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Fire-Resist Bio-Based Polyurethane for Structural Foam

Application
Chapter · April 2014

DOI: 10.1201/b16706-17
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Chapter 14
Fire-Resist Bio-based
Polyurethane for Structural
Foam Application
Khairiah Haji Badri and Amamer Musbah Omran
Redwan
Contents
14.1 Fire-Resist Bio-Based Polyurethane for Structural foam Application.... 387

14.1.1 Polyurethane (PU) and its Properties......................................... 387
14.1.2 Flame Retardant......................................................................... 388
14.1.3 Fire Retarded PU Composites...............................................................390
14.1.4 Palm-based PU........................................................................... 392
14.2 Preparation of Palm-Based PU Filled with Tris
(2, 4- Di Tert Butyl Phenyl Phosphite) ................................................... 393
14.2.1 2, 4-Ditert-Butylphenyl Phosphite as the Flame Retardant....... 393
14.2.2 (PKO)-based Monoester-OH .................................................... 395
14.2.3 PKO-Based PU and Its Fire Retarding Composites.................. 397
14.3 Properties of Palm-Based Polyurethane and Polyurethane
Composites.............................................................................................. 398
14.3.1 FTIR Spectroscopy Analysis...................................................... 398
14.3.2 Mechanical Properties................................................................ 400
14.3.3 Thermal Properties..................................................................... 405
14.3.4 Scanning Electron Microscope (SEM) Analysis........................ 414
14.4 Conclusion.............................................................................................. 417
386 Physical Chemistry of Macromolecules
Keywords........................................................................................................... 418
Acknowledgment............................................................................................... 418
References.......................................................................................................... 418
Fire-Resist Bio-based Polyurethane for Structural Foam Application 387
14.1 FIRE-RESIST BIO-BASED POLYURETHANE FOR STRUCTURAL

FOAM APPLICATION
14.1.1 Polyurethane (PU) and its Properties
PU is a versatile thermosetting polymer. Its properties are modified either by vary-

ing the microstructure or by dispersing either inorganic or organic fillers within
the PU continuous matrix (Oertel 1993). PU is a high molecular weight polymer
based on the polyaddition of polyfunctional hydroxyl group and isocyanate. There
are two types of polyhydroxyl compounds commonly used namely polyester and
polyether polyols. Polyester is a high molecular weight substance which contain
ester group as the repeating unit in the chain. The mechanical properties and mor-
phological structure of PU depend mainly on the polyol structure, molar mass
and its functionality and to a lesser extent, on the nature of the polyisocyanate
(Badri et al. 2000). PU foam is formed by gas evolution (either carbon diox-
ide or chlorofluorocarbon) trapped during the polymerization process between
the hydroxyl-containing group compound with polyisocyanate to form urethane
chain. The resulted foams would exhibit the relationship between physical and
mechanical properties with their chemical composition and density of materials
(Oertel 1993).
At present, most polyols used in PU industry are petrochemical-based where
crude petroleum oil is used as a starting raw material. However, this material
is becoming expensive, rate of depletion is high and they require high process-
ing technology. This necessitates looking at utilizing plants that can serve as an
alternative feed stock for monomers in polymer industry. Palm oil (Badri et al.
2000, Badri et al. 2001, Chian & Gan 1998), soybean oil (Guner et al. 2006), and
vernonia oil (Kolot & Grinberg 2004) have been converted to polyol to replace
petrochemical-based polyol.
The most important commercial PU products are foams that are commonly
classified as either flexible or rigid depending on their mechanical performance
and cross-link densities. Rigid PU foams are widely used in building insulation
and domestic appliances, due to their superior mechanical properties and low den-
sity. However, the PU industry is facing environmental challenges due to type
of auxiliary blowing agents used during the polymerization process (Zhong et
al. 2002). Due to that, n-pentane and hydrochlorofluorocarbon HCFC-141b are
of better choices compared to chlorofluorocarbon (CFC). However, uncertainty
about the cost and availability of chlorofluorocarbons has led the PU foam indus-
try to focus on pentane as the primary blowing agent, especially in construction
industry. Unfortunately, the inherent high flammability of pentane has resulted in
PU foams that fail to meet the required regulatory fire tests. Therefore, PU indus-
try has to respond to these challenges by designing additive packages (catalysts,
surfactants, cross-linkers, and flame retardants) that can overcome these flam-
mability shortcomings, while providing physical and mechanical properties com-
parable to those of rigid PU foams blown with HFC or HCFC (Tang et al. 2002).
Polyurethanes, like all organic materials, burn in the presence of oxygen (O2)
under the action of heat. This cause the generation of toxic smoke and reduces
O2 concentration in the surroundings. The application of PU, which is combus-
tible, leads to an increase in fire risk. Flame retardants have been widely used for
plastics, rubbers, coatings, and fibers to reduce the risks for applications in areas
where safety is essential, such as aircraft, building/construction, public transport,
and housings for electrical equipment. In these cases they have to be made incom-
bustible, or at least difficult to ignite and burn. The focus of the present study is to
enhance the mechanical and thermal properties and importantly the fire resistivity
of PU composites by using phosphite as an additive.
14.1.2 Flame Retardant
Flame retardant is a class of materials that when compounded into plastics, pro-
vides a specific reaction during combustion. These reactions cause the initially
flammable substances to ignite with more difficulty and will inhibit the propaga-
tion compared to the original substrate under laboratory test conditions (Frank
2000). Flame retardant is a substance that can be chemically inserted into polymer
molecules or physically blended in polymer after polymerization to suppress, re-
duce or delay the propagation of a flame through plastic materials. Combustion is
supported by three critical elements––energy, O2, and fuel. For flame retardants
to be effective, they must somehow interfere with one or more of those three ele-
ments.
Several mechanisms can account for flame retardant functions. Heat absorp-
tion can occur through the release of water during the burning process. Char form-
ing can occur that insulates the polymer substrate and also retard the fire by reduc-
ing the fuel needed to continue the burning process. Chemical reaction must occur
in the flame front for the fire to continue burning. These reaction can be halted
or slowed through interference by species (free radicals) generated from flame
retardant chemicals during the burning process. Flame retardants are added to
polymeric materials, both natural and synthetic, to enhance the flame retardancy
properties of the polymers (Innes & Innes 2001). There are two main categories of
flame-retardant chemicals, additive flame retardant and reactive flame retardant.
Additive flame retardants are the great majority of the flame retardant. They
include halogenated flame retardants (Lyons 1970), organophosphorus and nitro-
gen-based organic flame retardants (Lewin 2001). All of them are incorporated
into the plastic either prior to, during, or more frequently after polymerization
reaction. They are used especially in thermoplastics such as acrylonitrile buta-
diene styrene (ABS), polystyrene (PS), polycarbonate (PC), and thermoplastic
elastomers. Sometimes, an inorganic material is added to the compounds to show
synergistic effects. The most important one is antimony trioxide (Sb2O3) that has
no perceptible flame retardant effect on its own. Together with halogen-contain-
ing compounds, however, it produces a marked synergistic effect. One of the most
important disadvantages of these types of flame retardants (additives) is their vol-
atility and thus, their flame retardancy effect may be gradually lost (Pitts 1972).
A reactive flame retardant is just a small part relative to an additive flame
retardant. They are bonded chemically to the polymer chain together with other
starting components. This prevents them from bleeding out of the polymer and
vaporized, and thus their flame retardancy is retained. They have no plasticizing
effect and should not affect on thermal stability of the basic polymer. They are
used mainly in thermosets, especially polyesters, epoxy resins, and polyurethanes
in which they can be easily incorporated (Rumack et al. 1987). Their high price is
the limiting parameter for their wide application. Halogenated phenol and tetra-
chlorophthalic anhydride are example for reactive flame retardant.
Phosphites are the type of decomposed hydroperoxide secondary antioxi-
dants. The organic phosphite is used widely as affirmer to any polymer type and
to keep its physical polymer nature such as its color and molecular weight during
processing. Activity such as hydroperoxide decomposition decreased due to its
increasing ability in receiving electron and its group size attach to phosphite and
blocked aryl phosphite (Schwetlick 1990). Figure 1 shows a type of phosphite
antioxidant that is used as a stabilizer for polymer and is used in this study. Irgafos
168 is a phosphite type of antioxidant with low volatility and extreme resistant to
hydrolysis. It provides excellent antioxidizing stability to organic polymers, re-
sistance to discoloration and adds long-term protection against thermo-oxidative
degradation after processing.
FIGURE 1 The molecular structure of Irgafos 168 [tris (2, 4-di-tert-butylphenyl)

phosphite]. (Schwetlick 1990)
This type of phosphite can act as primary antioxidizing agent in the chain
scissoring and chain transfer agent in its reaction with alkyl peroxide and then
forms hindered aryloxyl radical that can prevent chain auto-oxidation reaction.
Nevertheless, hindered aryl phosphate’s activity as antioxidant in chain scissoring
is lower compared to hindered phenol (Schwetlick 1990). Trivalent phosphorus
compounds such as commercialized brand name Irgafos are excellent hydroper-
oxide decomposers. It is used as flame retardant and works once fire is set. Phos-
phite flame retardants dissociates into radical species that compete with chain
propagating and branching steps in the combustion process.
14.1.3 Fire Retarded PU Composites
The flame retardants are chemical substances used in various products such as
plastics, textiles, and furnishing foam to reduce their fire hazards by interfering
with the composition of the polymeric materials. The use of polymeric materials
as adhesives or as organic composites, for naval, aeronautic or electronic applica-
tions, becomes more and more important. However, one of the most important
disadvantages of these materials concerns is their thermal and fire resistance be-
haviors (Aseeva & Zaikov 1985).
To limit the flammability of these materials, it is necessary to incorporate
fire retardant (FR) in the polymer. The molecules containing phosphorous groups
belong to these fire retarding agents allowing improved material thermal and fire
properties. Phosphorus, silicon, and nitrogen compounds are the agents mostly
used for replacing halogenated compounds in flame retarding resins, especially
epoxies. The halogen free products are attractive and welcome worldwide. Or-
ganophosphorus polymers have already been the subject of several works be-
cause of the large variety of applications of these products. For example, they
can improve adhesive properties and are thus used as adhesion promoters, paints,
lacquers, and as adhesives. They are also used for fibers and films with a high me-
chanical resistance, as an ion exchanger and as lubricants (Spirckel et al. 2002).
Halogen-free flame retardants (HFFR) have also received much attention be-
cause of the absence of toxic gases and smokes during combustion compared
to halogen-type flame retardants. Intumescent flame retardants, containing phos-
phorus and nitrogen have become more and more attractive in various industrial
applications in recent years. During combustion, the HFFR forms an expanding
charred crust to protect the underlying polymeric material from further attack
from flame or heating (Zhu & Shi 2001). The action of flame retardants can occur
across both or either of the vapor phase and the condensed phase. Halogen-type
flame retardants usually follow the vapor phase mechanism while intumescent
systems containing phosphorus and nitrogen generally follow the condensed
phase mechanism. However, combustion is a complex process, there may be dif-
ferent mechanisms with different flame retardants.
For many years, halogenated hydrocarbons, such as CF3Br, were used as fire
suppressants. However, due to their high ozone depletion potential, they are no
longer being manufactured in industrialized countries, as stipulated in the 1990
Montreal Protocol. The search for effective replacements has led to a family of
organophosphorus compounds (OPCs) that have shown considerable promise as
flame inhibitors. The early work of Twarowski (1993) demonstrated that phos-
phine (PH3) accelerated radical recombination in hydrogen oxidation, and subse-
quent work by Korobeinichev et al. (2004) began to explain how OPCs inhibited
hydrogen flames and hydrocarbon flames. Chemically active flame inhibitors alter
flame chemistry by catalytic recombination of key flame radicals, especially H
and O atoms, and OH radicals. The H atoms are particularly important in flame
propagation, since the principal chain branching reaction in hydrogen and hydro-
carbon flames is H + O2 → OH• + O•. Fast elementary reactions interconnect these
small radical species, and removal of any of them through recombination reduces
concentrations of all of them correspondingly. Therefore, radical recombination
leads to fewer H atoms in the reaction zone, which leads to reduced chain branch-
ing and a lower burning velocity in a premixed flame (Korobeinichev et al. 1999).
The need for fire retarding building materials, such as rigid PU foam insula-
tion, has led to the development of many new phosphorus-containing polyether
and polyesters. Piechota (1965) has shown the value of phosphorus compounds
in such fire retarding systems, and that phosphorus-containing rigid PU foams
develop an optimum flame protection at phosphorus content of 1.5%. In general,
chemically bond phosphorus compounds are preferred over noncreative additive
types. The rigid PU foams containing chemically bond phosphorus flame retard-
ing agents retain essentially all of their phosphorus and most of the initial flame
resistance after exposure to various combinations of heat and moisture (Gjurova
et al. 1986). The test formulations employing noncreative flame retardants be-
came non-self-extinguishing because of loss of phosphorus during one or more
of the aging tests employed. Hydrolytic stability was the main determining factor
for retention of phosphorus in the reactive additives. The presence of phosphorus-
oxygen-carbon bonds, which are susceptible to hydrolysis in many compounds,
has made compounds containing them unsuitable for use under conditions of hu-
midity and heat. This has led to the interest in preparing phosphorus compounds
containing stable phosphorus-carbon bonds, especially compounds in which the
phosphorus moiety is linked to a carbon-carbon backbone. These compounds, in
turn, must also contain suitable groups for further reaction to form polyethers or
polyesters useful in preparing polyurethanes (Quinn 1970).
14.1.4 Palm-based PU
Palm oil is one of the most widely used plant oils in the world. It is produced from oil
palm tree which is grown in mass plantation in tropical countries such as Malaysia. In
Malaysia, a ton of its fresh fruit bunches (FFB) yields 200 kg crude palm oil and 40 kg
palm kernels which, in turn, yield about 50 wt%, or 20 kg of palm kernel oil (PKO). A
hectare of estate can yield 20–24 tons of FFB per year, which in turn yield 4 to 5 tons
of palm oil and 400–500 kg of PKO (Tuan Noor Maznee et al. 2001).
There is several research studies carried out that made use of palm oil for PU
preparation (Chian & Gan 1998; Tuan Noor Maznee et al. 2001). Palm oil consists
of mainly triglycerides (Tri-Gs), thus, it is necessary to introduce hydroxyl groups
to a molecule of Tri-G for urethane reaction (Badri 2012). PU which sometimes
is also known as urethane or isocyanate polymer has once been of the most im-
portant segments in the polymer industry for decades (Healy 1963). The onset of
urethane bond dissociation is somewhere between 150°C and 220°C, depending
on the type of substituent; the isocyanate and polyol. Saturated hydrocarbons are
known to have relatively good thermal and thermo-oxidative resistance compared

to polyether and polyester derived from petrochemicals.
The thermal stability of polyurethanes is also very much dependent on the
chemical structure of the polyols and diisocyanates used in their formation. Poly-
ols containing aromatic groups show higher thermal stability than that of aliphatic
polyols (Sarkar & Adhikari 2001). Javni and coworkers (2000) reported a study
on thermal stability of polyurethanes based on vegetable oils such as corn, saf-
flower, sunflower, peanut, olive, soybean, canola, and castor oil in air and also
in nitrogen by thermogravimetric analysis (TGA) and Fourier transform infra-
red (FTIR). In their study, natural oil-based PU had better initial stability in air
than the polypropylene oxide-based polyurethane (PPO-PU), while the latter was
more stable in nitrogen at initial stage of degradation, when the weight loss at
higher conversion is taken as the criterion of stability then oil based PU better
thermal stability both in air and nitrogen. The effect of soft segment content and
its molecular weight has been studied by Reimann et al. (2003) and Saraf et al.
(1985). The results showed that the degree of crosslinking and tensile properties
depend mainly on the ratio of soft/hard segments, and are unaffected by varia-
tions in the sequence length of the soft segment at a given soft segment content.
Polyurethane-nitrolignin (PUNL), a new network polymer, was synthesized from
a castor oil based-PU prepolymer and nitrolignin (NL) (Zhang & Huang 2001).
The results indicated that PUNL film with 2.8% NL content, was the most mis-
cible, and its tensile strength and elongation at break were 2 times higher than that
of PU film. The crosslink densities of PUNL films increased with the increase of
NL content until about 3%, similar to the variety of the mechanical properties.
Thermogravimetric analysis revealed that the thermal stability of PUNL films was
slightly higher than that of PU. The covalent bonds occurred between PU prepoly-
mer and the NL in the PUNL films, forming crosslink networks, which resulted
in the enhancement of mechanical properties and thermal stability. NL has a far
higher reactivity with PU than nitrocellulose.
14.2 PREPARATION OF PALM-BASED PU FILLED WITH TRIS (2, 4- DI

TERT BUTYL PHENYL PHOSPHITE)
14.2.1 2, 4-Ditert-Butylphenyl Phosphite as the Flame

Retardant
2, 4-ditert-butylphenyl phosphate (commercially known as Irgafos 168) is a hy-
drolytically stable phosphite processing stabilizer. It is a hydrophobic, high mo-
lecular weight (MW = 646 g/mol) compound. It has low volatility and extremely
high resistant to hydrolysis (Fischer et al. 1999). It provides excellent antioxi-
dant process stability to organic polymers, resistance to discoloration and adds
long-term protection against thermo-oxidative degradation after processing (Ciba
Specialty Chemicals 2003). In this study, it undergone sieving procedure and was
used without further treatment. An Endocott sieve was used to screen the FR into
a size of 45 µm in order to obtain uniformity of particle size and to avoid ag-
glomeration during preparation of the composites. The FR was analyzed using
Scanning Electron Microscope X-100 model Philips reveals an average size of 18
µm as shown in Figure 2.
FIGURE 2 The SEM micrograph of Irgafos 168 as a flame retardant.
The melting point was determined using digital melting apparatus model
Barnstead, UK. The moisture content was determined by drying of FR in the
conventional oven at 105°C for 20 h. It is insoluble in water. The moisture content
was 0.33% with melting point of 182°C. The physical properties of Irgafos 168
are tabulated in Table 1.
TABLE 1 Physical properties of Irgafos 168 as a flame retardant
Parameters Properties
Color White
State at room temperature Solid (Powder)
Average particle size, µm 18
Moisture content, % 0.33
Solubility in water Insoluble
Melting point, °C 182
FTIR Spectroscopy Analysis of FR
The FTIR spectroscopy analysis of the FR indicated the presence of low intensity
and broad peak at 3429 cm-¹ refer to OH (moisture) and sharp peak at 1491 cm-¹
and 1212 cm-¹ belong to C=C (aromatic). The P–O–C group respectively as sum-
marized in Table 2. The absorption peaks at 2961 cm-¹ and 2868 cm-¹ indicate the
CH3 and CH stretching respectively (Pavia et al. 2001).
TABLE 2 The FTIR spectroscopy analysis of Irgafos 168 as a flame retardant
Functional Group Wavenumber (cm-¹)
C=C (aromatic) 1602, 1491
CH3 (stretching) 2961
CH (stretching) 2868
P–O–C (stretching) 1212, 853
CH and CH3 deformation 1398
14.2.2 (PKO)-based Monoester-OH
The patented method described by Badri (2012) is used in preparing the PKO-
based monoester-OH (PE) through polycondensation and esterification processes.
The synthesis is carried out at temperature range of 185–195°C for 30 min with
nitrogen gas blanket. The production is managed by UKM Technology Sdn Bhd
through its pilot plant in MPOB-UKM Station, Selangor, Malaysia. The PE is
stored in a screw-tight container and used without further purification. The FTIR
spectroscopy analysis is carried out using Perkin Elmer spectrum V-2000 spec-
trometer for the liquid phase PE. Sodium chloride (NaCl) window was used. The
PE is scanned between wavenumbers of 4000 to 700 cm-¹. The moisture content
of PE is determined using Karl Fischer Titrator model Metrohm KFT 701 series
following ASTM D4672-91 standard. The PE is a golden yellowish liquid. It has
low moisture content (0.09%) and low viscosity (374 cps). These are advanta-
geous in formulating PU system especially when processing of end product is
concerned. The physical properties are summarized in Table 3.
TABLE 3 Physical properties of the PKO-based PE
Parameter Result
Color Golden yellow
Odor Odorless
State at room temperature Liquid
Density at 25°C, g/cm3 0.992
Viscosity at 25°C, cps 374
Moisture content at 25°C, % 0.29
The FTIR spectrum displays several absorption peaks as tabulated in Table 4.

The peak at 3472 cm-1 refers to the hydroxyl group O–H from free water mole-
cules overlapping with OH of the carboxylic acid. However, the broad and strong
peak at 3390 cm-1 refers to the hydroxyl group OH exists in ester chain. Peaks at
2924 and 2854 cm–¹ indicates the CH2 and CH3 scissoring respectively. Peaks at
1739 and 1622 cm-1 are carbonyl ester group (C=O) and carbamate (C–N) respec-
tively (Kenkel 1994). The ester synthesized is a substance with hydroxyl func-
tional group terminal. The presence of carbamate group indicates the formation
of bond between C of the fatty acid and N of the alcohol amine. Shifting of peaks
from 1746 cm-1 (C=O for carboxylic acid) to 1739 cm-1 indicates the formation
of ester linkage.
TABLE 4 The FTIR Analysis of the RBD PKO and PKO-based PE
Functional Groups Wavenumber
RBD PKO PE
OH (ester) 3472 3390
CH3 and CH2 2924, 2854 2924, 2854
C=O 1746 1739
C−N - 1622
14.2.3 PKO-Based PU and Its Fire Retarding Composites
The PE-based PU was prepared by reacting 90 g crude MDI with 90 g PE-based

resin (prepared based on ingredients in Table 5). The mixture was agitated vigor-
ously using a standard propeller with a speed of 2000 rpm until well-mixed (~60
seconds) at room temperature. The reaction time; cream time (CT), gel time (FT),
tack-free-time (TFT), and rise time (RT) were noted. These reaction times were
important in the preparation of PU composites in identifying the initial reaction
time and demolding time.
TABLE 5 Ingredients of the PE-based resin
Ingredients Part by weight, pbw
PE 90 90 90 90
Niax L5404 2 2 2 2
Glycerin 10 10 10 10
PMDETA 0.4 0.4 0.4 0.4
TMHDA 0.3 0.3 0.3 0.3
FR (wt% based on resin) 0 2 4 6
Total pbw 102.7 103.9 105.1 106.3
The free-rise density was calculated by dividing the mass of the foam in the
cup, with the capacity of the cup as shown in Equation (1):
(mass of the foam in the cup-mass of the cup), kg

Free-Rise Density (FRD), kg/m3 = (1)
capacity of the cup, m3
The FRD was set at the range of 37–39 kg/m3 to ensure the resulted mold-
ed foam is in the range of 42–45 kg/m3. The above procedures were repeated
and the mixture was poured into a pre-waxed mold, covered and screwed tight.
The PU was demolded after 30 min. The molded density was calculated using
Equation (2).
Mass of the molded PU, kg

Molded density (MD), kg / m3 = (2)
Volume of the mold, m3
The molded PU was conditioned for 16 h at 23 ± 2ºC before further charac-

terization following standard method BS 4370: Part 1: 1988. The FR-filled PU
composites were prepared by using the same procedure, but with the addition of
FR (by weight percent of resin) as shown in Table 5.
14.3 PROPERTIES OF PALM-BASED POLYURETHANE AND

POLYURETHANE COMPOSITES
14.3.1 FTIR Spectroscopy Analysis
The FTIR Spectroscopy analysis was carried out on Perkin Elmer spectrum
V-2000 spectrometer by potassium bromide (KBr) method for the solid sample of
PU and its composites. The samples were scanned at wavenumbers ranging from
4000 to 700 cm-¹. The differences in peaks of the control PU (0% FR), and the
FR-filled composites (2–6%) were observed to identify any chemical changes in
the urethane linkage.
Polyurethanes are linear polymers that have a molecular backbone containing
carbamate groups. This group, better known as urethane, is produced through
a chemical reaction between diisocyanate and polyamide. The FTIR spectra of
control PU is shown in Figure 3. The FTIR spectrum of FR-filled PU did not
show any significant different or any presence of new peaks compared to the
spectrum of the control PU except at one peak. This peak is attributed to the pres-
ence of P–O at 853 cm-1 and 905 cm-1 (as summarized in Table 6). It is not clearly
shown when 2% of FR is added but with increasing amount of FR it is obviously
shown as indicated in Figure 4. The FR only reacts with the radical that was pro-
duced during oxidation reaction of PU (Schwetlick 1990) and thus no indication

of chemical bonding between PU and FR.
FIGURE 3 The FTIR spectrum of control PU.
FIGURE 4 The FTIR spectrum for PU composite at 6% FR loading.

TABLE 6 The FTIR Analysis of the control PU and PU composites
Functional Wavenumber, cm-1

Groups
Control PU PU + 2% FR PU + 4%FR PU + 6%FR
N-H stretching 3401 3391 3392 3368
C–H Stretching 2925, 2848 2924, 2848 2926, 2848 2925, 2853
C=O Vibration 171 1736 1736 1737
N-H Vibration/ 1526 1528 1523 1528

bending
C=C Aromatic 1413, 1607 1413, 1607 1412, 1599 1412, 1601
stretching
P–O–C – – 853 853, 905
The FTIR spectrum of control PU shows the absence of free OH group; an

indication of a complete conversion of PE to urethane moiety (NH–C=O). A peak
at 3401 cm-1 is attributed to the stretching absorption of N–H group (overlapping
with OH peak) (Wang et al. 1999) and the corresponding N–H bending absorp-
tion (1526 cm-1) confirmed the presence of the secondary amine that constitutes
part of a urethane linkage. Urethane carbonyl absorption (NH–CO–O) occurs at
1700–1760 cm-1 (Mortley & Bonin 2007). A band at 2948 cm−1 is attributed to the
asymmetric stretching vibration of –CH3 and 2848 cm−1 which is formed from
urethane bond with PE. The sharp bands at 1607 cm−1 and 1413 cm−1 are both
assigned to the stretching vibration of C=C of aromatic ring (Sun et al. 2003). A
peak at 1719 cm-1 refers to carbonyl vibration and C–N stretching near 1219 cm-1
(Chattopadhyay et al. 2006). A strong absorption at 1595 cm-1 is due to the aro-
matic groups of C–NH bond (Czech et al. 2006).
14.3.2 Mechanical Properties
Shore D Hardness
A Portable shore D hardness indentor (Durometer Affri system Series 3300 MRS,
Affri Cee-Versea, Italy) is used, with measurement being conducted according to
ASTM D2240 standard to determine the hardness of the sample. The boards are
cut to samples with dimensions of 130 mm × 130 mm × 3 mm (length × width ×

thickness). The values of shore D hardness obtained represent mean of five speci-
men measurements.
A plot of shore D hardness index is shown in Figure 5 indicates the effect of
varying amount of FR in PU on shore D hardness index. Hardness is most com-
monly defined as resistance of polymer material to indentation. Indentation is the
pressing motion on a point at the sample with known force (Dowling 1999). Hard-
ness index may give an initial indicator to physical strength of the PU composites.
It increased with increasing amount of filler. This result is in close agreement with
research carried out by Badri et al. (2006) and Rusu et al. (2001), where compos-
ites with filler produced higher hardness index than without filler. The hardness
index increased by 8%, 27%, and 38% with 2%, 4%, and 6 % (w/w) of FR loading
respectively.
FIGURE 5 Shore D hardness index of the control PU and FR-filled PU composites.
Impact Strength
Impact testing is conducted according to ASTM D256-88 standard. The Izod

method is employed, using unnotched samples with dimensions of 63 mm × 13
mm × 3 mm (length × width × thickness) on a Zwick impact tester (Model 5101,
Zwick Roell Group, Atlanta, Georgia, USA ), with a pendulum energy of 2 J. The
impact strengths are calculated by dividing the energy (J) recorded on the tester
by cross-sectional area (mm²) of the specimens. The values of the obtained impact
strengths represented the mean of five specimen measurements.
Figure 6 shows the impact strength of the control PU and FR-filled PU com-
posites. The impact strength of materials reflected its ability to resist fracture.
Impact strength of the FR-filled PU composites decreased with increasing FR
content. This may be attributed to weaken interfacial bonding between FR and
PU matrix with higher amount of FR. The highest impact strength is observed
for control PU (6.9 k/m2). The PU composite with 6% FR has the lowest impact
strength compared to others, in agreement with research carried out by Liu and
Wang (2006) where red phosphorus (RP) and melamine cyanurate (MC)-encapsu-
lated RP (MERP) were used as FR. They observed that impact strength decreased
with increasing FR loading, but the situation is much better for MERP flame retar-
dant system due to better compatibility between MERP and the polymer matrix.
The impact strength decreased by 9%, 13%, and 17% from 2 to 4 and to 6% FR
loading respectively. The optimum loading is observed at 2% FR. The presence of
higher loading of FR embedded in the polymer matrix results in reduced ability
to absorb impact energy. The FR created matrix discontinuity, and each particle
acted as site of stress concentration, and led to micro-crack (Dvir et al. 2003).
FIGURE 6 Impact strength of the control PU and FR-filled PU composites.

The investigation of the impact strength of the composites revealed that the
impact strength of the PU control is higher than with FR -PU composites. This
again showed that composites with FR are not able to absorb more energy from
the matrix and distributed it efficiently in the composites. The impact strength
decreased as the percentage of FR loading increased.
Flexural Strength and Modulus
The flexural strength by means of three points bending testing is conducted ac-
cording to ASTM D790-86 standard. Samples are cut to dimensions of 130 mm
× 13 mm × 3 mm (length × width × thickness). The flexural test is carried out
by using a Universal Test Machine (Model 5525, Instron Corporation, Norwood,
Massachusetts, USA) at a cross-head speed of 3.1 mm/min. The values obtained
represented the mean of five specimen measurements.
Figure 7 and Figure 8 show the flexural strength and modulus of the control
PU and the FR-filled PU composites respectively. As the content of FR increased,
the flexural strength decreased. The reduction in strength is ascribed to the poor
adhesion between FR and PU matrix due to agglomeration of FR particles as ex-
hibited in the SEM micrographs.
FIGURE 7 Flexural strength of control PU and FR-filled PU composites.

The agglomeration becomes more dominant at higher content of FR and the

flexural strength reduced due to uneven dispersion of FR throughout the PU ma-
trix. This result is in agreement with the study reported by Jang et al. (1998) where
flexural strength of polymer composite decreased when amount of phosphate as
FR was increased.
Maximum flexural strength of polymer composite is observed on control PU
and reduced by 6% with addition of 2% FR. Further reduction is observed with
higher amount of FR (4% gave a reduction of 25% from the control PU). The
highest amount of FR gives the lowest flexural strength as shown in Figure 7
(reduction of 33% from the control PU for 6% FR).
Figure 8 describes flexural modulus of control PU and its composites. Flex-
ural modulus reflects the rigidity of the material. The modulus decreased by 5%,
16%, and 19% respectively when 2%, 4%, and 6% of FR are added to the PU
matrix. The lowest modulus is observed at 6% FR with modulus of 827 MPa.
Higher loading of FR decreased the wetting properties of the matrix and reduced
degree of encapsulation of matrix around FR. As such, the FR is exposed to direct
stress and low stress transfer. Parallel to impact strength scenario, this may also
lead to weak interfacial bonding between FR and PU matrix (Jang et al. 1998;
Rusu et al. 2001).
FIGURE 8 Flexural modulus of the control PU and FR-filled PU composites.

14.3.3 Thermal Properties
Thermogravimetric Analysis (TGA)
The TGA analysis serves as a diagnostic technique used to determine thermal

stability of the material and its fraction of volatile components by monitoring the
change in weight that occurs as it is being heated. Thermal stability and weight
loss of the PU and its composites was measured using a thermogravimetric ana-
lyzer model Shimadzu TGA-50 with temperature range from 30–600°C at a heat-
ing rate of 10°C/min under nitrogen gas blanket. Samples are placed in an alu-
mina pan holder in a mass range of 5–15 mg.
The thermogram of FR is shown in Figure 9. It is thermally stable up to 236°C
and this is higher than control PU (at 172°C). It undergoes single stage decompo-
sition at 230–295°C with total weight loss of 97%. Thermograms of control PU
and FR-filled PU composites with varying FR contents are as tabulated in Table
7. The TGA thermogram of control PU shows two main weight loss stages indi-
cating presence of two thermal degradation temperatures. It is stable at 172°C,
a common stability temperature for PU (Hepburn 1991). Initial weight loss of
about 14% commences at 172°C to 250°C. Control PU started to degrade at lower
temperature (175°C) compared to FR-filled PU composites loaded with FR. There
is an insignificant difference in the degradation temperature when FR is added.
However, total weight loss of FR-filled PU composites reduced down to 66.0%
with addition of 6% FR. The FR plays an important role in boosting the thermal
oxidative stability (Shao et al. 1999).
FIGURE 9 The TGA thermogram of the FR (Irgafos 168).

TABLE 7 The TGA results for the control PU and FR-filled PU composites with 2 wt%,
4 wt%, and 6 wt% of FR
Content of FR, wt% Tstable ,ºC T1,ºC Total weight

loss, %
0 172 172–495 95.2
2 175 175–496 91.6
4 175 175–497 86.3
6 173 173–500 66.0
Differential Scanning Calorimetry (DSC) Analysis
The thermal behavior of control PU and its composites were determined using a
Perkin Elmer Model DSC-7 differential scanning calorimeter interfaced to Model
1020 controller. The samples were analyzed from room temperature to 250°C (as
PU decomposed at a temperature more than 250°C) at a heating rate of 10°C/min.
the standard aluminum pan is used to analyze about 10 mg samples under nitrogen
gas atmosphere.
There is no evidence of the presence of melting and crystallization tempera-
tures peak in the DSC thermogram of the control PU and FR-filled PU composites.
The PU is an amorphous polymer (Fedderly et al. 1998). The PU is convenient-
ly described in terms of it characteristic glass transition temperature (Tg) which
identify the point where the material changes from rigid to a rubbery behavior
(Bernhard 2005). The Tg of control PU is observed at 60°C. The Tg of FR-filled
PU composites increased by 3.3% with loading of 2% FR. The Tg is associated
with mobility of the polymeric chains. Consequently, an increase in Tg can be at-
tributed to the presence of FR in the PU system which implies that the addition of
the flame retardant constrains the motions of the chains (Gregoriou et al. 2005).
But an insignificant improvement is observed with the addition of 4% and 6 %
FR as summarized in Table 7. The degree of interaction between particles of the
FR is not strong enough to modify the activation temperature of molecular move-
ments. The cross-linking phenomenon during the built-up of the polymerization
is disrupted by the presence of FR (Yakushin et al. 1999).
The same trend is observed for the specific heat capacity. The intensity of
the change in specific heat capacity (Δ Cp) is associated with Tg. Specific heat
capacity of control PU is 1392 J/kg·K. Specific heat capacity of the PU composite
increased by 5.8 % when 2% FR is added. However, specific heat capacity of FR-
filled PU composites decreased by 3.5% and 14% when 4% and 6% FR respec-
tively are added. A significant drop in specific heat capacity (Δ Cp) is observed
when more flame retardant is introduced to PU composites, therefore gradual and
linear reduction occurred according to addition of FR (Sarier & Onder 2007).
TABLE 8 The Tg and specific heat capacity of control PU and FR-filled PU composites
Samples Glass transition tem- Specific heat capacity (Cp) J/

peratures (Tg), °C kg·K
Control PU 60 1392
PU + 2% FR 62 1472
PU + 4% FR 61 1440
PU + 6% FR 57 1190
Bomb Calorimetric Analysis
The effect of FR on network structure of control PU and FR-filled PU composites

can be determined by measuring the enthalpy. The enthalpy from combustion was
tested with a bomb calorimeter. Bomb calorimeter model IKA C 4000 was used
to determine the initial enthalpy. One gram of PU composites is put in the sample
cup. The bomb was prepared by putting a wire (5 cm length) between two elec-
trodes. A thread was also tied on the divider of the two wires touching the sample.
The bomb was placed inside the chamber and was closed tightly with purging O2
at a pressure of 30 bar O2 into the chamber (Oelke & Zuehlke 1969; Arthur 1986).
The chamber was transferred to a container containing 1.8 L distilled water. The
monitoring is carried out using calorimeter IKA system.
Figure 10 presents the enthalpy of control PU and the FR-filled PU compos-
ites. It decreased by increasing the amount of FR. This trend is in good agreement
with results reported elsewhere (Toldy et al. 2006) where, they use OPCs and
combine them with montmorillonite nanoparticles, and use it to retard flame and
incorporate them in epoxy resin.
FIGURE 10 Enthalpy of the control PU and FR-filled PU composites.
Enthalpy of control PU is 30860 kJ/kg. When 2% FR is added to the PU ma-

trix, the enthalpy is 30740 kJ/kg. A PU composite with 4% FR showed enthalpy
of 30337 kJ/kg. The lowest enthalpy is observed for PU composite with 6% FR
(30180 kJ/kg). This is attributed to the fact that less energy is required to break the
bond due to the presence of FR.
Fire Resistivity Test
This test is carried out to determine the relative burning characteristics and flame
resistance properties. It measured and described the properties of materials, prod-
ucts or assemblies in reactions to heat and flame under controlled laboratory con-
ditions. The test results represented flaming plus glowing time in seconds, for a
material under the conditions of the test. ASTM D 5048-90 (procedure B-test of
plaque specimens) is conducted as shown in Figure 11.
FIGURE 11 Schematic diagram of fire test from ASTM D 5048-90: Procedure B.
Flammability tests are classified based on various characteristics of fire re-

sponse. In various flammability tests, the fire test is carried out to determine the
relative burning characteristic and flame resistance properties. Phosphite used in
this study has good flame retardancy and good thermal properties because the hy-
droperoxide decomposers prevent the split of hydroperoxides into highly reactive
alkoxy and hydroxyl radicals (Schkwetlic 1990). Figure 12 shows results of fire
test for control PU and its composites with varying amount of FR.
FIGURE 12 Burning rate of control PU and FR-filled PU composites.

The PU burns rapidly upon exposure to flame. It is highly combustible in

the absence of flame retardant (Reed et al. 2000). Burning rate for control PU
is higher than FR-filled PU composites. The burning rate of PU composites de-
creased significantly by 26.6% when 2% of FR added. The PU composite with
4% FR decreased by 21.5% and 17.7% with 6% FR. The FR shows excellence
fire retarding effect on the PU composites as reported in work (Jang et al. 1998).
The FR dissociates into radical species that compete with chain propagating and
branching steps in the combustion process.
One of the most damaging species in the oxidation process is the hydroper-
oxide. Under elevated temperature hydroperoxides decompose via hemolytic
cleavage to yield two free radicals. This step demonstrates the catalytic nature of
autoxidation. The destruction of hydroperoxides, which continually build up in
the polymer, is essential in protecting the polymer (Salamone 1996). Phosphites
prevent further formation of free radicals by decomposing unstable hydroperox-
ides prior to their homolytic cleavage. Instead, the unstable hydroperoxide forms
a stable product (Zhu & Shi 2001) as illustrated in Figure 13.
FIGURE 13 Phosphites prevent the split of hydroperoxides into extremely reactive
alkoxy and hydroxy radicals (Ciba Specialty Chemicals 2003).
The mechanism is shown below:
Mechanism 1: Phosphite reacts with peroxide
• •
R + O2 → R O2
• •
R O 2 + P(OR)3 → ROO P (OR)3
• •
ROO P (OR)3 → R O + O = P(OR)3
• •
R O + P(OR)3 → R O P (OR)3
• •
R O P (OR)3 → R + O = P(OR)3
•
2R O 2 → ROOR + O 2
Mechanism 2: Phosphite reacts with hydroperoxide
• •
R1OOH + P(OR)3 → [R 1O P (OR )3 H O]
• • •
[R1O P (OR )3 H O ] → R 1OH + O = P (OR )3
• •
R1OOH + P(OR)3 → [HO P (OR )3 R1 O]
• •
[HO P (OR )3 R1 O ] → R 1OH + O = P (OR )3
Dynamic Mechanical Analysis (DMA)
The DMA is conducted on a dynamic mechanical analyzer model TA Instrumen-

tation (DMA 2980). It is performed using a single cantilever at a frequency of 1
Hz. The sample was cut into a 25 mm × 12.5 mm × 3 mm specimens. The testing
temperature ranged from 25°C to 150°C with a heating rate of 5°C /min.
The DMA measures the deformation of a material in response to vibration
forces or sinusoidal wave. The storage modulus E´ refers to stiffness of mate-
rial and tan δ gives the amount of energy dissipated as heat during deformation
(Nielsen & Landel 1974). The investigation of dynamic storage modulus and in-
ternal friction over a wide range of temperature and frequencies has proven to be
very useful in studying the structure of polymers and the vibrational properties
in relation to end-use performance (Costa et al. 2005). It is conducted due to (a)
Tg determined from tan δ curves is more accurate than by other thermal methods
and (b) any decrease in elastic moduli accompanying Tg can be monitored by the
storage modulus (Lu et al. 2003).
The storage modulus of the FR-filled PU composites with 0%, 2%, 4%, and
6% FR is shown in Figure 14 (a). The DMA curve indicates a significant de-
crease in storage modulus E´ around the onset Tg of FR-filled PU composites.
Storage modulus of FR-filled PU composites with 2% and 4% FR decreases by
15% and 20% respectively, attributing to poor interaction between FR and PU
matrix as supported by SEM micrographs in the following section. Addition of
FR decreased storage modulus of the PU composites to a minimum value with
loading of 6% FR (975 MPa). The excess amount of FR in PU matrix gives out
poor mechanical properties resulting in reduction in flexural and impact strengths.
This finding was also obtained by Mat Amin and Badri (2007) where, an increase
in the amount of kaolinite in the polymer matrix reduced the mechanical strength
of the composite.
FIGURE 14 (Continued)

FIGURE 14 The DMA thermograms of control PU and FR-filled PU composites

exhibiting (a) storage modulus (b) loss modulus, and (c) tan δ.
The value of Tg is dependent on the chemical structure, flexibility of the mo-

lecular chain, steric hindrance, and bulkiness of side groups attached to the back-
bone chain (Mat Amin & Badri 2007, Song et al. 2005). Table 9 and Figure 14 (b)
show the onset Tg of loss modulus and tan δ obtained from DMA. The FR-filled
PU composite with 2% FR has the highest onset Tg (105°C).
TABLE 9 Storage and loss moduli and the onset glass transition (Tg) of control PU and
FR-filled PU composite extracted from DMA Analysis
Samples Storage modulus Loss modulus Tan δ Tg (ºC)

(MPa) Tg (ºC)
Control PU 1275 72.29 103.94
PU + 2% FR 1080 76.55 105.08
PU + 4% FR 1010 72.29 103.44
PU + 6% FR 975 69.34 98.85
Tan δ sometimes is referred to as internal friction or damping such as vibration

or sound damping. It is the ratio of energy dissipated per cycle to the maximum
potential energy stored during a cycle. Tan δ is also used to evaluate Tg of the
samples (Lu et al. 2003). Figure 14 (c) delineates the vibration of tan δ of the
control PU and FR-filled PU composites.
The Tg of tan δ for control PU corresponds to Tg of polymer system and occurs
at 103.9ºC. The Tg of the FR-filled PU composites increases to 105ºC with 2% FR
in the PU matrix. Further addition of FR at 4% and 6% loading in the PU compos-
ites indicates a shift in tan δ at a lower temperature. The cross-linking phenomena
during polymerization is disrupted by the presence of FR. The Tg measured by
DSC is lowered than by DMA due to differences in effective frequencies of the
two instruments. However, the relationship of Tg obtained from DMA is in agree-
ment with that attained by DSC.
14.3.4 Scanning Electron Microscope (SEM) Analysis
A Leo VP SEM-1450 SEM is used to study the interaction and distribution of FR

in the PU composites. The observation is made onto impact fractured samples.
The samples were coated with gold of thickness 20A with Bio-rad microscience
division-SC 500 to prevent electrical charging during examination. The observa-
tion is made at 250 times magnification on control PU (0% FR) and its composites
with 2%, 4%, and 6% FR.
The SEM micrographs support the findings in the analysis of mechanical
properties. Figure 15 (a) shows SEM micrographs for fractured surface of control
PU. The control PU has uniform structure with homogeneity in the matrix. SEM
micrograph (Figure 15 (b)) of the PU composite with 2% FR indicates uneven
distribution of FR particles in the PU matrix. This non-uniformity between FR
particles and PU matrix is due to weak interaction between both of them, as indi-
cated by poor mechanical strength of the PU composites. Increase of FR content
in the PU matrix by 4% causes initial agglomeration of particles, affecting ad-
versely on dispersion and distribution of FR particles in the PU matrix. This led to
further reduction in the mechanical properties of the PU composites; due to poor
adhesion between FR and PU matrix as shown in Figure 15 (c). Agglomeration
is clearly observed in PU composite with 6% FR as shown in Figure 15 (d). The
agglomeration becomes dominant at higher FR content creating a non-uniform
distribution of PU composites thus directly affecting the mechanical properties of
PU composites (Sumaila et al. 2006). The occurrence of particles agglomeration
is responsible for the FR–FR particle contacts instead of PU-FR particle contacts.
This shows that there is no physical interaction between FR particles and PU
matrix.
Figure 15 (Continued)

Figure 15 (Continued)

Figure 15 SEM micrographs of (a) PU control, (b) PU with 2% FR, (c) PU with 4%
FR, and (d) PU with 6% FR.
14.4 Conclusion
This study showed the effect of 2, 4-ditert-butylphenyl phosphite (FR) as fire

retardant on the mechanical and thermal properties (thermal stability and fire test)
of PU. Hardness index obviously increased with increasing amount of FR. How-
ever, impact strength of FR-filled PU composites decreased with increasing FR
content with the highest observed for control PU and the lowest for PU composite
with 6% FR. The optimum loading was observed at 2% FR. The maximum flex-
ural strength was observed on control PU but a reduction with loading of higher
amount of FR. The modulus decreased by 5%, 16%, and 19% when 2%, 4%, and
6% of FR were added to the PU matrix respectively. The lowest modulus was
observed at 6% FR. Thermal stability of PU composites was improved by the ad-
dition of FR, which may be attributed to excellent thermal stability of phosphite
as FR agent. The DMA curves indicated that storage modulus E´ decreased sig-
nificantly around the onset Tg of the PU composites. The fire test indicated lower
burning rate (from 5.30 mm/s to 2.80 mm/s) as the percentage loading of FR in-
creased. The enthalpy determined by bomb calorimeter supported the burning test
results. Enthalpy of PU composites decreased by 2%, 3%, and 5% when 2%, 4%
and 6% of FR were incorporated to the PU matrix, respectively. The observation

on the SEM micrographs indicated agglomeration of particles, affecting adversely
on dispersion and distribution of FR particles in PU matrix. This led to deteriora-
tion of the mechanical properties of PU composites.
KEYWORDS
•• 2, 4-Ditert-butylphenyl phosphite
•• Burning properties
•• Dynamic mechanical analysis (DMA)
•• Flame retardant
•• Palm-Based Polyurethane
Acknowledgment
These works on the preparation of fire retarding palm-based polyurethane are

based on ranges of polyurethane polyols produced at a larger scale at a pilot plant
in Universiti Kebangsaan Malaysia. It was commissioned in November 2011.
This is being brought into realization with the support of Universiti Kebangsaan
Malaysia under its entities UKM Technology Sdn Bhd and Centre for Collabora-
tive Innovation through a grant No. UKM-IF -1-2010-013. An appreciation is also
dedicated to School of Chemical Sciences and Food Technology, Polymer Re-
search Center and Faculty of Science and Technology for research facilities pro-
vided. Thanks to Ministry of Higher Education, Ministry of Science, Technology
and Innovation for other financial supports in research grants form. Major contri-
butions definitely came from graduates and colleagues of Universiti Kebangsaan
Malaysia. For special individuals who initiated this project, Zulkefly Othman and
in memory of Haji Badri Haji Zakaria and Hajah Fatimah Haji Ismail, my greatest
thanks to you.
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Fire-Resist Bio-Based Polyurethane for Structural Foam

Chapter · April 2014

Khairiah Haji Badri

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14.1 Fire-Resist Bio-Based Polyurethane for Structural foam Application.... 387

14.1 FIRE-RESIST BIO-BASED POLYURETHANE FOR STRUCTURAL

14.1.1 Polyurethane (PU) and its Properties

PU is a versatile thermosetting polymer. Its properties are modified either by vary-

FIGURE 1 The molecular structure of Irgafos 168 [tris (2, 4-di-tert-butylphenyl)

14.1.3 Fire Retarded PU Composites

known to have relatively good thermal and thermo-oxidative resistance compared

14.2 PREPARATION OF PALM-BASED PU FILLED WITH TRIS (2, 4- DI

14.2.1 2, 4-Ditert-Butylphenyl Phosphite as the Flame

FIGURE 2 The SEM micrograph of Irgafos 168 as a flame retardant.

TABLE 1 Physical properties of Irgafos 168 as a flame retardant

State at room temperature Solid (Powder)

Average particle size, µm 18

Moisture content, % 0.33

Solubility in water Insoluble

Melting point, °C 182

FTIR Spectroscopy Analysis of FR

TABLE 2 The FTIR spectroscopy analysis of Irgafos 168 as a flame retardant

Functional Group Wavenumber (cm-¹)

C=C (aromatic) 1602, 1491

CH3 (stretching) 2961

P–O–C (stretching) 1212, 853

CH and CH3 deformation 1398

14.2.2 (PKO)-based Monoester-OH

TABLE 3 Physical properties of the PKO-based PE

Color Golden yellow

State at room temperature Liquid

Density at 25°C, g/cm3 0.992

Viscosity at 25°C, cps 374

Moisture content at 25°C, % 0.29

The FTIR spectrum displays several absorption peaks as tabulated in Table 4.

TABLE 4 The FTIR Analysis of the RBD PKO and PKO-based PE

Functional Groups Wavenumber

OH (ester) 3472 3390

CH3 and CH2 2924, 2854 2924, 2854

C=O 1746 1739

14.2.3 PKO-Based PU and Its Fire Retarding Composites

The PE-based PU was prepared by reacting 90 g crude MDI with 90 g PE-based

TABLE 5 Ingredients of the PE-based resin

Ingredients Part by weight, pbw

PMDETA 0.4 0.4 0.4 0.4

TMHDA 0.3 0.3 0.3 0.3

FR (wt% based on resin) 0 2 4 6

Total pbw 102.7 103.9 105.1 106.3

(mass of the foam in the cup-mass of the cup), kg

Mass of the molded PU, kg

The molded PU was conditioned for 16 h at 23 ± 2ºC before further charac-

14.3 PROPERTIES OF PALM-BASED POLYURETHANE AND

14.3.1 FTIR Spectroscopy Analysis

duced during oxidation reaction of PU (Schwetlick 1990) and thus no indication

FIGURE 3 The FTIR spectrum of control PU.

FIGURE 4 The FTIR spectrum for PU composite at 6% FR loading.

TABLE 6 The FTIR Analysis of the control PU and PU composites