been successfully used for developing reaction-bonded SiC-based ceramic components [203]. 8.6. Propargyl novolac epoxy blend Partial propargylation of novolac permitted co-reaction of the remaining OH groups with an
Fig. 35. Determination of apparent gel time for oligomeric propargyl novolac at 170 8C by rheometry [202].
epoxy resin. Thus, partially propargylated oligomeric novolac resin with an extent of propargylation around 70% was used to formulate a dual cure thermoset when blended with a novolac epoxy resin [204]. The dual cure through phenol epoxy reaction and propargyl curing was evident both in DSC and DMA, as shown in Figs. 37 and 38, respectively. In DSC,
Fig. 34. Cure proles for propargyl novolac resin in air at different temperatures by parallel plate rheometry in controlled strain mode. [202].
Fig. 36. Dependence of gel time and cure time on temperature for oligomeric propargyl novolac resin [202].
473
Fig. 37. DSC of epoxy/propargyl novolac blends in presence of triphenyl phosphine. Heating rate 10 8C/min [204] (Reprinted from Polymer and Polymers Composites by permission, q2004 Rapra Technology).
the epoxy phenol cure peak occurs at , 135 8C and that due to propargyl cure at , 235 8C. The phenol epoxy reaction could be catalyzed by TPP, but this did not have any effect on the curing of propargyl ether groups. DMA showed more or less the same cure temperature regime, although the epoxy cure occurred at a slightly higher temperature, due to the absence of TPP. The DMA prole indicated the propargyl cure
Scheme 39. Dual cure sequences of partially propargylated oligomeric propargyl novolac (OPN)-epoxy blend [204]. (Reprinted from Polymers and Polymer Composites by permission, q2004 Rapra Technology).
Fig. 38. Non-isothermal DMA spectrum of epoxy/propargyl novolac blend in presence of triphenyl phosphine. Heating rate 5 8C/min, ( ) E00 ; () E0 [204] (Reprinted from Polymer and Polymers Composites by permission, q2004 Rapra Technology).
occurred in multi-steps. The cure sequences for the resin system are shown in Scheme 39. The isothermal DMA at 220 8C indicated that the propargyl curing requires about 2 h at this temperature for reasonable network build-up. This is in league with the observation for the pure PN resin (Fig. 34). Table 40 lists the glass laminate properties of the PN resin cured with different equivalent of EPN resin [204]. The mechanical properties are not signicantly dependent on composition. As a whole, the properties are better than those of the high molar mass PN polymers. Presence of epoxy reduces the gel time and makes the processing easier. The TGA of the blend (in Fig. 39) showed a decreasing thermal stability for the system on enhancing the epoxy-content. Addition of epoxy diminishes both the IDT Ti and the anaerobic char residue. The char residue at 750 8C is inversely proportional to the epoxy-content. DMA of the cured resin showed Tg . 300 8C for the PN systems. Tg decreased in the presence of epoxy. The adhesive characteristics of the PPN epoxy blend were also investigated.
474
Table 40 Glass laminate property of OPN (extent of propargylation 70%) and OPN-epoxy blend [204] (Reprinted from Polymers and Polymer Composites by permission, q2004 Rapra Technology) Polymer ref. Composition, (OH/EPN equivalent ratio 100:0 (OPN) 85:15 65:35 50:50 ILSS (MPa) Flexural strength (MPa) Compresive strength (MPa) Tg (8C)
PNEX-100 PNEX-8515 PNEX-6535 PNEX-5050
30 28 30 25
390 320 375 340
165 140 140 174
.350 .350 300 270
The variation of LSS with phenol epoxy ratio is shown in Fig. 40 for EPN and in Fig. 41 for DGEBA. The graphs also show the percentage retention of LSS at 100 8C. The adhesive properties of the PPN resin were signicantly enhanced by the reaction with epoxy. The optimum adhesive strength and retention of properties at high temperature were observed with a phenol epoxy equivalent ratio of 2:1 in both cases. A small proportion of epoxy boosted the adhesion signicantly. The strength was higher for DGEBA due to its better exibility and lower cross-link density in this case, in contrast to the rigid EPN system. However, the high temperature retention was nearly identical for these systems.
9. Phenolic resins with terminal acetylene groups Addition curable phenolic resins, bearing terminal ethynyl groups, anchored to a benzene ring through a phenyl azo linkage (ethynyl phenyl azo novolac, EPAN), were realized by a novel and simple synthesis strategy involving the coupling reaction between novolac and 3-ethynyl phenyl diazonium sulfate [205]. The synthesis is shown in Scheme 40. The diazo coupling was limited to the para position of the novolac and occurred to a maximum of 50 mol%. The molar mass, determined from GPC showed a downward drift with increase in degree of functionalization.
Fig. 39. TGA of propargyl novolac epoxy blend of varying composition(number denotes propargylepoxy ratio) in N2. () PNEX-100, ( ) PNEX-8515, ( ) PNEX-6535, ( ) PNEX5050, Heating rate 10 8C/min.[204] (Reprinted from Polymers and Polymer Composites by permission, q2004 Rapra Technology).
Fig. 40. Variation of lap shear strength and its retention at 100 8C with phenol epoxy ratio for partially propargylated novolac (PPN)/epoxy novolac system (EPN). [204] (Reprinted from Polymers and Polymer Composites by permission, q2004 Rapra Technology).
475
9.1. Curing of EPAN resins These resins showed a broad cure exotherm in DSC in the range 140 240 8C due to the curing of acetylene functions occurring by various reactions. Like other acetylene-polymers these are also hardened by a series of reactions, including trimerization [206], Glaser coupling [207], Strauss coupling [208], Diels-Alder reaction with participation of products of Glaser coupling and Strauss coupling, Diels-Alder coupling with the aromatic backbone, free radical polymerization with the formation of linear and branched products [209], etc.. The various mechanisms are depicted in Scheme 41. Spectral and GPC studies with model compound (3-ethnyl phenyl azo phenol, EPAP) gave evidence for Glaser coupling, trimerization and linear addition reactions. Fig. 42 shows the high resolution GPC proles of the soluble part of the polymerization product of EPAP, isolated in methanol and DMF. Unreacted EPAP appeared at an elution time of 23.5 min. The component at 22 min is the dimer formed by Glaser and Strauss coupling. The one at 20.1 min with approximately thrice the molar mass of the monomer is attributed to the cyclic trimer. GPC also showed the presence of a minor amount of higher molar mass species in this fraction. The methanol insoluble part (soluble in DMF) showed a multimodal distribution and indicated the presence of EPAP. The broad peak centered at 20 min encompasses the low molar mass oligomers formed by various mechanisms. The high molar mass products appeared as wellseparated peaks at 13, 11 and 10.5 min. This part, in all probability, contained the linearly polymerized polyenes and branched polymers anticipated with the proposed cure mechanism. 9.2. Thermal characteristics of EPAN resins The polymers exhibited enhanced thermal stability and anaerobic char in comparison to resole. The thermal stability and anaerobic char-yield of the polymers increased with enhanced cross-link density. Against a char residue of 60 62% in resole, EPAP gives 72 75% char at 700 8C. If the mass-loss during curing is also considered, the net gain in char is about 70% more than in resole. Isothermal pyrolysis
Fig. 41. Variation of LSS and LSS retention at 100 8C with phenolepoxy ratio for partially propargylated novolac (PPN)/ bisphenolA diglycidyl ether system (DGEBA). [204] (Reprinted from Polymers and Polymer Composites by permission, q2004 Rapra Technology).
This was attributed to the decreased hydrodynamic volume of the polymer resulting from its comb-like structure. This was conrmed form the trend in intrinsic viscosity of the resins as a function of the extent of diazo coupling. The molecular characteristics of polymers with varying extent of functionalization are given in Table 41.
Scheme 40. Synthesis of ethynyl phenyl azo phenolic (EPAN) resin [205] (Reprinted from Polymer by permission, q2002 Elsevier Science).
476
Table 41 Molecular characteristics of EPAN systems [205] (Reprinted from Polymer by permission, q2002 Elsevier Science) Polymer ref. Extent of azo coupling (mol%) h in THF, 30 8C (dl g21) Molecular weight by GPC, (g mol21) Mn Novolac EPAN-1 EPAN-2 EPAN-3 EPAN-4 0 24 35.8 43 49.7 0.155 0.134 0.085 0.107 0.074 700 520 430 350 330 Mw 1970 1570 1460 1240 1180 Mp 1840 2030 1950 1330 1110 108.5 69.68 36.55 37.45 24.42 h Mn (dl mol21)
at 700 900 8C showed that complete pyrolysis of the EPAN system is not achievable under these conditions. The TGA of resins with different acetylenecontent are shown in Fig. 43. The evolution in elemental composition under different pyrolysis conditions implied that the pyrolysis occurs mainly by loss of nitrogen and hydrocarbon. The higher proportion of char shows
the prospects for potential application of this resin in ablative compositions and in carbon/carbon composites. Non-isothermal kinetic analysis of the degradation reaction conrmed that degradation apparently occurred in a single kinetic step, with a decomposition rate almost independent of cross-link density [210]. These polymers yielded a considerably higher proportion of char, whose XRD analysis
Scheme 41. Various cure possibilities for acetylene groups (uncatalysed) [205] (Reprinted from Polymer by permission, q2002 Elsevier Science).
477
conrmed the presence of partial crystalline character, unlike the case for a conventional phenolic resin.
10. Phenolic resins with phenyl ethynyl groups Replacement of terminal acetylene groups by phenyl ethynyl function gives scope for improving further the thermal stability of phenolic networks due to the higher aromatic-content of the cross links. Phenyl ethynyl groups have, of late, received a great deal of attention as a means of thermally chain extending and cross-linking polymers [211,212]. On thermal curing, they provide a three-dimensional network exhibiting an excellent combination of properties including high glass transition temperature, good thermal stability, moisture- and solvent resistance, good toughness and mechanical properties.
Fig. 42. GPC traces of (-): ethynyl phenyl azo phenol polymer, (--): Methanol soluble fraction, (): methanol insoluble fraction in DMF, UV (280 nm) detection [205] (Reprinted from Polymer by permission, q2002 Elsevier Science).
10.1. Phenyl ethynyl functional addition-curable phenolic resins Phenyl ethynyl functional phenol formaldehyde (novolac-type, PEPFN) addition curable resins were synthesized by reacting a mixture of phenol and 3-(phenylethynyl)phenol (PEP) with formaldehyde in
Fig. 43. TGA thermograms of cured ethynyl phenyl azonovolac resins in N2. Heating rate: 10 8C/min. (): EPAN 1, (- - -): EPAN 2, ( ): EPAN 3, (---): EPAN 4, (----): Resole [205] (Reprinted from Polymer by permission, q2002 Elsevier Science).
Fig. 44. Monomer conversion with time for the polymerisation reaction of phenyl ethynyl phenol and phenol with formaldehyde [213] (Reprinted from Journal of Applied Polymer Science by permission, q2001 John Wiley and Sons).
478
Table 42 Composition and molecular weight characteristics of the PEPF resins (conversion: 7480%) [213] (Reprinted from Journal of Applied Polymer Science by permission, q2003 John Wiley and Sons) Polymer ref. PEP in PEP in Molecular weight by GPC feed copolymer (wt%) (wt%) Mn Mw Mp Mw =Mn DPn 24 49 73.8 100 780 820 620 650 3220 1600 4.1 2720 1400 3.3 1510 860 2.5 1270 960 1.9 6.5 5.9 4.4 3.2
in Fig. 44. The polymer was formed in about 74% yield after 10 h. Relatively narrow molar-mass distributed polymers were obtained in good yield. The copolymer composition nearly matched the feed composition. The presence of PEP led to reduced molar-mass and narrow distribution of the copolymers. The polymer properties are given in Table 42. 10.1.1. Cure and thermal characteristics of PEPFN resins The resin underwent thermal curing at around 250 275 8C, and the cure optimization was done by isothermal DMA at 275 8C. The cure time of 1 h is signicantly lower than the cure time for conventional phenyl ethynyl functional polymers. This points to an altered cure mechanism in these resins. The cure mechanism is proposed as a combination of acetylene addition [214] and by addition of phenol to the triple bond as implied in a model study [215]. Based on these, the cure mechanism depicted in Scheme 42 was proposed. The cure chemistry is not well understood. In many cases, the polyene formation by linear addition and cross linking is a widely accepted
PEPF 25 25 PEPF 50 50 PEPF 75 75 PEPF100 100
the presence of an acid catalyst [213]. The polymerization reaction was performed at 75 8C, and the reaction time was optimized by monitoring the reaction mixture by GPC at different time intervals. The molecular weight increased and the distribution became broader as the reaction progressed. The relative concentrations of the polymer and the starting phenol reactants were determined by measuring the area under the GPC curves corresponding to each component. The product evolution with time is shown
Scheme 42. Synthesis and likely cure mechanism for phenolphenyl ethynyl phenol [213] (Reprinted from Journal of Applied Polymer Science by permission, q2001 John Wiley and Sons).
479
mechanism for the curing of phenyl ethynyl-containing polymers [216]. The thermal stability and anaerobic char residue of the cured resins increased proportionate to the phenylethynyl-content, and these properties were improved over those of resol resin. These addition cure phenolics provided an overall increase in char of ` about 70% vis-a-vis resol resin when compared on the basis of the uncured resins. The thermograms of resins with varying degree of phenyl ethynyl functionalization are given in Fig. 45. The variation of IDT and anaerobic char with the phenyl ethynyl-content is shown in Fig. 46. 10.2. Condensation addition cure phenyl ethynyl phenolic resins The PEPFN resins have the disadvantage of the need for a very high cure temperature. This causes a processing difculty in that the resin tend to bleed away during molding at high temperatures. This can be avoided by conferring a partial condensation character to the resin, by synthesizing phenyl ethynyl functional resoles (PEPFR). The curing of resole at lower temperature facilitates the early gelation of the resin. Thus, phenolic resins bearing methylol and phenyl ethynyl functions and curing by a dual mechanism of both condensation and addition were synthesized by the reaction of 3-(phenyl ethynyl) phenol (PEP) with formaldehyde under alkaline conditions [217]. The synthesis and curing are shown in Scheme 43. Resins with varying relative concentration of the two functional groups were synthesized and characterized. GPC and NMR analyses conrmed that the resin contained a mixture of multi-methylol substituted phenols. It also contained some proportion of partially chain extended molecules. A typical high resolution GPC prole (of resoles derived from PEP) showing the product distribution is shown in Fig. 47. The molecular characteristics and the cure characteristics of the resoles are given in Tables 43 and 44, respectively. The methylol condensation occurred at practically the same temperature range as for conventional phenolic resins (, 130 160 8C). The ethynyl cure occurs at a lower temperature than the model compound. A two-stage cure was conrmed in both DSC and DMA analyses. The DMA spectrum is
Fig. 45. TGA traces of cured phenolphenyl ethynylphenol formaldeheyde (PEPFN) polymers in N2. Heating rate 10 8C/min [213] (Reprinted from Journal of Applied Polymer Science by permission, q2001 John Wiley and Sons).
shown in Fig. 48. The low temperature cure due to methylol condensation was conducive to early gelation of the system, at around 100 150 8C. The ultimate curing through addition reaction of phenyl
Fig. 46. Variation of Ti and char-yield (at 700 8C) for phenol phenyl ethynylphenolformaldeheyde polymers with phenyl ethynyl-content.
480
Scheme 43. Synthesis and curing of phenolphenyl ethynylphenolformaldeheyde (PEPFR) resin (PEPFR, resole type) [217] (Reprinted from Journal of Applied Polymer Science by permission, q2002 John Wiley and Sons).
ethynyl group, however, required heating at 275 8C for 2 h. The cured resins exhibited better thermal stability and anaerobic char residue in comparison to a conventional resole. The thermal stability and charyielding property showed a diminishing trend with enhanced methylol substitution. Resin with an F/P ratio less than unity offered excellent thermal stability, and anaerobic char-yield signicantly higher than that of the corresponding novolac (PEPFN). Methylene groups favored the initial degradation, whereas the higher temperature carbonization process was independent of the network structure. 11. Comparative thermal property of PMF, PN, EPAN and PEPFN resins On comparing the thermal stability of the additioncure phenolic resins belonging to PMF, PN, EPAN and PEPFN class as a function of composition, it was observed that in many cases, thermal stability and char-yield increase with increased cross linking via enhanced functionalization. Exceptions were noted in the case of the blend of PMF with allyl novolac and for propargylated novolac (PN resins). In these two cases, the thermal stability decreased with crosslinking due to the increase in the aliphatic-content in the cured polymer. The PMF resins exhibited least thermal stability and the EPAN systems were the most
thermally stable. The maximum char-yield was obtained for EPAN and PEPFR (with low methylol) concentration. The comparative thermograms can be found in Fig. 49 for resins with maximum thermal stability in each series [218].
12. Phenolic triazine resin (P T resins) Phenolic triazine (P T) precursor resin is a reaction product of novolac resin and cyanogen
Fig. 47. High resolution GPC of phenyl ethynylphenolformaldeheyde resole (PEPFR) resin.
481
Table 43 Characteristics of PEPFR resins [217] (Reprinted from Journal of Applied Polymer Science by permission, q2002, John Wiley and Sons) Polymer reference Formaldehyde/ phenol ratio (F/P) Relative ratio CH2 O /CH2from NMR Different components (%) in PEPFR resin from GPC
Monomer
Mono and dimethylol product 49 50.3 54.7
Dimer and higher oligomers
PEPFR- 1 PEPFR- 1.5 PEPFR -2
1 1.5 2
2.7 3.5 5
14.6 18.7 14.9
36.4 31 30.4
Table 44 Cure Characteristics of PEPFR resins from DSC. All temperatures are in 8C [217] (Reprinted from Journal of Applied Polymer Science by permission, q2002, John Wiley and Sons) Polymer reference Formaldehyde/ phenol ratio Methylol condensation DH (J/g) PEPFR-1 PEPFR-1.5 PEPFR-2 PEP 1 1.5 2 0 91.3 100.9 142.3 Ti 170 170 160 Tm 196 198 202 Te 230 230 220 Ethynyl cure Ti 260 270 255 300 Tm 300 320 280 320 Te 320 340 325 350
halide. P T network is formed by the thermal cyclotrimerization of the cyanate ester of novolac as shown in Scheme 44 [219,220]. It is an ideal matrix system for composites, because it combines the processibility convenience of epoxies and the thermal capabilities of polyimides and re resistance of phenolics. The absence of volatile by-products during cure renders them attractive matrices for voidfree moldings and composites. 12.1. Features of P T resins The key features of P T resins are Low melt viscosity, epoxy like handling, resinous consistency Long gel time and angle of ow, long-term thermal stability High solubility in low boiling solvents Feasibility of mixing: dry, wet and impregnation, ease of formulation Wide processing latitude, RTM processable Tg up to 399 8C depending on post cure conditions
Ultimate elongation and mechanical properties equal to high performance polyimide systems Very low toxicity Low Dk and low moisture absorption and thermal expansion Better thermo-oxidative stability than phenolics, ame resistant and low smoke generation. Stability comparable to polyimides
Fig. 48. DMA of phenyl ethynylphenol formaldeheyde resole resin showing two-stage curing [217]. (Reprinted from Journal of Applied Polymer Science by permission, q2002 John Wiley and Sons).
482
Fig. 49. Comparative thermograms of various addition-curable phenolic resin in N2, heating rate 10 8C/min. Phenol phenyl ethynylphenol formaldeheyde novolac (PEPFN), phenyl ethynylphenolformaldeheyde resole (PEPFR); phenolmaleimidophenolformaldehyde (PMF); propargyl novolac (PN); Ethynyl phenyl azo novolac (EPAN) and resole [218] (Reprinted from Polymer Degradation and Stabilisation by permission, q2001 Elsevier Science).
P T resin offers considerable processing exibility since their consistency ranges from low viscous liquids to semi solids, with gel temperatures that can be tuned by catalysis using a host of materials. However, the ultimate cure temperature has to be high (. 300 8) to achieve optimum cure and higher Tg (above 300 8C). In fact Tg is a function of the ultimate cure temperature as shown in Fig. 50. Post curing at temperatures above 300 8C ensures Tg of about 400 8C [221]. PT resins
possess better thermo-oxidative stability and charyield than conventional phenolics, because they are mostly cross-linked by triazine groups. The proximity of the hydroxyl groups in phenolic resin renders these methylene bridges thermo-oxidatively fragile, and the degradation process is accelerated by the number of dihydroxy phenyl methylene groups. The degradation process of phenolic resins has been discussed in length [222]. The widely accepted mechanism for oxidative degradation is as shown in Scheme 45. The hydroxy phenyl methylene group is the triggering point. PT resins, on the other hand, are cross-linked mostly by triazine phenyl ether linkages, which confer both thermo-oxidative stability and toughness to the system. The evidence for better thermo-oxidative stability is obtained from the thermal behavior of the systems in both air and inert atmosphere. The initial decomposition pattern in air and in inert atmosphere essentially superimpose, pointing to a non-oxidative mechanism of degradation for PT systems (see the thermograms in Fig. 51). The decomposition starts at around 420 8C and the char-yield is of the order of 65 70%. The char retains about 5% nitrogen. This char-yielding quality implies better prospects for application of this type of resin for thermo-structural uses in aerospace, in place of conventional phenolics. In fact, laser ablation studies on a series of ablatives including PT resin have conrmed their potentiality for such applications. It was found that the ablation energy was highest for the cyanate polymers, on exclusion of phthalocyanines, among the polymers tested [223]. Some ablative formulations for rocket nozzle applications contain P T resins as one of the components [224].
Scheme 44. General synthesis route for novolac cyanate and curing to phenolictriazine.
483
Fig. 50. Dependence of Tg on cure temperature for phenolictriazine (P T) resin [221] (Reprinted from Technical Brochure by permission, q1996 Lonza Ltd).
PT resins possess the general characteristics of cyanate esters with added thermal stability. The relative strain capabilities and thermal performances of some common thermosets are projected in Fig. 52. The moderate strain capability and high temperature capability conveys the comparative advantage of PT ` system vis-a-vis the other thermosets. The low moisture absorption, low dielectric properties and better hygrothermal performance project their potential for applications in many critical aerospace structures. The low moisture absorption and consequent reduced dimensional changes render it the matrix of choice for composites for optical support structures for satellite applications. Fig. 53 compares the relative hygrothermal properties of common thermosets, among which, the PT systems are seen to occupy a comfortable position.
Scheme 45. Thermal degradation mechanism of phenolformaldehyde resins.
484
Fig. 53. Comparative hygrothermal performances of common thermosets [238] (Reprinted from Advances in Polymer Science by permission, q2001 Springer Verlag). Fig. 51. Thermograms of cured phenolictriazine (PT-30) resin in air and N2. Heating rate 10 8C/min [202].
12.2. Properties of P T systems P T resin is commercially available under the trade name Primaset P-T-15, P-T-30, P-T-60 and P-T-90, which essentially differ in their molar masses [221]. The characteristics of the resin are listed in Table 45. The gel time can be tuned by catalyst concentration. The generally recommended catalysts are zinc
octoate/nonyl phenol, cobalt naphthenate, copper salts etc. The neat resin properties of cured PT systems are given in Table 46. Although PT possesses a very high Tg ; its neat resin mechanical properties are inferior to those of other common thermosets. On the other hand, the PT composites exhibit excellent mechanical properties and thermo-mechanical prole, as is evident from the typical data displayed in Table 47. Although the properties diminish at high temperature,
Table 45 Characteristics of different PT resins [221] (Compiled from Technical Brochure by permission, q1996 Lonza Ltd) Property Consistency Sp. gravity (g/cc) Viscosity (mPa s), 93 8C Viscosity (mPa s), 121 8C Gel-time (min, 200 8C, uncatalysed) Gel-time (min, catalyzed) P-T-15 Viscous liquid P-T-30 Viscous liquid 1.25 200 P-T-60 Semisolid 1.28 25000 P-T-90 Powder 1.24
1.245
80
1500
.20 30
20
Fig. 52. Comparative temperature- and strain capabilities of common thermosets [238] (Reprinted from Advances in Polymer Science by permission, q2001 Springer Verlag).
.30 (200 8C)
,5 (177 8C)
,5 (177 8C)
C.P. Reghunadhan Nair / Prog. Polym. Sci. 29 (2004) 401498 Table 46 Typical neat resin properties of PT resin [221] (Compiled from Technical Brochure by permission, q1996 Lonza Ltd) Property Tg (8C) Dk (1 MHz) Dissipation factor Ti (from TGA, 8C) Char-yield (%) CTE (8C21, 40 315 8C) Tensile strength (MPa) Tensile modulus (GPa) Elongation (%) Flexural strength (MPa) Flexural modulus (GPa) Compressive strength (MPa) Value Up to 400 3.1 0.007 410450 6570 2.8 1025 41.4 4.07 2 110 4.7 317
485
Table 49 Comparative mechanical and thermal properties of PT and phenolic resins [225] (Reprinted from 30th Int SAMPE Tech Conf by permission, q1998 Society for the Advancement of Materials and Process Engineering) Property Ti (TGA) 8C Tg ; 8C (DMA) Char-yield, % at 1100 8C Ultimate elongation (%) Flexural strength (MPa) Flexural modulus (MPa) Compressive strength (MPa) CTE, 1025/8C Rockwell hardness (M scale) PT resin 450 400 6668 2 95.2 4626 306 22 125 PF resin (hexa-cured) 350 121 55 0.3 47.6 2517 102 65 93
Table 47 Typical composite properties of PT resin [221] (Compiled from Technical Brochure by permission, q1996 Lonza Ltd) Property E-Glass laminate Carbon UD composite 24 8C SBSS (MPa) Flexural strength (MPa) Flexural modulus (GPa) 53.8 558 34.8 184 1480 175 260 8C 55.8 986 170 316 8C 50.3 882 160
the values are still in the acceptable limits for many structural applications. Their ageing characteristics are also excellent (refer to data in Table 48). Das has compared the thermal and mechanical properties of
Table 48 Thermal ageing data on PT/carbon bre UD composite [221] (Compiled from Technical Brochure by permission, q1996 Lonza Ltd) Temperature (8C) Ageing time (h) Flexural strength (MPa) 1650 1830 1520 1050 1410 1750 1650 Flexural modulus (GPa) 124 132 123 137 128 120 117 SBSS (MPa)
phenolic and P T resins [225]. Almost all of the data in Table 49 speak about the superiority of the latter system for both mechanical and thermal properties. The high char-yielding property is conducive to better ame resistance in actual re situations. The LOI comparison given in Fig. 54 shows its superiority even to phenolics. The P T resin systems have been successfully employed in lament winding of cylindrical structures such as pressure bottles, which retain 83% of their room temperature properties at 288 8C [219,226]. The exural strength of PT/T-300 rings is 339 MPa, which only drops to 284 MPa at 288 8C. The apparent modulus drops from 98.6 to 93.8 GPa. The mechanical
288
316
0 100 200 500 1000 100 200
151 119 112 106 86 93.8 94.5
Fig. 54. Comparative limiting oxygen index values of common thermosets [225] (Reprinted 30th Int SAMPE Tech Conf by permission by permission, q1998 from Society for the Advancement of Materials and Process Engineering).
486
Table 50 Comparative mechanical properties of P T-carbon bre composites (ber: 5864 vol%) [226] Property PT 24 8C Flexural strength (Celion 6000) (MPa) Flexural modulus (GPa) SBSS (CelionT-650/42) (MPa) SBSS (CelionT-650/42, polyimide sized) (MPa) 2482 103107 145165 69 330 8C 1379 110 145152 50 PMR-15 24 8C 1930 103117 103 315 8C 965 103 50
properties of PT composites are comparable to those of PMR-based composites, especially at high temperature (refer to Table 50). Considering their ease of processibility, PT has an edge over the PMR systems. Their carbon composites have been experimented as actuators in turbine engines, with signicant advantage over other high performance systems [227]. A NASA report compared the mechanical properties of composite and char residues of 27 modied phenolic resins including PT resins, to those of conventional
phenolic resin [228]. Cyanate, epoxy, allyl, (meth)acrylate and ethynyl derivatives of phenolic oligomers were reviewed. Novolac cyanate along with propargyl novolac resins provided an anaerobic char-yield of 58% at 800 8C, whereas a modied epoxy novolac provided 59% char. A phosphazene derivative was effective in enhancing the char-yield. The novolac cyanate, epoxy novolac and methacrylate epoxy novolac were investigated for their composites. The methacrylate epoxy novolac/graphite epoxy
Scheme 46. Synthesis of cyanate ester and phenolictriazine resin from cardanol novolac [231].
487
provided SBSS of 93.3 MPa at ambient conditions whereas the novolac cyanate provided a value of 74 MPa. Novolac cyanate- and epoxy novolac-based composites showed good property retention after ageing at 204 8C for 12 weeks. A recent evaluation of the composite materials of three high performance matrices as a low-cost substitute for titanium components for the control surfaces on hypersonic aircraft showed the superiority of the PT systems. The tensile, shear and compressive strength of the three materials were tested at high temperature. The matrix materials and test temperatures included (a) Polyetheramide (PEAR), 205 260 8C (b) BMI, 260 427 8C and (c) Phenolic Triazine (PT), 370 538 8C. While strength values for all materials decreased substantially (25 100%) with increasing temperature, the distinct advantage of PT systems were evidenced in the evaluation [229]. The Lonza Group has claimed some resin formulations based on P-T systems for specic applications [230]. In a typical case, a patent claims storage-stable prepolymer compositions that are rapidly curable at elevated temperatures. This comprises of a mixture of prepolymerized and nonprepolymerized novolac cyanates of specied structure, useful as resin components for the manufacture of printed circuit boards or in binders for abrasive products. The mixture has a refractive index of 1.58, and contains highly dispersible silicon dioxides and/or particulate or brous llers. The compositions are solid at ambient temperature and can be ground to powders that will ow. 12.3. Structurally modied P T resins Several structural modications of novolac cyanate have been attempted. Thus, introduction of a exible pentadecenyl group in a P T network decreased the shelf life of the precursor and the thermal stability of the cured resin [231]. The resin was synthesized by cyanation of cardanol novolac or its mixed novolac with phenol. The synthesis of the cyanate ester and the resultant PT resin are shown in Scheme 46. The cross linked cyanate ester of homo- and copolymers of 4-hydroxy phenyl maleimide (HPM) were synthesized and thermally cured to imido phenolictriazine [232]. The synthesis of a typical copolymer of HPM, its cyanate ester and the resultant imido phenolic triazine are depicted in Scheme 47.
However, the polymer showed inferior initial decomposition properties, although the char-yield was signicantly higher. The cyanate ester of PMF resins was also been synthesized [233]. The imidemodied novolac (PMF) is described in Section 6. The cyanate ester underwent a two-stage cure, implying independent cure of both the cyanate and maleimide groups. However, the cured imido phenolic triazine exhibited poorer thermal stability and anaerobic char residue, attributed to the interference of the rigid imide groups in the char forming reactions of the triazine groups at higher temperature. The structures of the cyanate ester and the imido phenolic triazines are shown in Scheme 48. The scheme has neglected the presence of a very minor concentration of methylol groups present in the parent phenolic resin (PMF). A patent claims preparation of a low molar mass novolac cyanate ester prepolymer (Mn 310 g/mol) from the corresponding novolac resin. The prepolymers are claimed useful as coatings, adhesives and as matrix in copper clad laminates for printed circuit boards [234]. There are few reports on cyanate esters of other polyhydric phenols. Different grades of poly(4-cyanato styrene) (PCS, normal, polymer and novolac grades) and copolymers of 4-cyanato styrene with butadiene (PCS-BD) or MMA (PCS-MMA) as comonomers have been prepared by Gilman et al. [235]. Flammability tests, performed using micro scale combustion calorimeter, showed signicant differences in the ammability of the cured polymers. The ammability decreased with increasing branching of the cyanatophenyl styrene. The best results were obtained for novolac grade polycyanatophenyl styrene. The structures of the various polymers are shown in Scheme 49. Copolymer PCS-BD showed properties similar to poly(cyanato styrene), probably through cross linking of the unsaturated monomer at high temperature. The PCS-MMA copolymer showed the least ame resistance. On a comparative scale, the PT resins exhibited the best ame resistance. The thermal properties of these polymers were not discussed. In a related work, copolymers of styrene with 4-vinyl phenyl cyanate or 2,6-dimethyl-4-vinyl phenyl cyanate were prepared via free radical polymerization [236]. The copolymers were sensitive to UV light and cross-linked on irradiation with 254 nm UV radiation. Interestingly, the cyanate groups in the latter copolymer underwent rearrangement
488
Scheme 47. Cyanate ester of copolymer of hydroxy phenyl maleimide (HPM) and curing to imidophenolic triazine [232] (Reprinted from European Polym Journal by permission, q2000 Elsevier Science).
Scheme 48. Imidophenolictriazine derived from phenolmaleimidophenolformaldehyde resin [233]. (Reprinted from European Polym Journal by permission, q2001 Elsevier Science).
489
Scheme 49. Structures of various grades of cyanato phenyl styrene polymers [235] (Reprinted from 42nd Int SAMPE Symp by permission, q1997 Society for the Advancement of Materials and Process Engineering).
to the isocyanate during irradiation whereas, both the copolymers yielded cyanurate networks on thermal curing. Nano composites of PT and clay have also been reported [237]. 12.4. P T/epoxy blends For many applications, epoxy resins require improvement in their properties. Their main drawbacks in adhesive, coating, PCB and other industrial applications include, high moisture absorption, high Dk , poor re resistance, high smoke evolution, low Tg ; etc. Modication by way of a co-reaction with PT resin improves Tg ; hot-wet performances, decreases Dk , and moisture absorption and improves re resistance. Although many pathways have been proposed for cyanateepoxy co-reaction [238], the most accepted mechanism involves formation of oxazoline groups in the network as shown in Scheme 50. The key features and advantages of P-T/epoxy blends over the epoxy resin systems are [221]: Cost competitive Enhanced modulus, compressive strength and hardness
Improved electrical properties, low moisture absorption Lower cure shrinkage Desirable re, smoke and toxicity properties Enhanced Tg over epoxies (180 300 8C) No amine curative needed Stable materials for RTM hot-melt, and solution prepregs
Scheme 50. General co-reaction between cyanate ester and epoxy group.
490
12.5. Thermal degradation of P T resins The thermal degradation phenolic triazine has been investigated, along with that for eight other cyanate esters [239]. The evolved gases were analyzed by FTIR and GC/MS. A three-step degradation was concluded. The steps are (1): random scission and cross linking of the hydrocarbon backbone between 400 and 450 8C; (2) breakdown of the triazine ring between 500 and 750 8C, with liberation of low molecular weight volatile compounds and the formation of a primary residue; and (3) decomposition of the primary residue between 500 and 750 8C, with the elimination of alkenes and hydrogen, leaving a secondary carbonaceous char containing residual oxygen and nitrogen. Substituted benzene and phenols were identied in the decomposition products. A strong peak in the gas chromatogram at m=z 44 was attributed to a mixture of CO2 and HOCN. In PT resin, this amounted to 38.52%. The benzene derivative and phenol derivatives were 8.7 and 39.8%, respectively. The rest 10.46% could be due to products such as aryl cyanates, aryl cyanates, amines, etc. 12.6. Applications of P T resins The major areas where PT systems are preferred are: Aero-space composite structures Low CME satellite structures and optical support components Cylindrical structures and pressurized bottles Actuators in turbine engines Thermo-structural applications in nozzles Radoms and high signal speed printed circuit boards
13. Outlook The foregoing discussion has presented a consolidated view of the recent developments in non-conventional, addition curable phenolic resins. Phenolic resin still commands considerable research and industrial interest. Innovative research is focused on means to address the shortcoming of these systems in terms of processibility and oxidative
resistance. The introduction of addition-cure phenolics is a partial answer to these problems. The allylphenol BMI system is suited for void-free composite systems for structural applications. In this case, the advantages in mechanical performances are usually achieved at the cost of the thermal capabilities. Although the absolute adhesive strength is not high, their high temperature retention is good; rendering them suited for high temperature applications. Phenol-epoxy systems are excellent for high strength structural and adhesive applications, but their low Tg limits the application even at moderately high temperatures. However, their amenability for structural modication permits designing systems with tailored properties. Polybenzoxazines, combining several salient features required of a high performance matrix, possess good prospects for application in several engineering areas. Their exibility for molecular design, amenability for blending and compounding are added advantages. Poly amide ether resins derived from bisoxazoline phenolics also claim similar design exibility and performance proles, but surprisingly, they are yet to dominate the market. Some of the resin systems described show good prospects for immediate use in composites for aerospace structural and thermo-structural applications. P T resin ranks top among them, with ease of processibility, excellent thermo-oxidative stability and thermo-mechanical prole. With good mechanical performance, and high temperature capability surpassing even the PMR resins, they appear to offer an immediate solution for many challenging problems in aerospace composite structural engineering. Although their neat resin properties are not commendable, composites fabricated with them are very strong and ame-and high temperature resistant. However, the high cure temperature of P T systems is an impeding factor. The comparative property of various common thermosets in Table 13 is suggestive of the relative merits of each system. The structural modications of novolacs by incorporation of groups such as ethynyl, phenyl ethynyl, phenyl maleimide, propargyl etc., have been successful in conferring addition curable nature to phenolics, resulted in enhanced thermal stability and char-yield. Pending data on mechanical properties, the industrial utilities of these systems are
491
yet to be judged. The prohibitive cost and the high cure temperature of some of these new systems may impede their easy acceptability in industrial applications.
Acknowledgements At many phases of the work described here, the author has associated with his colleagues, R.L. Bindu, C. Gouri and Dona Mathew. The encouragement and support received from V.C. Joseph, R. Ramaswamy, K.N Ninan and K.S. Sastri are thankfully acknowledged. Permissions granted by John Wiley and Sons, Elsevier Sciences, Springer Verlag, M/s. Lonza Ltd, SAMPE, SAGE Publications, Kluwer Academics, Brill Academic Publishers, Rapra Technology and American Chemical Society for reproduction of data from their publications are gratefully acknowledged.
References
[1] Kopf PW, Little D. Phenolic Resins. In: Grayson M, editor. Kirk-Othmer, 3rd Edition. Encyclopaedia of Chemical Technology, vol. 18. New York: Wiley; 1991. p. 603. Kopf PW, Little AD. In: Mark HF, Bikales NM, Overberger CG, Menges G,, editors, 2nd Ed. Encyclopaedia of Polymer Science and Engineering, vol. 11. New York: Wiley; 1988. p. 4594. [2] Gardziella A, Pilato LA, Knop A. Phenolic Resins, Chemistry, Applications, Standardization, Safety and Ecology, 2nd edition. Heidelberg: Springer; 2000. [3] Knop A, Pilato LA. Phenolic Resins: Chemistry Applications and PerformanceFuture Directions. Heidelberg: Springer; 1985. [4] Phenli UA. In: Salamone JC, editor. Phenolic Resins: Polymeric Materials Encyclopaedia, vol. 7. Florida: CRC Press; 1996. p. 5305. [5] Matsumoto A. In: Salamone JC, editor. Phenolic Resins: Polymeric Materials Encyclopaedia, vol. 7. Florida: CRC Press; 1996. p. 5039. [6] Reghunadhan Nair CP, Bindu RL, Ninan KN. Recent advances in phenolic resins. Metals Materials and Processes, vol. 9(2). Mumbai: Meshap Science Publishers; 1997. pp. 179 200. [7] Reghunadhan Nair CP. Non-conventional phenolic resins. J Sci Ind Res 2002;61:1733. [8] Katzman HA, Mallon JJ, Barry WT. Polyarylacetylenematrix composites for solid rocket motor components. J Adv Mater 1995;4:21 7. [9] Golfarb IJ, Lee CY-C, Arnold FE, Helminiak TE. In: Serani TM, editor. High Temperature Polymer Matrix Composites. Park Ridge, NJ: Noyes Data Corporation; 1987.
[10] Moroz SA, Gorbachev SG, Chekina OV. Structure and properties of allylphenol formaldehyde resins. Plast Massy 1987;8:345. [11] Savoskin VM, Gontarevskaya NP, Borbulevich AI, Protsenko EI, Lunev LV. Synthesis of allyl derivatives of phenols. Plast Massy 1984;6:1011. [12] Ambika Devin K, Reghunadhan Nair CP, Ninan KN. Dual cure phenolepoxy resins, characterisation and properties. Polym Polym Compos 2003;11(7):18. [13] Enoki T, Okubo H, Ishii K, Shibahara S. Curing reactions of maleimide resins. IV. Effects of catalysts on the reactions of N-phenylmaleimide/allyl compound systems. Netsuku Kasei Jushi 1991;12:918. [14] Wagner-Jauregg TH. Structure of addition product from N-nbutyl maleimide and styrene. Tetrahedron Lett 1967;13: 11756. [15] Reyx D, Campistron I, Caillaud C, Villatte M, Cavedon A. Thermal reactions between N-phenyl maleimide and 2-allyl phenol as a model for crosslinking reaction in bismaleimide polymerisation with diallylbisphenol-A. Makromol Chem Phys 1995;196:77585. [16] Cunningham ID, Brownhill A, Hamerton I, Howlin BJ. The Ene reaction between maleimide and allyl substituted aromatics. Tetrahedron 1997;53:1347394. [17] Phelan JC, Sung CSP. Fluorescence characteristics of cure products in bis(maleimide)/diallylbisphenol-A resin. Macromolecules 1997;30(22):6837. Phelan JC, Sung CSP. Cure characterization in bis(maleimide)/diallylbisphenol-A resin by uorescence FT-IR and UV-reection spectroscopy. Macromolecules 1997;30(22):6845 51. [18] Mijovic J, Andjelic S. Study of the mechanism and rate of bismaleimide cure by remote in-situ real-time ber optic near-infrared spectroscopy. Macromolecules 1996;29: 239 46. [19] Shibahara S, Enoki T, Yamamoto T, Motoyoshiya J, Hayashi S. Curing reactions of bismaleimide resins catalysed by triphenyl phosphine, high resolution solid-state 13C NMR study. Polym J 1996;28(9):752 7. [20] Shibahara S, Yamamoto T, Yamaji T, Motoyoshiya J, Hayashi S. Thermal-reactions of n-phenylmaleimide and mono-functional or di-functional allylphenols. Polym J 1998; 30(5):4049. [21] Morgan RJ, Shin E, Rosenberg B, Jurek A. Characterisation of the cure reactions of bismaleimide composite matrices. Polymer 1997;38(3):63946. [22] Boey FYC, Song XL, Rath SK, Yue CY. Cure reaction for modied diallylbisphenol-A/diaminodiphenylsulfone/bismaleimide. J Appl Polym Sci 2002;85(2):227 35. [23] King JJ, Chaudhari M, Zahir S. A new bismaleimide system for high performance applications. 29th In SAMPE Symp 1984;29:392403. [24] Stenzenberger HD. Addition polyimides. Adv Polym Sci 1994;117:167217. [25] Gu AJ, Liang GZ, Lan LW. A high-performance bismaleimide resin with good processing characteristics. J Appl Polym Sci 1996;62(5):799803.
492
C.P. Reghunadhan Nair / Prog. Polym. Sci. 29 (2004) 401498 1. Polyurethane/allyl novolac resin ABCPs. Eur Polym J 1999;35(6):1139 48. Chiang WY, Tsai CD. Synthesis and properties of maleimide-terminated polyurethane ab cross-linked Polymers iipolyurethane allyl nonyl novolac resin bismaleimide diphenyl methane ABCPs. Angew Makromol Chemie 1998; 260(11):1115. Gouri C, Reghunadhan Nair CP, Ramaswamy R. Reactive alder-ene blend of diallyl bisphenol-A novolac and bisphenol-A-bismaleimide: synthesis, cure and adhesion studies. Polym Int 2001;50:40313. Gouri C, Reghunadhan Nair CP, Ramaswamy R. Adhesive characteristics of alder-ene adduct of diallyl bisphenol-A novolac and bisphenol-A-bismaleimide. High Perform Polym 2000;12:497 514. Gouri C, Reghunadhan Nair CP, Ramaswamy R, Ninan KN. Thermal decomposition characteristics of Alder-ene adduct of diallyl bisphenol-A novolac with bismaleimide: effect of stoichiometry, novolac molar mass and bismaleimide structure. Eur Polym J 2002;38:503 10. Gouri C, Reghunadhan Nair CP, Ramaswamy R. Hightemperature adhesives based on Alder-ene reaction of diallyl bisphenol-A novolac and bismaleimide: effect of BMI structure and novolac molar mass. Polym Polym Comp 2003;11(4):311 20. Culbertson BM, Tiba O, Deviney ML, Tufts TA. Bisoxazoline-phenolic resin step-growth copolymerisation: New systems for electronic, mould making and resin transfer molding. 34th Int SAMPE Symp 1989;34:2483 97. Deviney ML, Kampa JJ. Resin transfer molding and compression molding of eight-inch thick bisoxazoline phenolic thermoset bre glass composite. 42nd Int SAMPE Symp 1997;42:24 32. Rogers JK. Latest advanced composite materials combine strength with processibility. Plastic Tech 1988; 34(8):319. Culbertson BM, Tiba O, Deviney ML. Bisoxazoline phenolic resins: new thermosetting poly(amide ether) materials for improved performance composites. 20th Int SAMPE Tech Conf 1988;20:590604. Annual report of Southwest Research Institute. PO Drawer 28510, San Antonio, Texas 78228-0510; 1996. Innovative holdings. PEAR properties. htm; 2001. Innovative holdings and technologies Inc. Dekar A, Stretz H, Koo J. Flame retardant properties of novolac phenolic/bisoxazoline amended with an epoxyterminated siloxane and clay nanocomposites. Polym Mater Sci Engng 2000;83:105 6. Roslaniec Z. Block copolymers and terpolymers and poly(etheresteramide) blends. Polimery 1999;44(78): 481 8. Huber T, Voit B, Wolf D. Perfectly branched and hyperbranched poly(ether amide)s. Macromol Symp 1999; 142:13343. Frank B, Carola C, Freddy G, Stefan G, Thomas H, Petra P, Brigitte V. High Perform Polym 2001;13(2):S21S31.
[26] Li ZM, Xu M, Lu A, Zhang MD, Huang R. A diallyl bisphenol-a ether and diallyl phenyl ether modied bismaleimide resin system for resin transfer moulding. J Appl Polym Sci 1999;74(7):1649 53. [27] Morgan RJ, Jurek A, Yen A, Donnelan T. Toughening procedures and performances of bismaleimide-carbon composites. Polymer 1993;34:83542. [28] Shiomi H, Kamio K, Hasegawa Y, Hirano Y. (Sumimoto Chemical Co). Thermosetting resin potting compositions. Japan Kokai Tokkyo Koho, JP. 03,237,150 (91,237150), 1991. Chem Abstr 116; 1992. p. 85492. [29] Mai KC, Huang JW, Zeng HM. Studies of the stability of thermoplastic-modied bismaleimide resin. J Appl Polym Sci 1997;66(10):196570. [30] Iijima T, Nishina T, Fukuda W, Tomoi M. Effect of matrix compositions on modication of bismaleimide resin by nphenylmaleimidestyrene copolymers. J Appl Polym Sci 1996;60(1):3745. [31] Naito S, Saito Y, Shiomi H. (Sumitomo Bakelite Co Ltd). Thermosetting resin compositions. Japan Kokai Tokkyo Koho. JP. 01, 289,21 (89,289821), 1989; Chem Abstr. 112 1990. p. 159870. [32] Yan YH, Shi XM, Liu JG, Zhao T, Yu YZ. Thermosetting resin system based on novolac and bismaleimide for resintransfer moulding. J Appl Polym Sci 2002;83(8):16517. [33] Arita Y, Hirako K. (Sumito Durez Co). Japan Kokai Tokkyo Koho. Fire and heat resistant maleimide resin composition. JP. 06, 493,25 (94,49325) 1994; Chem Abstr, 121; (1994). p. 110623. [34] Harris GJ. Werkstoffe UK. Midland Silicones Ltd, XYLOK210, Technical Bulletin. 22; 1971. p. 227. [35] Stenzenberger HD, Konig P. New functionalized poly(arylene ether ketones) and their use as modiers for bismaleimide resins. High Perf Polym 1993;5:12337. [36] Gu AJ, Liang GZ, Lan LW. Modication of polyaralkyl phenolic resin and its copolymer with bismaleimide. J Appl Polym Sci 1996;59(6):975 9. [37] Zhang BY, Li P, Chen XB. Inuence of composition on the properties of BMI neat resins and BMI/T300 composites. Polym Polym Compos 1998;6(3):1559. [38] Kuang WF, Cai XX, Jiang LX. Synthesis of a new siliconecontaining bismaleimide copolymer. Chin J Polym Sci 1997; 15(3):2315. [39] Dao B, Hodgkin JH, Morton TC. The utility of 2-naphthol derivatives as Diels-Alder based co-reactants for bismaleimides. High Perform Polym 1997;9(4):413 27. [40] Liang GZ, Fan J. Novel modied bismaleimide resins with improved ablativity. J Appl Polym Sci 1999;73(9):1623 31. [41] Chiang WY, Chang DM. Mechanical and dynamic properties of graft polyurethane/allyl novolak resin simultaneous interpenetrating network. Polym Int 1996;39(1):55 60. [42] Chiang WY, Chang DM. Synthesis and properties of simultaneous interpenetrating networks based on poly(urethaneepoxy)/allyl novolac resin. J Mater Sci 1997; 32(18):4985 90. [43] Chiang WY, Tsai CD. Synthesis and properties of maleimide-terminated polyurethane AB cross linked polymers.
[44]
[45]
[46]
[47]
[48]
[49]
[50]
[51]
[52]
[53] [54] [55]
[56]
[57]
[58]
C.P. Reghunadhan Nair / Prog. Polym. Sci. 29 (2004) 401498 [59] Culbertson BM, Tong YH, Schricker SR. Synthesis and ringopening reactions of tetraphenyl-substituted bisoxazoline monomers for preparing new thermosets and composites. Polym Adv Technol 2000;11(1):914. [60] Tong Y, Gao F, Huang Y, Schricker SR, Culbertson BM. Synthesis of ether-linked bisoxazolines and their use in stepgrowth polymerization reactions with phenolics. Polym Adv Technol 2002;13(5):311 9. [61] Ishida H. Versatile Phenolic stands up to the heat. Modern Plastics International 1998;6:8790. (Kaplan WA, Compiler). [62] Ishida H, Rodriguez Y. Curing kinetics of new benzoxazine-based phenolic resin by DSC. Polymer 1995;36:3151 8. [63] Ishida H, Allen D. Rheological characterisation during cure of near-zero shrinkage polybenzoxazines. ACS Polym Mater Sci Engng 1995;73:4967. [64] Ishida H, Allen D. Physical and mechanical characterisation of near-zero shrinkage polybenzoxazines. J Polym Sci-B 1996;34(6):101930. [65] Shen SB, Ishida H. Development and characterization of high-performance polybenzoxazine composites. Polym Comp 1996;17(5):710 9. [66] Ishida H, Low HY. A study on the volumetric expansion of benzoxazine-based phenolic resin. Macromolecules 1997; 30(4):1099 106. [67] Riess G, Schwob JM, Guth G, Lande B. In: Culbertson BM, McGrath JE, editors. Advances in polymer synthesis. New York: Plenum Press; 1985. [68] Ishida H, Sanders DP. Regioselectivity of the ring-opening polymerization of monofunctional alkyl-substituted aromatic amine-based benzoxazines. Polymer 2001;42(7):3115 25. [69] Hayakawa T, Osanai Y, Niizeki K, Haba O, Ueda M. The curing reaction of 3-aryl substituted benzoxazine. High Perform Polym 2000;12(1):23746. [70] Ishida H, Allen DJ. Gelation behaviour of near zero shrinkage polybenzoxazine. J Appl Polym Sci 2001;79: 40617. [71] Yu D, Chen H, Shi Z, Xu R. Curing kinetics of benzoxazine resin by torsional braid analysis. Polymer 2002;43:31638. [72] Wang YX, Ishida H. Cationic ring-opening polymerization of benzoxazines. Polymer 1999;40(16):456370. [73] Wan XB, He JB, Xu N, Xue Q, Ishida H. New heat-resistant polybenzoxazine synthesized by electrochemical method. Chem J Chinese Univ 2001;22(3):506 7. [74] Shen SB, Ishida H. Synthesis and characterisation of polyfunctional naphthoxazines and related polymers. J Appl Polym Sci 1996;61(9):1595 605. [75] Ishida H, Sanders DP. Improved thermal and mechanicalproperties of polybenzoxazines based on alkyl-substituted aromatic-amines. J Polym Sci-B 2000;38(24):3289301. [76] Huang MT, Ishida H. Dynamic-mechanical analysis of reactive diluent modied benzoxazine-based phenolic resin. Polym Polym Comp 1999;7(4):23347. [77] Kimura H, Matsumoto A, Sugito H, Hasegawa K, Ohtsuka K, Fukuda A. New thermosetting resin from Poly( p-vinylphe-
493
[78]
[79]
[80]
[81]
[82]
[83]
[84]
[85]
[86]
[87]
[88]
[89]
[90]
[91]
[92]
nol) based benzoxazine and epoxy-resin. J Appl Polym Sci 2001;79(3):555 65. Tietze R, Blyakham Y, Bhatt P, Chaudary M. Benzoxazines, new chemistry for building advanced printed wiring boards. 46th Int SAMPE Symp 2001;46:1451 7. Kim HJ, Brunovska Z, Ishida H. Synthesis and thermal characterization of polybenzoxazines based on acetylenefunctional monomers. Polymer 1999;40(23):656573. Kim HJ, Brunovska Z, Ishida H. Synthesis and thermal characterisation of polybenzoxazines based on acetylenefunctional monomers. 43rd Int SAMPE Symp 1988;43: 13709. Kim HJ, Brunovska Z, Ishida H. Molecular characterisation of the polymerisation of acetylene-functional benzoxazine monomers. Polymer 1999;40:1815 22. Kanchanasopa M, Yanumet N, Hemvichian K, Ishida H. The effect of polymerization conditions on the density and Tg of bisphenol-A and hexauoroisopropylidenecontaining polybenzoxazines. Polym Polym Comp 2001; 9(6):36775. Liu JP, Ishida H. High-yield synthesis of uorinated benzoxazine monomers and their molecular characterisation. Polym Polym Comp 2002;10(3):191203. Brunovska Z, Lyon R, Ishida H. Thermal properties of phthalonitrile functional polybenzoxazine. Thermochim Acta 2000;357(8):195 203. Choi S-W, Ishida H. Preparation of dendritic macromolecules containing benzoxazine moiety. Polym Prepr (American Chemical Society, Division of Polymer Chemistry) 2001;42(2):433 4. Ishida H, Allen DJ. Mechanical characterisation of copolymers based on benzoxazine and epoxy. Polymer 1996; 37(20):448795. Kimura H, Matsumoto A, Hasegawa K, Ohtsuka K, Fukuda A. Epoxy-resin cured by bisphenol-A based benzoxazine. J Appl Polym Sci 1998;68(12):190310. Blyakhman Y, Tontisakis A, Senger J, Chaudhari A. Novel high performance matrix systems. 46th Int SAMPE Symp 2001;46:53345. Kimura H, Murata Y, Matsumoto A, Hasegawa K, Ohtsuka K, Fukuda A. New thermosetting resin from terpenediphenol-based benzoxazine and epoxy-resin. J Appl Polym Sci 1999;74:226673. Rimdusit S, Ishida H. Development of new class of electronic packaging materials based on ternary-systems of benzoxazine, epoxy, and phenolic resins. Polymer 2000;41(22): 79419. Rimdusit S, Ishida H. Kinetic study of curing process and gelation of high performance thermosets based on ternary systems of benzoxazine, epoxy and phenolic resins. 46th Int SAMPE Symp 2001;46:1466 80. Rimdusit S, Ishida H. Gelation study of high processibility and high-reliability ternary-systems based on benzoxazine, epoxy, and phenolic resins for an application as electronic packaging materials. Rheol Acta 2002;41(12):1 9.
494
C.P. Reghunadhan Nair / Prog. Polym. Sci. 29 (2004) 401498 curing behaviour and properties of polybenzoxazines. Polymer 2002;43(1):4553. Su Y-C, Kuo S-W, Yei D-R, Xu H, Chang F-C. Thermal properties and hydrogen bonding in polymer blend of polybenzoxazine/poly(N-vinyl-2-pyrollidone). Polymer 2003;44:218791. Phiriyawirut P, Magaraphan R, Ishida H. Preparation and characterisation of polybenzoxazine-clay immiscible nanocomposite. Mater Res Innovations 2001;4(23):18796. Shi ZX, Yu DS, Wang YZ, Xu RW. Investigation of isothermal curing behaviour during the synthesis of polybenzoxazine-layered silicate nanocomposites via cyclic monomer. Eur Polym J 2002;38(4):727 33. Ishida H, Rimdusit S. Very high thermal-conductivity obtained by boron nitride-lled polybenzoxazine. Thermochim Acta 1998;320(1 2):17786. Huang MT, Ishida H. Investigation of the boron nitride/ polybenzoxazine interphase. J Polym Sci-B 1999;37(17): 236072. Dansiri N, Yanumet N, Ellis JW, Ishida H. Resin transfer molding of natural ber-reinforced polybenzoxazine composites. Polym Comp 2002;23(3):352 60. Suprapakorn N, Dhamrongvaraporn S, Ishida H. Effect of CaCO3 on the mechanical and rheological properties of a ring-opening phenolic resin-polybenzoxazine. Polym Comp 1998;19(2):126 32. Low HY, Ishida H. An investigation of the thermal and thermo-oxidative degradation of polybenzoxazine with a reactive functional-group. J Polym Sci-B 1999;37(7): 647 59. Low HY, Ishida H. Structural effects of phenols on the thermal and thermo-oxidative degradation of polybenzoxazine. Polymer 1999;40:4365 76. Kim HJ, Brunovska Z, Ishida H. Dynamic mechanical analysis on highly thermally stable polybenzoxazines with an acetylene functional group. J Appl Poly Sci 1999;73: 857 62. Hemvichian K, Ishida H. Thermal-decomposition processes in aromatic amine-based polybenzoxazines investigated by TGA and GC-MS. Polymer 2002;43:4391402. Hemvichian K, Laobuthee A, Chirachanchai S, Ishida H. Thermal-decomposition processes in polybenzoxazine model dimers investigated by TGA-FTIR and GC-MS. Polym Degrad Stab 2002;76(1):115. Kim HD, Ishida H. Study on the chemical-stability of benzoxazine-based phenolic resins in carboxylic acids. J Appl Polym Sci 2001;79(7):120719. Macko JA, Ishida H. Behaviour of a bisphenol-A-based polybenzoxazine exposed to ultraviolet-radiation. J Polym Sci-B 2000;38(20):2687701. Macko JA, Ishida H. Structural effects of phenols on the photo-oxidative degradation of polybenzoxazines. Polymer 2001;42(1):227 40. Hale A, Macosko CW. DSC and NMR studies of the imidazole accelerated reaction between epoxides and phenols. J Appl Polym Sci 1989;38:125369.
[93] Ishida H, Low HY. Synthesis of benzoxazine functional silane and adhesion properties of glass-ber-reinforced polybenzoxazine composites. J Appl Polym Sci 1998;69(13):255967. [94] Kimura H, Matsumoto A, Hasegawa K, Fukuda A. New thermosetting resin from bisphenol A-based benzoxazine and bisoxazoline. J Appl Polym Sci 1999;72(12): 15518. [95] Kimura H, Taguchi S, Matsumoto A. Studies on new-type of phenolic resin (ix) curing reaction of bisphenol A-based benzoxazine with bisoxazoline and the properties of the cured resiniicure reactivity of benzoxazine. J Appl Polym Sci 2001;79(13):23319. [96] Shen SB, Ishida H. Dynamic-mechanical and thermal characterisation of high-performance polybenzoxazines. J Polym Sci-B 1999;37(23):325768. [97] Brunovska Z, Ishida H. Thermal study on the copolymers of phthalonitrile and phenylnitrile-functional benzoxazines. J Appl Polym Sci 1999;73(14):2937 49. [98] Ishida H, Lee YH. Infrared and thermal analyses of polybenzoxazine and polycarbonate blends. J Appl Polym Sci 2001;81(4):1021 34. [99] Ishida H, Lee YH. Study of exchange-reaction in polycarbonate-modied polybenzoxazine via model-compound. J Appl Polym Sci 2002;83(9):1848 55. [100] Ishida H, Lee YH. Synergism observed in polybenzoxazine and poly(epsilon-caprolactone) blends by dynamic-mechanical and thermogravimetric analysis. Polymer 2001;42(16): 69719. [101] Ishida H, Lee YH. Study of hydrogen-bonding and thermalproperties of polybenzoxazine and poly-(epsilon-caprolactone) blends. J Polym Sci-B 2001;39(7):73649. [102] Takeichi T, Agag T, Zeidam R. Preparation and properties of polybenzoxazine/poly(imide siloxane) alloys: in situ ringopening polymerisation of benzoxazine in the presence of soluble poly(imidesiloxane). J Polym Sci-A 2001;39(15): 263341. [103] Takeichi T, Guo Y. Synthesis and characterisation of poly(urethanebenzoxazine) lms as novel type of polyurethane/phenolic resin composite. J Polym Sci-A 2000;38: 4165 76. [104] Takeichi T, Guo Y. Preparation and properties of poly(urethane-benzoxazine)s based on monofunctional benzoxazine monomer. Polym J 2001;33(5):43743. [105] Jang J, Seo D. Performance improvement of rubber-modied polybenzoxazine. J Appl Polym Sci 1998;67(1):1 10. [106] Ishida H, Lee YH. Dynamic-mechanical and thermalanalysis of reactive poly (butadiene-co-acrylonitrile) rubber-modied polybenzoxazine resin. Polym Polym Comp 2001;9(2):121 34. [107] Agag T, Takeichi T. Polybenzoxazine-montmorillonite hybrid nano composites: synthesis and characterisation. Polymer 2000;41(19):708390. [108] Ishida H, Allen DJ. Physical and mechanical characterisation of near zero shrinkage polybenzoxazines. J Polym Sci-B 1996;34(6):101930. [109] Takeichi T, Zeidam R, Agag T. Polybenzoxazine/clay hybrid nanocomposites: inuence of preparation method on the
[110]
[111]
[112]
[113]
[114]
[115]
[116]
[117]
[118]
[119]
[120]
[121]
[122]
[123]
[124]
[125]
C.P. Reghunadhan Nair / Prog. Polym. Sci. 29 (2004) 401498 [126] Ogato M, Kinjo N, Kawata T. Effect of cross linking on physical properties of phenolHCHOnovolac cured epoxy resins. J Appl Polym Sci 1993;48:583601. [127] Tyberg CS, Bears K, Sankarapandian M, Shih P, Loos AC, Dillard D, Mcgrath JE, Rife JS, Sorathia U. Structure property correlation of void-free phenolicepoxy matrix materials. Polymer 2000;41:5043. [128] Tysberg CS, Bears K, Sankarapandian M, Shih P, Loos AC, Dillard D, Mcgrath JE, Rife JS, Sorathia U. Tough, voidfree, ame retardant phenolic matrix materials. Constr Build Mater 1999;13:343 53. [129] Han S, Kim WG, Yoon HG, Moon TJ. Curing reaction of biphenyl epoxy resin with different phenolic functional hardeners. J Polym Sci-A 1998;36(5):773 83. [130] DiBenedetto AT. Prediction of the Tg of polymers: a model based on the principle of corresponding states. J Polym Sci-B 1987;25:1949 69. [131] Han S, Kim WG, Yoon HG, Moon TJ. A kinetic-study of biphenyl type epoxyxylok resin system with different kinds of catalysts. Bull Kor Chem Soc 1997;18(11):1199203. [132] Han S, Yoon HG, Suh KS, Kim WG, Moon TJ. Cure kinetics of biphenyl epoxy-phenol novolac resin system using triphenyl phosphine as catalyst. J Polym Sci-A 1998;37: 71320. [133] Choi IJ, Han S, Yoon HG, Kim WG. A Kinetic-study of offstoichiometric biphenyl epoxy-dicyclopentadiene type phenolic resin system. Polym Korea 1998;22(5):839 48. [134] Han S, Kim WG, Yoon HG, Moon TJ. Kinetic-study of the effect of catalysts on the curing of biphenyl epoxy resin. J Appl Polym Sci 1998;68(7):1125 37. [135] Fainleib A, Galy J, Pascault JP, Sue HJ. Ways of synthesis of polymer networks based on diglycidyl ether of bisphenol-A, bisphenol-A, and sulfanilamidekinetics study. J Appl Polym Sci 2001;80(4):580 91. [136] Biernath RW, Soane DS. In: Salamone JC, Rife J, editors. Contemporary topics in polymer science, vol. 7. New York: Plenum Press; 1992. p. 103. [137] Reghunadhan Nair CP, Ambika Devi K, Krishnan K, Ninan KN. Kinetics of triphenyl phosphine-catalysed thermal cure of diallyl bisphenol A-novolac epoxy blend. In: Pillai CGS, Ramakrishnan KL, Ravindran PV, Venugopal V, editors. Proceedings, THERMANS 2001, Mumbai: Bhabha Atomic Research Centre; 2002. p. 134 6. [138] Luo XW, Ping ZH, Ding JP, Ding YD, Li SJ. Mechanism studies on water sorption and permeation in epoxy-resin by impedance spectroscopy. 2. Cure kinetics of o-cresol novolac resin with esteried phenol novolac resin. J Macromol Sci Pure Appl Chem 1997;A34(11):227991. [139] Nagai A, Kokaku H, Ishii T. Relationship of structure and properties of phosphine-containing catalysts in reactions with epoxy and phenol compounds. J Appl Polym Sci 2002; 85(11):2335 41. [140] Smirnov YN, Dyachkova SL, Russ. J Appl Chem 2000; 73(5):8705. [141] Tai HJ. Chemical shrinkage and diffusion-controlled reaction in a cresol novolac epoxy. J Polym ResTaiwan 2000;7(4): 2217.
495
[142] Yoon HG, Han S, Kim WG, Suh KS. Cure kinetic-model of biphenyl-type epoxy/phenol novolac resin system considering active complex-formation. Polym Korea 1999;23(4): 507 16. [143] Kim WG, Yoon HG, Lee JY. Cure kinetics of biphenyl epoxyresin system using latent catalysts. J Appl Polym Sci 2001;81(11):271120. [144] Hsieh TH, Wang TL, Ho KS, Wang YZ. Chemo-rheological analysis of an epoxy-novolac molding compound. Polym Engng Sci 2000;40(2):41829. [145] Kim HY, Moon KS, Han S, Kim JM, Ryu JH, Yoon HG. Chemo-rheological study of biphenyl-type epoxy/phenol novolac resin system. Polym Korea 1999;23(1):105 12. [146] Chen YC, Chiu WY, Lin KF. Kinetic study of imidazole cured epoxy-phenol resin. J Polym Sci-A 1999;37:323342. [147] Chen YC, Chiu WY. The structural properties of imidazole cured epoxyphenol resins. Polymer 2001;42:5439 48. [148] Park SJ, Seo MK, Lee JR. Isothermal cure kinetics of epoxy/ phenolnovolac resin blend system initiated by cationic latent thermal catalysts. J Polym Sci-A 2000;38(16): 294556. [149] Park SJ, Seo MK, Lee JR. Relationship between viscoelastic properties and gelation in the epoxy/phenol novolac blend system with N-benzyl pyrazinium salt as a latent thermal catalyst. J Appl Polym Sci 2001;79(12): 2299 308. [150] Hamazu F, Akashi S, Koisumi T, Takata T, Endo T. Novel benzyl ammonium salt having an aromatic group on sulfur atom as a latent thermal initiator. J Polym Sci, Part A: Polym Chem 1991;29:167580. [151] Goh Y, Ijima T, Tomoi MJ. Novel quaternary ammonium borates as latent catalysts for epoxyphenolic resin. Polym Sci-A 2002;40:2689701. Goh Y, Ijima T, Tomoi MJ. Thermal latency of novel chelating borates catalysts as latent catalysts for epoxyphenolic resin. Polym Sci-A 2002;40: 270216. [152] Kobayashi M, Sanda F, Endo T. Application of (triphenyl phosphine methylene) boranes to thermally latent catalysts for polyaddition of bisphenol A diglycidyl ether with bisphenol A: model systems of epoxy-novolac resin. Macromolecules 2001;34(5):11346. [153] Kobayashi M, Sanda F, Endo T. Substituent effect of (triphenyl phosphinemethylene) boranes on latent catalytic activity for polyaddition of bisphenol-A diglycidyl ether with bisphenol A: model system of epoxy-novolac resin. Macromolecules 2002;35:346 8. [154] Tysberg CS, Shih P, Verghese KNE, Loos AC, Lesko JJ, Rife JS. Latent nucleophilic initiators for melt processing phenolicepoxy matrix composites. Polymer 2000;41(26): 903348. [155] Tysberg CS, Sankarapandian M, Bears K, Shih P, Loose AC, Dillard D, Mcgrath JE, Rife JS, Sorathia U. Structure property relationship of void-free phenolicepoxy matrix materials. Polymer 2000;41(13):505362. [156] Ochi M, Yoshinaka S, Shimizu Y. Effect of the chemical structure of phenolic curing agents in the network structure
496
C.P. Reghunadhan Nair / Prog. Polym. Sci. 29 (2004) 401498 and mechanical properties of cured epoxy resins containing a mesogenic group. Kobunshi Ronbunshu 1997;54(4):217 23. Strehmel V, Wetzel H, Strehmel B. Attaching of exible chains to novolac on the basis of bisphenol A. J Appl Polym Sci 1996;60(8):12219. Tseng FP, Chang FC, Lin SF, Lin JJ. Preparation and epoxy curing of p-nonylphenol/dicyclopentadiene adducts. J Appl Polym Sci 1999;74(9):2196 206. Kaji M, Nakahara K, Endo T. Synthesis of a bifunctional epoxy monomer containing biphenyl moiety and properties of its cured polymer with phenol novolac. J Appl Polym Sci 1999;74(3):6908. Kaji M, Nakahara K, Ogami K, Endo T. Synthesis of a novel epoxy resin containing pyrene moiety and thermal properties of its cured polymer with phenol novolac. J Appl Polym Sci 2000;75(4):52835. Tai HJ, Wang JB, Chou HL. Polym Comp 2000;21(6): 9539. Tai HJ, Wang JB, Chou HL. Synthesis and properties of vinyl siloxane modied cresol novolac epoxy for electronic encapsulation. J Appl Polym Sci 2001;79(4):652 61. Ho TH, Wang CS. Modication of epoxy resin with siloxane containing phenol aralkyl epoxyresin for electronic encapsulation application. Eur Polym J 2001;37(2): 267 74. Sugihara S, Okada S, Ohtsuka H, Yamaki J. Effects of surface state of plastics on adhesive strength in electro-less plating. J Appl Polym Sci 1996;59(11):17518. Ochi M, Tsuyono N, Nakanishi K, Murata M. Effect of network structure on thermal and mechanical properties of biphenol-type epoxy resins cured with phenols. J Appl Polym Sci 1995;56:1161 7. Liu YL. Flame retardant epoxy resins from novel phosphorous-containing novolac. Polymer 2001;42(8):3445 54. Liu YL, Wu CS, Chang TC. Flame-retardant epoxyresins from o-cresol novolac epoxy cured with a phosphoruscontaining aralkyl novolac. J Polym Sci-A 2002;40:2329. Shieh JY, Wang CS. Synthesis of novel ame retardant epoxy hardeners and properties of cured products. Polymer 2001;42(18):761725. Shieh JY, Wang CS. Effect of organophosphate structure on the physical and ame-retardant properties of an epoxy resin. J Polym Sci-A 2002;40:369 78. Wu CS, Liu YL, Chiu YS. Epoxy resins possessing ame retardant elements from silicon incorporated epoxy compound cured with phosphorus or nitrogen containing curing agents. Polymer 2002;43:427784. Summer MJ, Sankarapandian M, Mcgrath JE, Rife JS, Sorathia U. Tough, void-free, ame retardant phenolic matrix materials. Polymer 2002;43(19):5157. Reghunadhan Nair CP, Bindu RL, Ninan KN. Phenolic resins bearing maleimide functions; synthesis and characterisation. J Polym Sci Part A Polym Chem 2000;38:64152. Bindu RL, Reghunadhan Nair CP, Ninan KN. Maleimidefunctional phenolic resins: thermal characteristics and properties of composites. J Appl Polym Sci 2001;80:166474. [174] Pyriadi TM, Abdulameer I. Preparation of phenol formaldehyde resins containing pendant isoimide and their isomerisation to stable resins. J Polym Sci-A 2000;38(18): 324452. [175] Bindu RL, Reghunadhan Nair CP, Ninan KN. Addition- cure phenolic resins based on alder-ene reaction. J Appl Polym Sci 2001;80:73749. [176] Gouri C, Reghunadhan Nair CP, Ramaswamy R. Adhesive and thermal characteristics of maleimide-functional novolac resins. J Appl Polym Sci 1999;73:695 705. [177] Gouri C, Reghunadhan Nair CP, Ramaswamy R. Effect of elastomer modication on the adhesive characteristics of maleimide-functional novolacepoxy resins. J Appl Polym Sci 1999;74(9):2321 32. [178] Gouri C, Reghunadhan Nair CP, Ramaswamy R. Thermoplastic lm adhesives based on phenol-functional acrylic terpolymers: mechanical and adhesion characteristics. J Adhes Sci Technol 2001;15(7):82340. [179] Gouri C, Reghunadhan Nair CP, Ramaswamy R. Thermosetting lm adhesives based on phenol-functional acrylic terpolymers. J Adhes Sci Technol 2001;15(6):70326. [180] Dirlikov SK. Propargyl terminated resins, a hydrophobic substitute for epoxy resins. High Perform Polym 1990;2(1): 67 77. [181] Douglas WE, Overend A. Curing reactions in acetyleneterminated resin. 1.Uncatalysed cure of aryl propargyl ether terminated monomers. Eur Polym J 1991;27:1279 87. [182] Douglas WE, Overend AS. Curing reactions in acetyleneterminated resins. Part 4. IR and NMR study of catalysed polymerisation of aryl prop-2-ynyl ether-terminated monomers. J Mater Chem 1993;3:1019 24. [183] Douglas WE, Overend AE. Cyclotrimerisation versus nonaromatic polyene formation in catalysed cure of aryl propargyl ether terminated monomer. Polymer 1993;34: 15445. [184] Grenier MFL, Sangler C. Prepolymers with propargyl termianl residues. 1. Simulation of reaction mechanism and kinetics of monofunctional models. Eur Polym J 1997;33: 1125 34. [185] Reghunadhan Nair CP, Bindu RL, Krishnan K, Ninan KN. Bispropargyl ether resins; synthesis and structure thermal property correlations. Eur Polym J 1999;35(2):235 46. [186] Balcar H, Kalisz T, Sedlacek J, Blechta V, Matejka P. Polymerization of nitrophenyl propargyl ethers with transition-metal catalysts and characterization of polymers. Polymer 1998;39(18):44437. [187] Loughran GA, Reinhardt BA, Arnold FE, Solosky EJ. Thermal and thermal mechanical properties of acetylene terminated phenylene systems. Org Coat Plast Chem 1980; 43:77782. [188] Okubo H, Suzuki K, Enoki H. Resin compositions for semiconductor sealants. Jpn Kokai Tokkyo Koho JP 04,15, 217 (92 15,217). Japan: Sumitomo Bakelite Co Ltd; 1990. [Chem Abstr 117 1992 9490]. [189] Bilalov NM, Naibova TM, Akhundova EsA, Agakisheva MA. Modication of phenolformaldehyde resin by propar-
[157]
[158]
[159]
[160]
[161] [162]
[163]
[164]
[165]
[166] [167]
[168]
[169]
[170]
[171]
[172]
[173]
C.P. Reghunadhan Nair / Prog. Polym. Sci. 29 (2004) 401498 gyl glycidyl ether. Azerbaidzhanskii Khimicheskii Zhurnal 1984;1:979. Chem Abstr, 101 1984, 231395. Enoki H, Suzuki K, Okubo H. Thermosetting resin compositions with dimensional stability and heat resistance. Japan Kokai Tokkyo Koho, JP.04, 137,56 (92, 13756) Sumito Bakelite Co; 1992. [Chem Abstr 117 1992, 9477]. Enoki H, Suzuki K, Okubo H. Thermosetting resins with good workability andcurability for laminates. Japan Kokai Tokkyo Koho JP. 04,13,752 (92, 13752) Sumito Bakelite Co; 1992. [Chem Abstr 117 1992, 9474]. Enoki H, Suzuki K, Okubo H. Heat and moisture resistant siloxane -modied phenolic resin. Japan Kokai Tokkyo Koho JP.04,13,754(92, 13754) Sumito Bakelite Co; 1992. [Chem Abstr 117 1992, 9475] and Heat and moisture resistant siloxane-modied phenolic resin and maleimide resin composition for sealing of semiconductor devices. JP 04, 13,755 (92, 13755); 1992. [Chem Abstr 117 1992, 9476]. Furutani H, Ida J, Nagano H. Novel Soluble propargyletherterminated ester-imide prepolymers. I-Their syntheses and characteristics. High Perform Polym 2000;12(4):471 9. Furutani H, Ida J, Nagano H. Novel propargyl etherterminated ester-imide prepolymers: II. Matrix resins for high-temperature-use composites. High Perform Polym 2000;12(4):481 7. Furutani H, Ida J, Nagano H. Novel propargyletherterminated ester-imide prepolymersIIIthermoset/thermoset blend prepolymers as matrix resins for composites. High Perform Polym 2000;12(4):48996. Agag T, Takeichi T. Novel benzoxazine monomers containing p-phenyl propargyl ether: polymerisation of monomers and properties of polybenzoxazine. Macromolecules 2001; 34(21):7257. Bindu RL, Reghunadhan Nair CP, Ninan KN. Additioncure phenolics based on propargyl ether functional novolacs: synthesis, curing and properties. Polym Int 2001;50:651 8. Bindu RL, Reghunadhan Nair CP, Ninan KN. Thermal characteristics of the propargyl ether novolac phenolic resins. J Macromol Sci Pure Appl Chem 2003;A40(4):35769. Hug R, Frater GY, Hansen HJ, Schmidt H. Thermal behaviour of cyclopropa[c]chromenes. Helv Chim Acta 1971;54:30627. Zsindely J, Schmidt H. Sigmatropic rearrangement of aryl propargyl ethers. Synthesis of 1,5-dimethyl-6-methylenetricyclo[3,2,1.2,7]oct-3-en-8-one derivatives. Helv Chim Acta 1968;51:1510 4. Pomeranz UK, Hansen HJ, Schmidt H. On the catalysed curing of phenyl propargyl ether. Helv Chim Acta 1973;56: 2981. Reghunadhan Nair CP. Unpublished results. Reghunadhan Nair CP, Narenthranathan PK, Packirisamy S. Unpublished results. Reghunadhan Nair CP, Gouri C, Dhanya V. Dual cure thermoset based on propargyl novolac-epoxy system, synthesis and properties. Polym Polym Comp 2004; 12: 4961.
497
[190]
[191]
[192]
[193]
[194]
[195]
[196]
[197]
[198]
[199]
[200]
[201]
[202] [203] [204]
[205] Reghunadhan Nair CP, Bindu RL, Ninan KN. Addition curable phenolic resins based on ethynyl phenyl azo functional novolac. Polymer 2002;43(9):2609 17. [206] Landis AL, Bilow N, Boschan RH, Lawrence RE, Aponyi TJ. Acetylene-terminated polyimide terephthalonitrile N,Ndioxide copolymers. Polym Prepr Am Chem Soc Div Polym Chem 1974;15:5336. Landis AL, Bilow N, Boschan RH, Lawrence RE, Aponyi TJ. Homopolymerizable acetylene-terminated polyimides. Polym Prepr Am Chem Soc Div Polym Chem 1974;15:53741. [207] Glaser C. Annalen 1870;137:154. ref. 118 in Sergeev VA, Yu A, Chernomordik AS, Kurapov. Oligomers and polymers with reactive acetylenic groups. Russ Chem Rev, 53 (1984) 518 539. [208] Strauss F. Annalen 1905;342:190. ref. 117 in Sergeev VA, Yu A, Chernomordik AS, Kurapov. Oligomers and polymers with reactive acetylenic groups. Russ Chem Rev, 53 (1984) 518 539. [209] Viehe HE, editor. The chemistry of acetylenes. New York: Dekker; 1969. [210] Bindu RL. Modied phenolic resins and their composites. PhD Thesis. Kerala University, India; 2000. [211] Pater RH. Thermosetting polyimides: a review. SAMPE J 1994;30(5):29 38. [212] Connell JW, Smith Jr JG, Hergenrother PM. Oligomers and polymers containing phenyl ethynyl groups. J Macromol Sci Rev Macromol Chem Phys 2000;C40(23):207 30. [213] Reghunadhan Nair CP, Bindu RL, Ninan KN. Addition-cure phenolic resins with phenyl ethynyl functions, synthesis, characterisation and thermal properties. J Mater Sci 2001; 36(17):41517. [214] Hergenrother PM, Smith Jr. JG. Chemistry and properties of imide oligomers end-capped with phenyl ethynyl phthaloc anhydrides. Polymer 1994;1994:485764. [215] Wood KH, Orwoll RA, Jensen BJ, Young PR, McNair HM. Cure chemistry of phenyl ethynyl terminated oligomers. 42nd Int SAMPE Symp 1997;42:127182. [216] Fang X, Rogers DF, Scola DA, Stevens MP. A study of the thermal cure of phenylethynyl-terminated imide model compound and a phenyl ethynyl-terminated imide oligomer. J Polym Sci-A 1998;36:46170. [217] Reghunadhan Nair CP, Bindu RL, Ninan KN. Condensationaddition-type phenolic resins with phenyl ethynyl functions: synthesis, characterisation, and thermal properties. J Appl Polym Sci 2002;81:33717. [218] Reghunadhan Nair CP, Bindu RL, Ninan KN. Thermal characteristics of addition-cure phenolic resins. Polym Degrad Stab 2001;73(2):2517. [219] Das S, Prevorsek DC, De Bona BT. Phenolic triazine, a versatile high performance thermoset for composite applications. 21st Int SAMPE Tech Conf 1989;21:972 83. [220] Das S, Parsippany, Prevorsek DC. Cyanato group containing phenolic resins; phenolic triazines (PT) derived therefrom US Pat 4, 831 086; May, 1989. [221] Primaset PT. Technical product brochure. Switzerland: Lonza Ltd; 1996.
498
C.P. Reghunadhan Nair / Prog. Polym. Sci. 29 (2004) 401498 triazines thereof: synthesis and thermal properties. Eur Polym J 2000;36:1195208. Mathew D, Reghunadhan Nair CP, Ninan KN. Imido phenolictriazines derived from maleimide-functional novolac, synthesis and thermal properties. Eur Polym J 2001;37: 315 21. Ikekuchi, N., Nozaki, M., Heat-resistant polycyanuratecontaining phenol novolac-type cyanate ester pre-copolymers with improved storage stability. Japan Kokai Tokkyo Koho JP 11, 124,433; 1999. A2 19990511. [Chem Abstr 130 1999, 338839]. Gilman JW, Haris JrRH, Brown JE. Flammability studies of new cyanate ester resins. 42nd Int SAMPE Symp 1997;42: 105261. Kern W, Cifrain M, Schroder R, Hummel K, Mayer C, Hofstotter M. Polymers with pendant cyanate ester groups; synthesis and thermal curing and photocrosslinking. Eur Polym J 1998;34(7):987 95. Gilman JW, Harris RH, Jackson CL, Morgan AB, Brassell LD, Hunter DL. Phenolic cyanate ester clay nanocomposites: effect of ammonium ion structure on ammability and nanodispersion. Book of Abstracts. 219th ACS National Meeting, San Francisco, CA, March 26 30, 2000; 2000, PMSE-217. Reghunadhan Nair CP, Mathew D, Ninan KN. Cyanate ester resins: recent developments. Adv Polym Sci 2001;54:199. Ramirez ML, Walters R, Savitsky EP, Lyon RE. Thermal decomposition of cyanate ester resins. Report no DOT/FAA/ AR-01/32, US Department of Transportation (Federal Aviation Administration), Washington DC; September, 2001.
[222] Conley RT. Thermal stability of polymers. New York: Marcel Decker; 1970. p. 11. [223] Cozzens RF, Walter P. Laser pyrolysis characterised cyanurate network polymers. J Appl Polym Sci 1987;34:60 616. [224] Miks MW, Shigly JK. Addition-polymerisation resin system for bre reinforced nozzle ablative components. US Pat 5, 645,219 Thiokol Corporation; 1997. [225] Das S. Multifunctional cyanate esters for aircraft interior applications. 30th Int SAMPE Tech Conf 1998;30:12737. [226] Das S, Prevorsek DC, De Bona BT. Phenolictriazine resins yield high performance thermoset composites. Modern Plast Int 1990;6:647. [227] Couch BP, McAllister LE. The application of PT resins to high temperature aerospace structures. 35th Int SAMPE Sympo, 35 2298-2311 and Couch BP. Workshop IX-9 1990; 93:1989. [228] Delano CB, McLeod AH., Synthesis of improved phenolic resins. NASA-CR-159724, Acurex nal report 79-25/AS, September 1979. [229] High temperature short term response. Information bulletin, Composite Centre, University of Southern California, Source: Internet, October, 2002. [230] Gmuer M, Daum U, Heyl F, Brigitta H, Alessandro PF. US2001-331300P, 20011114. Lonza Ag, Switz. [231] Reghunadhan Nair CP, Bindu RL, Joseph VC. Cyanate esters based on cardanol-modied novolacs, synthesis and thermal characteristics. J Polym Sci-A 1995;33:6217. [232] Mathew D, Reghunadhan Nair CP, Ninan KN. Pendant cyanate functional vinyl polymers and imidophenolic
[233]
[234]
[235]
[236]
[237]
[238] [239]

Advances in Addition-Cure Phenolic Resins

Uploaded by

Copyright:

Available Formats

Advances in Addition-Cure Phenolic Resins

Uploaded by

Document Information

Original Title

Copyright

Available Formats

Share this document

Share or Embed Document

Sharing Options

Did you find this document useful?

Is this content inappropriate?

Copyright:

Available Formats

Advances in Addition-Cure Phenolic Resins

Uploaded by

Copyright:

Available Formats

Prog. Polym. Sci. 29 (2004) 401498 www.elsevier.

Advances in addition-cure phenolic resins

C.P. Reghunadhan Nair / Prog. Polym. Sci. 29 (2004) 401498

C.P. Reghunadhan Nair / Prog. Polym. Sci. 29 (2004) 401498

DSC EPAN EPAP EPN FTIR FTMS

C.P. Reghunadhan Nair / Prog. Polym. Sci. 29 (2004) 401498

T5 Te TEM Terp-Bz Tg TGA TGMDA THF Ti

TPP TPS TTT UD Va Vba VBP VP VRTM WLF

C.P. Reghunadhan Nair / Prog. Polym. Sci. 29 (2004) 401498

C.P. Reghunadhan Nair / Prog. Polym. Sci. 29 (2004) 401498

C.P. Reghunadhan Nair / Prog. Polym. Sci. 29 (2004) 401498

C.P. Reghunadhan Nair / Prog. Polym. Sci. 29 (2004) 401498

Scheme 3. Components of Matrimide 5292.

C.P. Reghunadhan Nair / Prog. Polym. Sci. 29 (2004) 401498

Scheme 5. Synthesis of Allyl-xylok and curing with bismaleimide.

C.P. Reghunadhan Nair / Prog. Polym. Sci. 29 (2004) 401498

C.P. Reghunadhan Nair / Prog. Polym. Sci. 29 (2004) 401498

C.P. Reghunadhan Nair / Prog. Polym. Sci. 29 (2004) 401498

C.P. Reghunadhan Nair / Prog. Polym. Sci. 29 (2004) 401498

C.P. Reghunadhan Nair / Prog. Polym. Sci. 29 (2004) 401498

C.P. Reghunadhan Nair / Prog. Polym. Sci. 29 (2004) 401498

1.9 2.8 4.1

C.P. Reghunadhan Nair / Prog. Polym. Sci. 29 (2004) 401498

335 ,380 ,380 190,260,300 150,210,320

355 ,380 ,390 190,260,345 150,210,350

C.P. Reghunadhan Nair / Prog. Polym. Sci. 29 (2004) 401498

Scheme 8. Addition polymerisation of bisoxazolinephenolic system.

C.P. Reghunadhan Nair / Prog. Polym. Sci. 29 (2004) 401498

Fig. 8. Dependence of Tg on PBOX/phenolic composition [49].

C.P. Reghunadhan Nair / Prog. Polym. Sci. 29 (2004) 401498

608.1 28.3 403.4

C.P. Reghunadhan Nair / Prog. Polym. Sci. 29 (2004) 401498

90 237 194 5134 4879 5030

RTM resin infusion Pre-preg lamination RTM

C.P. Reghunadhan Nair / Prog. Polym. Sci. 29 (2004) 401498

C.P. Reghunadhan Nair / Prog. Polym. Sci. 29 (2004) 401498

C.P. Reghunadhan Nair / Prog. Polym. Sci. 29 (2004) 401498

Polyetherimide Phenolic resin PBZ

C.P. Reghunadhan Nair / Prog. Polym. Sci. 29 (2004) 401498

103 3.8 2.6 31 1.122 180

126 4.5 2.9 18 1.195 170

C.P. Reghunadhan Nair / Prog. Polym. Sci. 29 (2004) 401498

Va/DGEBA VBa/DGEBA VP/DGEBA VBP/DGEBA Va/CNE VBa/CNE VP/CNE VBP/CNE

174 143 165 118 209 177 209 160

0.63 0.6 0.64 0.6

C.P. Reghunadhan Nair / Prog. Polym. Sci. 29 (2004) 401498

Pth-PBZ Pth-polyimidea Pth-diamineb

596 550 500

450 510 500

Phthalonitrilepolyimide. Phthalonitrile cured by diamine (2%).

C.P. Reghunadhan Nair / Prog. Polym. Sci. 29 (2004) 401498

C.P. Reghunadhan Nair / Prog. Polym. Sci. 29 (2004) 401498

31 5334 1.2 132 4602 228 3505 0.94 168 171

Undisclosed structure. TGMDA DDS.

C.P. Reghunadhan Nair / Prog. Polym. Sci. 29 (2004) 401498

C.P. Reghunadhan Nair / Prog. Polym. Sci. 29 (2004) 401498

C.P. Reghunadhan Nair / Prog. Polym. Sci. 29 (2004) 401498

C.P. Reghunadhan Nair / Prog. Polym. Sci. 29 (2004) 401498

C.P. Reghunadhan Nair / Prog. Polym. Sci. 29 (2004) 401498