2731 Bartram Road, Bristol, PA 19007 800-541-0559 www.unitedchem.

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Formulating Silicone Adhesives Gels and Sealants

John H. MacMillan Ph .D. Ph.D.
1

Silicone Technology is a wide and mature science spanning the gamut of materials from commodity lubricants to high performance defense coatings. This paper will give an overview of the basic technology and classes of silicone fluids. Cure types,basic formulations,applications,catalyst types and blending methods will all be discussed. United Chemical Technologies (UCT) is a major manufacturer of high quality silicones. During the discussions the catalog numbers for the corresponding UCT product will be introduced when appropriate. In many chemical reactions the reacting groups are color coded for clarity. For those wanting additional detail on industrial manufacturing methods for bulk silicones, the Kirk Othmer Encyclopedia (Ref 1) is an excellent guide. More recent advances in high performance silicone materials are reviewed by Brook (Ref 2) in an excellent text. Before we discuss basic silicone structures and curing mechanisms,it is necessary that the reader be familiar with simple silicone structural terminology and other common industrial terms. Figure 1 and Table 1 review the structural features and industrial terms commonly encountered.

Figure 1

Silicones INTRODUCTION
CH3 CH3 Si CH3 O

Me Si Me O

D unit

( )
CH3 Si O CH3 n

CH3 Si CH3 CH3

(Me 3 SiO)

M unit

O Me Si O O

T unit

O O Si O
3

Q unit

Table 1 Common Terms

Basic Terminology
Cure: Crosslink a liquid polymer system to where it forms an elastic gel ( sets up and solidifies). Addition Cure: Platinum Catalyzed, Examples: PC072, PC075, PC085 Condensation Cure: Tin, Zinc Catalyzed, Examples: PC040, PC050 Peroxide Cure: Peroxide Catalyzed, Example: PC010 RTV : Room Temperature Vulcanizabe (curable) system, Usually an addition or condensation cure resin.

The most basic class of silicones is the conventional inert polydimethylsiloxane series. They are trimethylsiloxy terminated and possess no reactive chemical functionality. These fluids find utility as plasticisers, lubricants, defoamers, in high temperature baths, and cosmetic products. Typical service temperatures are to 250 celsius. UCT offers the full line of these materials from very low to gum like viscosities. Table 2 is a compilation of this series.

Table 2 Conventional Silicone Fluids

Product#

Viscosity

Specific Gravity

Refractive Index

Flash Point

Pour Point

Polydimethylsiloxanes Trimethylsiloxy Terminated CAS No. (63148-62-9) PS034 PS035 PS036 PS037 PS037.5 PS038 PS038.5 PS039 PS039.5 PS040 PS041 PS041.2 PS041.5 PS042 PS043 PS044 PS045 PS046 PS047 PS047.5 PS048 PS048.5 PS049 PS049.5 PS050 .65 1.0 1.5 2.0 3.0 5.0 7.0 1.0 2.0 5.0 100 200 350 500 1,000 5.000 10,000 12,000 30,000 60,000 100,000 300,000 600,000 1,000,000 2,500,000 .761 .818 .853 .873 .898 .918 .930 .935 .950 .960 .966 .968 .970 .971 .971 .973 .974 .974 .976 .976 .977 .977 .978 .978 .978 1.3750 1.3825 1.3880 1.3900 1.3935 1.3970 1.3980 1.3990 1.4000 1.4015 1.4025 1.4030 1.4031 1.4033 1.4034 1.4035 1.4035 1.4035 1.4035 1.4035 1.4035 1.4035 1.4035 1.4035 1.4035 -1 38 63 79 100 135 150 163 232 285 315 315 315 315 315 315 315 315 315 315 321 321 321 321 321 -68 -85 -75 -80 -70 -65 -65 -65 -65 -65 -65 -60 -60 -55 -50 -48 -48 -46 -43 -42 -41 -41 -41 -39 -38

Branched Polydimethylsiloxane CAS No. (68037-74-1) PS052 50 cSt. 0.97 1.4030

279

-85

Polydimethylsiloxane Emulsion PS053.5 30% silicone antifoam in water. Used to defoam biological mixtures by adding 2-50 mg/liter.

Although conventional fluids are stable thermally to 250 celsius, many high performance coating applications require higher temperature stability. Introduction of aromatic groups (phenyl rings) raises thermal stability to greater than 300 celsius. The indices of refraction and the rigidity of cured resins are also increased over conventional fluids. Figure 2 describes these materials in more detail. They are available with curable vinyl terminals at the polymer terminals and containing variable viscosities and mole percentages of phenyl groups. The most utilized UCT product line of curable aromatic silicones is the PS732-PS793 series of vinyl terminated fluids.

Figure 2 Thermal Silicones

CH3 CH3 Si CH3 O

( )( )
CH3 Si Si - O O m CH3 n

CH3 Si CH3 CH 3 CH3

CH3 Si CH3 O

( )
Si - O CH3

CH3 Si CH3 CH3

The most commonly used high temperature silicone fluids are the phenyl containing siloxanes. The phenyl group is usually incorporated in two ways. It may be introduced as a phenylmethylsiloxane or a diphenylsiloxane. As phenyl groups replace methyl groups in a polysiloxane, several changes occur. Lubricity, oxidation resistance, thermal stability and shear resistance are enhanced. For polymethylphenyl siloxane the service temperature is -55 to 290 C. In a closed oxygen-free system the polymethylphenylsiloxanes are stable for thousands of hours at 230C. The materials are used in heating baths. The tetrachlorophenyl-dimethylsiloxane copolymer is well-suited for metal to metal lubrication. They are also used as base oils for high temperature lubrication. The phenyl group also introduces rigidity in the silicone chain. When substitution exceeds 75 mole percent the polymers are solid. Diphenylhomopolymers demonstrate liquid crystal behavior between 250C and 500C. Silanol terminated polydiphenylsiloxane is a glassy solid useful as a resin intermediate. The refractive index also increases with phenyl concentration. At 15-20 mole percent phenyl concentrations the refractive index matches that of amorphous silica and transparent compounds may be prepared.

Figure 2 Thermal Silicones (Contd)

At low phenyl concentrations these fluids are dielectric coolants. They also function in place of standard dimethylfluids where extended service temperature is necessary. One special class of phenyl fluids are the dimer, trimer and tetramer fluids (see section on diffusion pump fluids). Because the introduction of a moderate concentration of phenyl groups also improves lubricity, members of the family have found utilization as lubricants for instruments and timing devices. High phenyl content fluids are also used as heat transfer media and chromatographic stationary phases. The polymethylphenylsiloxanes exhibit good radiation resistance by remaining serviceable up to 200 megarads exposure. The compressibility of phenyl containing siloxanes is reduced in comparison to dimethyl fluids. Polymethylphenylsiloxane has a compressibility of 5.5% at 20,000 psi. Dimethyl phenylmethylsiloxane copolymer has a compressibility of 6.5% at 20,000 psi.

Silicone fluids typically show low solubility in petroleum oils. Addition of long hydrocarbon chains on the backbone increases solubility in these oils and also the lubricity. The fluids are then of utility as oil well defoamers and cosmetic lubricants. These fluids are described in detail in Figure 3. The UCT product line is shown in Table 3.

10

Figure 3 Polymethylalkylsiloxanes
CH3 CH3 CH 3 Si CH3 O

( )
(CH2 )m Si O CH3 n

CH3 Si CH3 CH3

Silicones can be modified to impart organic characteristics to their inorganic structure, which makes them more compatible with organic materials such as petroleum oils and synthetic resins. Replacement of a methyl group with longer chain aliphatic moieties produces silicones with properties that more closely resemble hydrocarbons. When compared to polydimethylsiloxanes, methylalkylsiloxanes have greatly improved lubrication characteristics and greater compatibility with organic materials. The fluids have higher viscosity-temperature coefficients, lower compressibility and decreased oxidation stability. This last characteristic has been substantially overcome by compounding the fluids with stabilizers such as BHT or DSTDP or copolymerizing them with aromatic siloxanes as internal stabilizers. Lubrication properties are optimized when the alkyl unit is at least eight carbons long. Polymethyloctylsiloxane is useful as a lubricant for soft metals such as aluminum, zinc and copper. It is also useful as a rubber or plastic lubricant especially when mated against steel or aluminum. Polymethyloctylsiloxane is also employed in aluminum machining operations. With increasing length of the alkyl substituent the melting point increases. As the pour point of the alkyl modified siloxanes increases, the resemblance and compatibility with hydrocarbon oils increase. Polymethyltetradecylsiloxane has a high degree of hydrocarbon compatibility and maintains liquid behavior at room temperature. Polymethyloctadecylsiloxane is a creamy solid with a melting point just above room temperature. It is compatible with paraffin wax. It is used as a component in thread and fiber lubricant formulations and as a process aid in melt spinning. Methylalkylsiloxane reduces the surface tension of many non-aqueous solvents allowing them to act as wetting and leveling agents in coating and ink formations. 11

Table 3 Polymethylalkylsiloxanes
Prod#
PS130 PS130.5

Description [CAS#]
Polymethyloctadecylsiloxane [68607-75-0] (70%) Dimethyl (30%) Methyloctadecyl Siloxane Copolymer Polymethyltetradecylsiloxane [76684-67-8] (70%) Dimethyl (15%) Dodecyl (15%) Tetradecyl Siloxane Terpolymer (50%) Dimethyl (25%) Dodecyl (25%) Tetradecyl Siloxane Terpolymer Polymethylhexadecylsiloxane (35-40%) Methyloctyl- (3-4%) Vinylmethyl (56-64%) Dimethylsiloxane Terpolymer Polymethyloctylsiloxane Propylmethyl Homopolymer Vinyldimethyl Terminated

Visc. Visc.
250-300 250-350

SG
0.89 0.892

Rl
1.443 1.44

PP
50

ST
39.5

PS134 PS134.5

1500-3000 150-200

0.89 0.916

1.455 1.43

PS134.8

150-200

0.903

PS135 PS136.5

0.88 500-600 0.93

1.451 (50) 1.437

35

PS140 PS141

600-1000 200

0.91

1.445 1.43

-50

30.4

12

The most outstanding thermal stability and solvent resistance is imparted by the inert fluorosilicones (see description in Figure 4). Indices of refraction are considerably lower than for conventional fluids. See the UCT product catalog for more information. Curable versions of this series are UCT catalog number PS184.5, a silanol fluid, and PS185, a vinyl fluid. The curing chemistries for these classes of silicone will be described later.

13

Figure 4

F F C CH 2 CH 3 CH 3 Si CH 3 F

Fluorosilicones

( )
CH 2 Si O CH 3 n

CH 3 Si CH 3 CH 3

Many advantages of fluorocarbons and silicones are combined in fluorosilicones. Fluorination of compounds usually enhances their thermal stability. In the case of the polysiloxanes, fluorination usually begins at the gamma position of an alkyl chain. Due to the electropositive nature of silicon, fluorination at the alpha and beta positions generally results in poor thermal stability. As a consequence, commercial fluorosilicones are currently limited to trifluoropropyl substituted methyl fluids. The materials are useful from -40 to 285 C in a wide range of aggressive service environments. The fluids are excellent lubricants under extreme pressure conditions. Trifluoropropylmethylsiloxane fluids have a compressibility of 7.45% at 20,000 psi. They are not miscible with fuel or oils. Trifluoropropylsilicone fluids have achieved a number of unique applications due to their chemical and solvent resistance, lubricity and thermal stability. They have been employed in mechanical vacuum pumps where moisture and high temperature oxygen exposure is encountered. They are used as defoamers in processes involving solvent-based wash solutions. They have been employed as grease bases when formulated with thickeners such as PTFE. Their high density has led to their use as flotation media for inertial guidance systems. Longer chain fluorinated silicone fluids demonstrate increased solvent resistance and have been employed as partitioning phases in gas chromatography. Acoustic velocities in fluorosilicones are lower than in conventional silicones, allowing sonar lens development. Copolymers of fluoroalkylsiloxanes with dimethylsiloxanes exhibit improved boundary lubrication properties while maintaining excellent solvent and chemical resistance. They also form high performance greases when thickened with fluoropolymer powders. Such greases have been used in sealed transmissions and other extreme pressure applications. Other fluorocopolymers have been employed as lubricants for electrical contacts and precision timing devices. 14

Silicone fluids typically show limited water solubility and must be emulsified. To impart such solubility long chain polyethylene oxide or polyethylene oxide/polypropylene oxide chains are grafted on to the silicone backbone. Figure 5 and accompanying text describes this series. See the UCT product catalog for more information. Available materials are non curable and are typically used as surfactants or defoamers.

15

Figure 5 Hydrophilic Silicones

Hydrophilic silicones are non-reactive fluids that have been modified to give them slight to complete solubility in water. Their chemical description is polyalkylene oxide modified polydimethylsiloxanes. The typical structure of a hydrophilic silicone is: (CH2)3 (OCH2CH2)X CH3 Si OCH3

(CH3)3SiO

( )( )
Si - O O CH3 m CH3 n

Si(CH3)3

Polydimethylsiloxanes prepared as copolymers with alkene oxides are widely used as surfactants. By altering the amounts of alkene oxide (hydrophile) and dimethylsiloxane (lipophile) the desired surfactant properties may be balanced. The higher the alkene oxide content the higher the hydrophilicity. Materials with ethylene oxide contents 75% and higher are freely soluble in water, as well as other commonly used organic solvents such as methanol, isopropanol, acetone, xylene, and methylene chloride. PS071 is a low molecular weight water soluble fluid that is used in lithographic and photographic plates to facilitate wetting and spreading of developers. It is also used as an anti-fogging treatment for glass and plastic optical surfaces. PS073 is used as an anti-foam in water-based coatings. PS072 is a water soluble copolymer employed as a lubricant for fibers and plastics. It also imparts anti-tack and mar resistant qualities coatings. PS071, PS072 and PS073 all have excellent long term hydrolytic stability. PS071 and PS072 provide slip in flexographic and gravure inks. PS073.5 reduces the static charge generation of fiber substrates and has been incorporated into rolling oil formulations for metal drawing and stamping. The coefficient of thermal expansion is 8 x 10C.

16

The silicone fluids described to this point are non reactive, that is, they are not readily cured to solid elastomers. Table 4 summarizes many of the uses of these materials. Usually applications involve adding the liquid to a formulation as a plasticiser or stabilizer. Uses also include lubricants in machinery and high temperature bath oils.

17

Table 4 Silicone Fluid Selection Guide

Function
Performance Additive

Application
Surfactant/Antifoam

Fluid Class
Conventional (Low Viscosity) Hydrophilic or Fluorosilicone Organic Compatible Conventional (Low Viscosity) Hydrophilic Thermal Conventional (Low Viscosity) Fluorosilicone Thermal Hydrophilic Thermal Conventional (Intermediate Viscosity) or Thermal Conventional (Intermediate Viscosity), Thermal or Fluorosilicone Thermal Low Temperature

Hydrocarbon Compatibility Flow Control Wetting Radiation Resistance Acoustical Optical Heat Transfer Sonobuoy Sound Coupling Optical Coupling Fluid Anti-fog Agent Heat Treatment Bath Constant Temperature Bath Temperature Measurement Device Closed Loop Heating Refrigerated Systems 18

Silicone Fluid Selection Guide (contd)

Function
Working Media

Application
Fluid Clutch Smart Fluids Hydraulic Fluid

Fluid Class
Conventional or Thermal Conventional or Organic Compatible Low Temperature, Conventional or Thermal Conventional (Intermediate Viscosity) Conventional, Thermal Conventional, Thermal or Fluorosilicone Conventional Conventional or Thermal Thermal Thermal (Oligomeric)

Brake Fluid Shock Absorber General Damping

Meter Damping Timing Devices Magnetic Amplifier Diffusion Pump 19

Silicone Fluid Selection Guide (contd)

Function
Lubrication

Application
Mold Release

Fluid Class
Conventional Organic Compatible Emulsion Organic Compatible Organic Compatible Organic Compatible Thermal or Fluorosilicone Low Temperature Conventional or Organic Compatible Hydrophilic Organic Compatible Thermal or Fluorosilicone Organic Compatible Thermal (Chlorophenyl) Conventional, Thermal or Fluorosilicone 20

Aluminum Machining and Extruding Die Casting Ball Bearing and Gear Lubrication

Airborne Radar Rubber/Plastic Contact Fiber/Plastic Contact Metal/Plastic Contact

Metal/Metal Contact Grease

Silicone Fluid Selection Guide (contd)

Function
Dielectric Coolant/Fluid

Application
Transformers, Rectifiers Capacitors Magnetron Dielectric Impregnation of Porous Substrate

Fluid Class
Conventional Conventional Thermal Conventional

21

The basic feed stocks employed in homogeneous platinum catalyzed silicone resin systems are vinyl fluids, whose structural types are outlined in Figure 6, and hydrosilicones, outlined in Figure 8. Vinyl fluids are typically blended in the base or part A side while hydrosilicones are put into the crosslinker or part B side. The A side and B side convention is sometimes violated and inverted by major turn key formulation manufacturers. Technical datasheets and MSDS sheets should be reviewed for unequivocal determination of each sides identity. United Chemical Technologies is also a major manufacturer of these silicone resins. Table 5 and Table 6 list these materials and their most common applications.

22

Figure 6 Vinyl Fluids

Me CH 2 CH Si Me O

( )
Me Si O Me n CH 2 CH O Si m Me
23

Me Si Me CH CH 2

Vinyl Terminated Siloxanes

Me Me Si Me

( )( )
Me Si O Me n

Me Si Me Me

Vinyl Functional Copolymers

Vinyl functional silicones are commonly cured by two routes. The addition cure route involves adding a silicon hydride functional group to a terminal vinyl double bond. The catalyst is a homogeneous platinum catalyst of the Karstedt (Ref 4) type. These cures can be either at room or high temperature, depending on the activity of the catalyst. We will describe these platinum catalysts in more detail later (see Figure 15). The second route involves cures catalyzed by a high temperature radicle induced polymerization , initiated via decomposition of an organic peroxide. Both of these routes are illustrated in Figure 7. In a later section we will discuss in detail the advantages of the platinum catalyzed route over the peroxide route for curing silicone resins.

24

Figure 7 Cure of Vinyl Silicones Si-CH = CH2

VINYL FUNCTIONAL SILICONES
CH3 H + H2C=CH Si CH3 O Pt O O Si CH3 CH2 CH2 O O Si CH3 CH3 Si CH3 O

addition cure

O O Si CH3 CH3 + H2C=CH

CH3 Si CH3 O RO - ROH O

O Si CH3 CHCH2 CH2

CH3 Si CH3 O

peroxide activated cure

25

The complete product line of United Chemical Technologies vinyl silicones is listed in Table 5. PS437 through PS449.5 are di-functional at the the polymer terminals ( the ends). These fluids are the base resins incorporated into the Part A of two part silicones employing platinum catalysis. These formulations will be described and illustrated in later sections. PS422 through PS488 are poly (>2) functional in vinyl, either in the backbone or at the terminals. These resins are additives to the di functional fluids in Part A to impart greater hardness and tear strength. Q resins (see Figure 1 nomenclature) are also used as additives to improve tear strength and abrasion resistance. PS496 and PS498 are representative members of this class offered by UCT. PS437 and PS925 are efficient cure retarders for the platinum based addition cure silicone curing systems.

26

Table 5 Vinyl Fluids

Description (CAS #) Viscosity Weight % Vinyl SG Primary Use in RTV Addition Cure Systems Polydimethylsiloxane, Vinyldimethyl Terminated CAS No. [68951-99-5]
PS437 PS438 PS441 PS441.2 PS442 PS443 PS444 PS445 PS447.6 PS448 PS448.5 PS449 PS449.5 2-3 4-6 100 200 500 1000 5000 10,000 65,000 100,000 165,000 600,000 1,000,000 0.01-0.02 0.03-0.07 0.18-0.26 10-12 7-9 12-14 0.919 0.93 0.97 0.97 0.97 0.97 0.97 0.97 0.97 0.97 0.97 0.98 0.98 Main polymer for High Consistency RTV systems High strength RTV systems Base polymer or part of Polymer blend of liquid RTV systems Cure moderator or as an inhibitor

Polydimethylsiloxane, Monovinyl, Mono n-Butyldimethyl Terminated

PS491 10,000 0.05-0.1 0.98

27

Table 5 Vinyl Fluids(CONTD)

Description (CAS #) Viscosity Weight % Vinyl SG Primary Use in RTV Addition Cure Systems
Peroxide or Pt cure

Vinyldimethyl, Dimethylsiloxane Copolymer, Trimethylsiloxy Terminated CAS No. [67762-94-1]

PS422 PS424 PS426 250 1000 1000 1.0 7-5 1.0

Vinyldimethyl, Dimethylsiloxane Copolymer, Vinyl Dimethyl Terminated

PS493 1000

Divinylmethyl Terminated, Polydimethyl Siloxanes

PS483 PS488 1000 100,000

Vinyl Q-resin Dispersion

PS496 PS498 4000-6000 165,000 1.02 1.02 High strength RTV systems

Vinylphenylmethyl Terminated Dimethyl Siloxanes

PS463 1000

T-structure Polydimethylsiloxane with vinyl at branchpoint

PS408 50-75

T-structure Polydimethylsiloxane with vinyl at branch terminus

PS410 300-500 0.99

Cyclic Vinylmethyl, Dimethyl Siloxanes CAS No. [2554-06-5]

PS925 3-7

28

The other component of the two part RTV platinum curable silicones is a hydrosilicone crosslinker (see Structure 1 of Figure 8). This crosslinker typically contains hydrosilicone in the backbone of the polymer. Silanol fluids (see Structure 2 of Figure 8) may also be formulated with hydrosilicones and a tin or zinc catalyst. Hydrogen gas results which blows the polymer matrix on curing. These blown silicone systems are useful in cushioning materials. The other major use of hydrosilicones is as selective reducing agents (Ref 3). Equations for these chemistries are shown in Figure 9.

29

Figure 8
CH3 CH3 Si CH3 O H Si O

Structure 1
CH3 Si CH3 CH3

( )
CH3

Organo-Hydrosiloxane Polymers and Copolymers

HO

( )
Me Si O Me
30

Structure 2

Silanol Terminated and Related Polydimethylsiloxanes

Figure 9 CHEMISTRY OF HYDRIDE FUNCTIONAL POLYMERS

Hydride Functional siloxanes undergo three main classes of reactivity: Hydrosilylation, dehydrogenative coupling and hydride transfer.

Hydrosilylation
O O Si O H + H 2 C=CH CH3 Si CH3 O Pt O O Si O CH 2 CH 2 CH3 Si CH3 O

Dehydrogenative Coupling
O O Si O OH + H CH 3 Si CH3 O Sn(OOCR) 2 O O Si O O CH3 Si CH3 O + H
2

( )
H O Si O CH 3 n

CHO +

Reduction
Bu3SnH

NO2

( )
O O Si O CH3 n

CH2OH + NO2

31

Table 6 lists the complete line of UCT hydrosilicones. PS118PS122 are hydrosilicone homopolymers with trimethylsiloxy terminals and backbones consisting entirely of methylhydrosiloxy groups. These are very potent crosslinkers. They also are used as starting materials to graft on alkyl or other functionalities via the hydrosilylation reaction. PS122.5-PS124.5 are more moderate crosslinkers containing varying molar amounts of methyl hydrosiloxane in the backbone, the remainder being dimethylsiloxane. Specialized crosslinkers with cyano, octyl or phenyl functionality in the backbone are offered in PS124 through PS129.5. Hydrosilicone chain extenders are use extensively to soften platinum cure formulations and impart greater elongation. They are di functional in hydride at the polymer terminals. UCT offers a complete line of these with catalog numbers PS537 through PS545.

32

Table 6 Hydrosilicones
Description [CAS #] Viscosity Wt% Methyl Hydro Specific Gravity Refractive Index 1.382 0.99 0.99 0.99 (50-55%) (30-35%) (15-18%) 0.99 0.99 0.99 1.395 1.396 1.397 1.394 1.399 1.400 70 125 RTV Crosslinker for addition cured Pt catalyzed systems 300 50 100 121 Blowing Agent Crosslinker Flash Point Uses Polymethylhydrosiloxane, Trimethylsilyl Terminated CAS No. [63148-57-2] PS118 PS119 PS120 PS122 PS122.5 PS123 PS123.5 2-5 20 30 85 10-15 25-30 25-35

Methyl Hydro, Dimethylsiloxane Copolymer, Trimethylsilyl Terminated CAS No. [68037-59-2]

PS123.8 PS124.5

7500 2500 250-275

(0.5-1.0%) (4-6%)

0.97 0.97

1.404 1.404

33

Table 6 Hydrosilicones (CONTD)

Description [CAS #] Viscosity Wt% Methyl Hydro Specific Gravity 1.07 0.93 0.91 Refractive Index 1.446 1.435 1.440 1.500 0.905 0.971 0.971 0.974 1.395 1.403 1.403 1.403 Flash Point Uses Methyl Hydro, Cyanopropylmethyl Siloxane Copolymer PS124 PS125 PS125.5 PS129.5 PS537 PS542 PS543 PS545 1000-3000 200-400 300-600 75-100 2-3 500 1000 10,000 (3-4%) (40-60%) (25-30%) (45-50%) Methyl Hydro, Methyloctyl Siloxane Copolymer

Methyl Hydro, Phenylmethyl Siloxane Copolymer, Dimethylsiloxy Terminated Polydimethylsiloxane, Hydride Terminated

34

The physical properties of silicone resins are intimately related to the structure of the starting monomer units. Table 7 is a summary of these structure/property relationships. Trends commonly experienced by polymer formulators are the increased rigidity and decreased elongation on introduction of aromatic groups into the backbone of the silicone.

35

Table 7 Effect of Monomers on the Properties of Silicone Resin Films

Property hardness brittleness stiffness toughness cure speed tack CH3SiCl3 increase increase increase increase much faster decrease C6H5SiCl3 increase increase increase increase (CH3)2SiCl2 decrease decrease decrease decrease (C6H5)2SiCl2 decrease decrease decrease decrease much slower increase CH3(C6H5)SiCl2 decrease decrease decrease decrease slower increase

some increase slower some decrease increase

36

Other monomeric short chain silane end cappers, cross linkers and chain extenders are employed where the formulator desires a more rigid structure or more tightly defined stoichiometry. Figure 10 lists the most commonly available commercial products and their United Chemical Technologies catalog numbers.

37

Figure 10
Me O Me Si Me Me Si Me O O Me2Si Si Me O O

Typical Silicone Monomers

Me2 Si Si Me2 O O SiMe2 Si Me2 O
5

Hexamethylcyclotrisiloxane

H7260
Ph Ph Si Ph O Si O Ph Ph O Si O Si Ph Ph Ph

Octamethylcyclotetrasiloxane

Decamethylcyclopentasiloxane

O9810

D3770
Ph

Ph Si Ph

OH

Ph Si O Me Si O

Si

Me

OH

Me Ph

Octaphenylcyclotetrasiloxane

Diphenylsilanediol

Trimethyltriphenylcyclotrisiloxane

O9817

D6150

T3800

38

Figure 10 (contd)
H2C CH SiO H3C 3-4 O O HMeSi 3-4 Si MeH MeH Si O O SiMeH

CF3
Me

SiO

Vinylmethylcyclosiloxane

PS925
Me Me Si Me O Me Si Me Me

Trifluoropropylmethylcyclosiloxanes

Methylhydrocyclosiloxane

T2844
Me H2C = CH Si Me O Me CH3 Si Me CH2 = CH2 H CH3 Si

T2000

CH3 O Si H CH3

Hexamethyldisiloxane

H7310

Divinyltetramethyldisiloxane

Tetramethyldisiloxane

D6210

T2030

39

Typical commercial silicone sealants are formulated to give high elongation, moderately hard elastomers. Table 8 is an overview of typical cured rubber physical properties for representative industrial sealants. UCT silicones are extensively used by these compounders as base resins for both one and two part systems. The high gas permeability of silicones is quantitatively illustrated in Table 9. This property results in their extensive use in contact lens formulations (Figure 11) to allow oxygen transmission to the cornea. This property also allows small mammals to breathe in a low viscosity silicone medium.

40

Table 8 Cure Properties of Typical RTV Silicone Rubbers

One-component general-purpose One-component construction sealant Two-component adhesive sealant Two-component molding compound

Property hardness, Shore A durometer tensile strength MPa elongation tear strength

30 2.4 400 0.80

22 1.0 850 0.35

50 3.5 200 0.52

60 5.5 220 1.75

41

Table 9 Permeability of Silicone Elastomers

CAS Registry No. (63148-62-9) Permeability Temperature C 25 25 25 30 70 26 26 31 31 Gas CO2 O2 air butane butane CO2 O2 CO2 O2 (cm3-cm)/(s-cm2-kPa) -7 x 10 405 79 44 2.0 1.7 79 13 237 40

Type Dimethyl silicone

fluorosilicones nitrile silicones

(63148-56-1) (70775-91-6)

42

Figure 11
Hard oxygen-permeable contact lenses allow correction of a wider range of visual defects without compromising wearer comfort (courtesy R. Capozza, Syntex Ophtalmics)

The low toxicity and high gas permeability of silicones are shown in this experiment, in which snails completely immersed in 3-5-ctsk polydimethylsiloxane lived for more than 72 h (authors experiment constructed from unpublished work of R. LeVier)
43

The inertness and low toxicity of silicones allows them to be used extensively in medical and prosthetic applications, as illustrated in figures 12 and 13. While UCT does not warrant silicones for medical use, its customers have qualified a wide variety of formulations in a plethora of devices. The most recent qualification is in the Abiocor artificial heart device.

44

Figure 12
Here actor Dustin Hoffman has aged to 121 years for the film Little Big Man.

The mask and other appliances are made of silicone and bonded by PSAs. These materials are non-sensitizing and used in a wide range of bonding applications, including surgical dressings, ileostomy and colostomy appliances, and toupes (courtesy Dow-Corning Corp.)
45

Figure 13

Silicone medical devices and the body: Numerous medical devices are made from silicone-containing polymers.
46

Ultraviolet (UV) curable silicones are a specialized application with unique advantage but also limitations. UV curing allows a continuous curing process by passing the coated substrate through a high intensity UV light bank. If this technology is available the advantages of no premixing, humidity effect or heating are obvious. UV technology has the following limitations. A) Need for thin coats (typically 20 micron or less). B) Need for high power mercury arc lamp type UV device. C) Inhibition by oxygen. D) Need for adding photoinitiator (typically several hundred ppm). Good photoinitiators are the Irgacure series of substituted acetophenones. The UCT product line of UV curable silicones is summarized in Table 11. Among the most popular products are: PS560. Monomethacryl functional silicone for grafting of a silicone backbone into a methacrylate cure resin. PS583 Difunctional silicone methacrylate giving soft UV cures. PS851 Methacrylate with functionality in backbone. Gives moderately hard ( Shore A ~ 20-30) UV cures. A good photoinitiator is Irgacure 851 (2,2-dimethoxyphenylacetophenone). PS2067 Cyclic high functionality methacrylate, gives very hard (Shore A > 50) cure with minimal elongation.

47

Methacrylate & Acrylate-Functional Polymers

Acryloxypropyl-functional silicones undergo UV and visible light polymerization in the presence of photoinitiators such as ethylbenzoin. Methacryloxypropyl-functional silicones undergo the same general chemistry as the vinylsilicones, but possess several significant reactivity differences. They copolymerize readily with methacrylate monomers and undergo light activated polymerization.

48

Table 10

Methacrylate & Acrylate-Functional Polymers

Product # PS560 Description Polydimethyl siloxane MonomethacryloxyPropyl terminated Polydimethyl siloxane Methacryloxypropylterminated (Acryloxypropyl) Methyl (Methacryloxypropyl) Methyl (Methacryloxypropyl) Methyl (Methacryloxypropyl) Methyl (Methacryloxypropyl) Methyl Methacrylate Functional T-structure PS406 PS 901 PS 901.5 Methacryloxy Propyl Poly(Methacryloxypropylmethyl)Siloxane (Includes Cyclics) Poly(Acryloxypropylmethyl)-Siloxane (Includes Cyclics) 49 25-50 Acrylate Homopolymers 25-125 100 1.10-1.12 0.97 Viscosity 1000 Specific Gravity Mole % Comonomer

PS583

2000

1.00

Polydimethyl Siloxane, Methacrylate & Acrylate Functional Copolymers PS802 PS851 PS852 PS853 PS854 80-120 1000-2000 10000 2500 0.98 0.98 0.92 0.91 0.98 15-20 2-3 5 8 16

Lens Monomers are low molecular weight silane additives for contact lens formulations. They greatly increase the permeability of the lens to oxygen and moisture. United Chemical Technologies is a basic manufacturer of lens monomers. Figure 14 shows the most common silane lense monomers.

50

Figure 14 Lens Monomers

O CH2 = CCO(CH2)3Si(OSiMe3)3 CH3 O Me Me CH2 = CCO(CH2)3SiOSiMe CH3 Me Me

M8559

Methacryloxypropyltris (trimethylsiloxy)silane

M8547
Methacryloxypropylpentamethyldisiloxysilane

Me Me

CH2 = CCO(CH2)3Si(OSiOSiMe)3 CH3 Me Me

Methacryloxypropyltris(pentamethyldisiloxanyl)silane

51

Figure 14 Lense Monomers (Contd)

O OH OSiMe3 CH2 = CCO(CH2)OCH2CHCH2O(CH2)3SiMe CH3 OSiMe3

Methylbis(trimethylsiloxy)silylpropylglycerolmethacrylate

Me Me

CH2 = CCO(CH2)4SiOSi(CH2)4OCC = CH2 CH3 Me Me CH3

Bis(Methacryloxybutyl)tetramethyldisiloxane

B2408.5
52

This article will attempt to highlight the benefits of homogeneous platinum catalysts of the Karstedt type (Ref 4) over other catalyst systems commonly used in curing polydimethylsiloxane resins. The technology is also applicable to organic synthesis where an active silyl functionality needs to be grafted onto an olefinic moiety. These platinum catalysts are described in detail in Figure 15 and Table 11 . Advantages over the older Speiers catalyst (chloroplatinic acid in ethanol) are summarized in Table 12. Table 13 is a compilation of the many features and benefits offered by the United Chemical Technologies line of Homogeneous Platinum Catalysts.

53

Figure 15 Platinum Vinylsiloxane Catalysts

Platinum vinylsiloxane complexes have found extensive use as catalysts for promoting hydrosilylation reactions. The bond forming chemistry proceeds according to the following equation:
Platinum Catalyst

Application
Applications include two part silicone compositions (RTV addition cure systems) utilized in dental impression compounds, prototype molding, sealants, and electronic coating applications. Cure time is reduced from hours to minutes in RTV systems due to the solubility of these catalysts in dimethylsiloxane polymers. For hydrosilylation reactions or two part RTV systems, it is recommended that platinum catalysts be utilized at the 5-50 ppm range based on total formulation weight. The reactivity of PC072, PC075, and PC085 can be modified using inhibitors such as UCTs products designated D6210 and T4290 to achieve optimum reactivity characteristics. Reactivity rates are PC072 > PC075 > PC085.

SiH + CH2 = CHSi

SiCH2CH2Si

Typical Properties
Product PC072 PC075 PC085 Platinum1 Content > 2% > 2% > 2% Carrier Xylene Linear Silicone Fluid Cyclic Silicone Fluid Cure time2 5.0 - 8.5 5.0 - 10.0 10.0 - 15.0

Assay Test Method No. UCT0001

In minutes standard RTV system, Test Method No. UCT0002

54

Table 11 Homogeneous Platinum Catalysts

Minimum

Product

Percent Platinum (1)

10 2 1 2 2 2 3 5 1 2 3 1 2.1
55

Carrier

PC065 PC072 PC073 PC074 (CLEAR) PC074.5 PC075 PC075.3 PC075.5 PC076 PC085 PC085.3 PC086 PC088.3

Linear Inhibitor Xylene Xylene Xylene Octamethylcyclotetrasiloxane Linear Silicone Linear Silicone Linear Silicone Linear Silicone Cyclic Silicone (Ashbeys Catalyst) Cyclic Silicone Cyclic Silicone Octanol/Octanal (Lamoreauxs Catalyst)

1. Standard UCT atomic absorption method.

Table 12
Advantages of Platinum (0) Vinyl Siloxane Complexes PC065-PC086 Over Chloroplatinic Acid, H2PtCl6 1) Homogeneous. 2) Higher reactivity. 3) Reactivity is fine tuned by choice of solvent and inhibitor. 4) No corrosive HCl or chloride byproducts. 5) Colorless catalyst solutions are available.

56

Table 13 Features and Benefits

Features
Consistent reactivity profile.
High Clarity, Low Color. Customized platinum levels available. Specialized packaging available. Wide variety of catalyst activities for room temperature and high temperature cure profiles. Complete catalyst product line to serve Platinum-based, Peroxide-based, and Condensation-based Silicone cures.

Benefits
Just in time delivery, very competitive pricing.
Less customer problems with final cured product. Our platinum catalysts are more reactive and selective than chloroplatinic acid. Our platinum catalysts require low formulated platinum concentrations (5-30 ppm). Platinum catalyzed cures evolve no volatile byproducts. Our homogenous platinum catalysts have more consistent reactivity than heterogeneous catalysts due to irregular surface effects in the latter.
57

While homogeneous platinum catalyzed resins have many processing advantages over peroxide cure systems (see Table 14), United Chemical Technologies is a full service company that offers a comprehensive line of peroxide catalysts. Figure 16 describes this product line and gives starting process conditions. The peroxide catalysts are supplied as pastes in inert silicone to allow easier compounding into the formulation.

58

Figure 16 Peroxide Catalysts

Applications
Peroxide catalysts are best used for low vinyl containing polymers (for example - UCT's products PS255, PS264, PS268, PS286) which can be cured at elevated temperatures using peroxide. The benzoyl peroxide catalyst has less tendency to scorch than dichlorobenzoyl peroxide and is therefore favored for thin sections. Peroxide loading is approximately 0.2-1.0% and curing is at 125-150C.

Peroxide catalysts are primarily used for the cross linking of silicone rubber compounding.

Typical Properties
Product PC010 PC020 Chemical Description 2,4-Dichlorobenzoyl peroxide Benzoyl peroxide Carrier Polydimethyl siloxane Polydimethyl siloxane Concentration 50% 50%

59

Table 14
Advantages of Addition Cure (Platinum) Over Peroxide Cure Systems:

A) Lower curing temperatures possible. B) No acidic byproducts (e.g., benzoic acid from benzoyl cure). C) No frothing from oxygen byproduct of cure. D) No oxidative degradation of elastomer possible.

60

High molecular weight silicone gum stock is curable utilizing both peroxide and platinum based catalysts if the gum contains vinyl functionality. Table 15 lists the complete UCT product line. Of these all but PS240 contain vinyl groups and are curable with a homogeneous platinum catalyst plus hydrosilicone crosslinker.

61

Silicone Gums
Silicone gums are high molecular weight linear polydiorganosiloxanes that can be converted from a highly viscous plastic state into a predominantly elastic state by crosslinking. They are base stocks for most traditional silicone rubbers. The principal method of producing rubbers is to cure at elevated temperatures with peroxides. Elevated temperature cure gums usually have molecular weights ranging from 500,000 to 900,000. A variety of groups, including trifluoropropyl, cyanopropyl, phenyl, and vinyl, are used to substitute for methyl groups in order to impart specific cure, mechanical or chemical properties to silicone rubbers. Introduction of phenyl groups reduces elasticity, increases radiation resistance and useful temperature range. Phenyl groups reduce crosslinking efficiency. Trifluoropropyl groups increase solvent resistance. Introduction of low percentages of vinyl groups reduces the vulcanization temperature and imparts greater elasticity and lower compression set to rubbers. Peroxide cure gums may be trimethylsiloxy or vinyldimethylsiloxy terminated. Most gum stocks have methylvinylsiloxane chain components. The peroxides most commonly used are benzoyl peroxide and bis(dichlorobenzoyl) peroxide. Other peroxides are restricted to more specific systems. Dicumyl peroxide, for example, can be used only for vinyl containing polymers. Generally, peroxide loading is 0.2 to 1.0% and cure is at 125-155. Trifluoropropylmethylsiloxane compounds are often stabilized with red iron oxide.

62

Table 15 Silicone Gums

Product # Description Normal Cure System Used Peroxide Peroxide PS240 PS255 Poly (Dimethylsiloxane), gum Poly (Dimethylsiloxane) - (0.1-0.3%) (Methylvinylsiloxane) Copolymer, Gum PS264 Poly (Dimethylsiloxane) - (5-6%) - (Diphenyl) (0.1- 0.3%) - (Methylvinylsiloxane) Copolymer, Gum PS268 Poly (Dimethylsiloxane) - (15%) - (Diphenylsiloxane) (0.1-0.3%) - (Methylvinylsiloxane) Copolymer, Gum PS286 Poly (Methyl-3,3,3-Trifluoropropyl) - (1-2%) (Methylvinylsiloxane) Copolymer, Gum Peroxide Peroxide

Peroxide

63

Typical formulated silicone rubber systems require substantial molar excesses of hydrosilicone over vinyl fluid to achieve optimal physical properties. The desired mix ratio depends on the chain length of the vinyl terminated silicone and percent hydride in the backbone of the crosslinker. Table 16 lists theoretical mix ratios for three commercial United Chemical Technologies vinyl fluids when compounded with three hydrosilicones of varying hydride content (refer to tables 4 and 5). Ratios are computed at a 1.5/1.0 SiH/Vinyl molar ratio. Less potent crosslinkers, such as PS123.8, and higher viscosity vinyl fluids, such as PS445, give softer cures at equivalent molar ratios.

64

Table 16 Starting Ratios of Hydrido Siloxanes (parts) to 100 parts of Vinylsiloxanes

Vinylsiloxane PS443 PS445 PS735 PS123.8 80.8 11.5 11.9 PS123.5 4.2 1.8 1.9 PS123.0 2.1 0.9 0.9

Formulation is based upon molar ratio of 1.5 Si-H to 1.0 vinyl. Filled formulations may require up to 3x the amounts listed for optimal physical properties.

65

Experienced formulators and compounders can startup new materials research with little guidance, but for those new to silicone formulation Tables 17-18 are convenient starting points. The crosslinker, catalyst and plasticiser levels can all be varied to achieve the formulators unique cure profile and physical properties requirements. Other general guidelines are: a:) For two part systems, always put the platinum catalyst in the A (vinyl or base) side to avoid slow reaction of the catalyst with the hydrosilicone. b:) Plasticiser and vinyl fluid can be partially mixed with the B (hydrosilicone) side to achieve a better mix ratio. Care must be taken to avoid metal contamination on the B side if this approach is taken. c:) Avoid: Contact with platinum catalyst poisons such as tin salts, mercaptans, PVC beakers or amino compounds.

66

Table 17 Starting Formulation, Molding RTV Silicone

This formulation has low modulus and durometer but is useful as a molding compound. No special procedure or apparatus is required and the procedure may be modified by varying the ratios of concentration to accelerate or retard the cure rate. Alternatively, the cure rate may be retarded by addition of T2160 inhibitor.

PS443 SS0216 PS123 PC075

(Vinyl Fluid) (Filler) (Hydrosilicone) (Catalyst)

100 parts 50 parts 3-4 parts 150-220 ppm

With a spatula or tongue depressor, stir the PS443 into the SS0216. A plastic beaker or coffee cup is a convenient disposable recepticle. After producing a uniform paste, stir in the PS123. This paste is stable at room temperature if stored. For activation add the platinum solution dropwise with eyedropper or syringe and rapidly stir with spatula. Expect a 5-10 minute work life. Let cure overnight at room temperature to optimize physical properties.

67

Table 18 Starting RTV Formulation

PART A PS443 SS0216 PC075 TOTAL: (Vinyl Fluid) (Filler) (Catalyst) 82g 17.85g 0.15g 100g PS443 PS123 TOTAL: PART B (Vinyl Fluid) (Hydrosilicone) 90g 10g 100g

Prepare parts A and B separately. Mix 3 parts A with one part B. Cure at ambient conditions for four hours. Physical Properties Tensile Strength Tear Strength

Shore A 20-30 Elongation 400-500%

3.5 Mpa (500psi) 16N/mm(91ppi)

68

Simple formulating technique for small scale development work is illustrated in Figure 17. No expensive equipment is required and physical properties such as Shore A durometer hardness and elongation are easily measured. Other physical properties such as tear strength or modulus will require more sophisticated instrumentation.

69

Figure 17 How To Use UCTs PETRARCH Silicones

1. WEIGHING: Weigh A and B in the

recommended ratios.

2. MIXING: Use a spatula to make a

homogenous mixture of A and B.

3. DEAIRING: Place the mixed

silicone in a vacuum chamber (desiccator) and apply vacuum until foam collapses. 70

4. POURING: Pour mix into mold

or form avoiding entrapment of air.

How To Use UCTs PETRARCH Silicones (Contd)

5. CURING: Follow the recommended

cure schedule

6. DEMOLDING THE FINISHED PART

71

In contrast, scale up to commercial silicone resin requirements will require specialized blending equipment to achieve uniform mixing. High viscosities and filler levels necessitate such an investment. Alternatively, formulations may be sub contracted to experienced adhesives manufacturers. Figure 18 shows typical large scale equipment and Figure 19 illustrates intermediate scale equipment for scale up to kilogram level.

72

Figure 18 Large Scale Formulation Equipment

50 gallon high speed disperser produced by Applied Silicone Corp, Ventura, California

73

Figure 19 Kilogram scale formulation equipment

Hauschild Speed Mix from FlackTek Inc., Landrum South Carolina

One gallon Double Planetary Mixer produced by Charles Ross & Son Company, Hauppauge, New York
74

While United Chemical Technologies is a major manufacturer of the basic building blocks for silicone rubber formulations,UCT also offers turn-key pre blended formulations for those customers who do not want to do their own development work. Figure 20 begins an extensive discussion of formulation techniques and also describes our most popular two part kits. PEM10 is a two part RTV platinum catalyzed system that cures to a clear silicone elastomer. PEG060 is a two part RTV platinum cure system that cures to a soft silicone gel. Adjusting the crosslinker (part B) level up or down can make the systems harder/softer for individual specialized requirements.

75

Figure 20
Two Part Elastomeric Sealant Kits
Prototype and Model Making Silicones How Modeling Silicones Work The silicones are supplied as two part kits with A and B parts, containing at least three components: 1. Base 2. Crosslinker 3. Catalyst
The base, typically a moderate viscosity vinyl fluid, and crosslinker, typically a hydrosilicone, combine with each other to form the cured product. The catalyst, often a platinum derivative, is premixed with the base, so most kits have only two parts. They are referred to as vinyl-addition silicones. Other materials can be added by the craftsman to modify the basic properties of the silicones. These include fillers, softening agents, pigments, dyes, additional catalyst or cure retarders. The modifiers are added to the base. After mixing these components, the crosslinker is added. All of UCTs kits are in ready-to-use form with responses and strengths most widely desired. Only the experienced modellist should consider blending materials other than pigments and dyes, such as softening agents and fillers.

76

Two Part Elastomeric Sealant Kits

Mixing
It is important to obtain a homogenous mix of the silicones and to avoid entrapment of air. Mixing can be accomplished with a spoon or mixing stick. If air is entrapped as bubbles, cured rubber will contain weak areas and detail will be lost. In most systems vacuum de-airing is desirable. Some systems will de-air on standing for 5 to 20 minutes, particularly if the mix container is tapped sharply or placed on a vibrating surface. Bubbles on mold surfaces can be reduced by brushing a layer of catalyzed mix over the surface before pouring.

Work Life
All silicone systems are designed to have a work life of 30 to 90 minutes. The work life can be extended by adding a cure retarder to the initial mix. The work life can be shortened by adding catalyst or warming the mix.

Curing
Most UCT silicones will cure at room temperature in 24 hours. The cure can be accelerated by heating the silicones. At a temperature of 110C(240F) most will cure within two hours.

Materials to Avoid
The A Part, B Part and catalyzed mixture of A/B can be cure-inhibited by certain contaminants. Avoid contamination with amines, sulfur, chloride or tin containing compounds. These materials are found in epoxy, natural rubber, PVC and moisture cure silicones, respectively.

77

Two Part Elastomeric Sealant Kits

PEM-10 Description
PEM-10 silicone elastomer is supplied as a two part kit consisting of liquid base and curing agent. When the base and the curing agent are thoroughly mixed in a 10:1 weight ratio, the liquid mixture will cure in thick or thin sections to a flexible, transparent elastomer ideally suited for electrical/electrical potting and encapsulating`applications.

Uses
Equipment modules Relays, power supplies and magnetic amplifiers Transformers, coils and ferrite cores Connectors Fiber optic waveguide coatings Encapsulation of circuit boards

Mixing
PEM-10 silicone elastomer is supplied in two parts, a lot-matched base and curing agent, mixed in a ratio of 10 parts base to one part curing agent, by weight. For best curing results, glassware or tinned cans with glass or metal stirring implements should be used. Mix with a smooth action that will minimize the introduction of excess air.

78

Two Part Elastomeric Sealant Kits

PEM-10 Physical Properties Base viscosity at 25C, 5500 centipoise Specific Gravity at 25C, 1.05 Mixed Viscosity at 25C, 3900 centipoise Pot Life at 25C, 2 hours Cure Time at 25C, 24 hours Cured Physical Properties Appearance, Transparent Hardness Shore A, 40 Tensile Strength MPa (psi), 6.20 (900) Elongation Percent, 100 Tear Strength die B kN/m (ppi), 2.6 (15) Brittle Point Centigrade, -65 Refractive Index at 25C, 1.430

Storage and Shelf Life

When stored in original unopened containers at or below 32C, PEM-10 has a shelf life of 12 months from date of shipment from United Chemical Technologies, Inc.

Packaging
PEM-10 silicone elastomer, base and curing agent, is shipped in kits containing both the base and curing agent in separate containers. Each kit contains the appropriate weight of curing agent for the amount of base. Complete kits are available in 1.1, 8.8, 44 and 495-lb (0.5, 4, 20 and 225-kg) quantities, net weight.

79

Two Part Elastomeric Sealant Kits

PEG-60
Description
PEG-60 is a silicone gel. A silicone gel is a solid with fluid characteristics. PEG-60 maintains good cohesion, high instantaneous deformation and good resilience. It is clear with a range of firmness that varies from slow flowing to free standing. The temporarily deformable material has found application in soft tissue prosthesis and shock adsorption. It may be characterized as a viscoelastic substance of which only a small portion is crosslinked by an addition cure mechanism. Variation of base components gives a wide range of firmness. Properties, Mixed Viscosity, centistokes @25C, 1000 Specific Gravity @25C, 0.97 Penetration mm, 150-250

Processing
PEG-60 is a 2 part addition cure system. The system comprises an A and B which, as supplied, are mixed in a 10 to 1 ratio. After thoroughly mixing 10 parts A to 1 part B, allow mix to de-air cure at 115-120C for 30-60 minutes or at room temperature for 48 hours. If penetration of the cured gel is either too firm or too soft for the given application, the A part to B ratio can be changed: Too firm-low penetration-change A to B ratio to 11:1, 12:1, 13:1, etc. Too soft-high penetration-change A to B ratio to 9:1, 8:1, 7:1, etc. At each ratio, re-cure and check penetration until desired softness is achieved.

80

A quite old silicone curing technology involves use of silanol fluids (Figure 21) cured with a zinc or tin catalyst and a wide variety of crosslinkers such as polysilicate, oxime or acetate. Figure 21 also illustrates generation of a moisture curable tetra acetato functional silicone, by reaction of a silanol fluid with a triacetate functional silane (UCT number M8980). Table 19 lists the complete UCT line of silanol fluids. All are difunctional with the silanol groups at the polymer terminals. Table 20 lists moisture curable silicone prepolymers with acetoxy or alkoxy functionality. Materials in Table 20 are curable with zinc or tin alkanoate catalysts (see Figure 23).

81

Figure 21

Si-OH
CH3 HO Si CH3 O

( )
CH3 Si O CH3 n O CCH3 O

CH3 Si CH3 OH

Silanol Functional Polymers

O CH3 HO Si CH 3 O O CH3CO H3C Si O CH3 Si CH3 O O

( )
CH3 Si O CH3 n

CH3 Si CH3

OCCH3 OH + 2 CH3 Si

OCCH3 O

CH3CO O

( )
CH3 Si O CH3 n

CH3 Si CH3 O

OCCH3 Si CH3

OCCH3 O

Condensation cure

82

Table 19
Polydimethylsiloxanes, Silanol Terminated
Product # [CAS #] PS340 PS340.5 PS341 PS342.5 PS343 PS343.5 PS343.8 PS344.5 PS345.5 PS347.5 PS348.7 PS349.5 15-35 45-85 100 750 1000 2000 3500 8000 18,000 50,000 125,000 175,000 800,000 1,200,000 Viscosity Functionality Weight % 4.0-6.0 0.9-1.2 0.8-0.9 0.2 0.1 0.09 0.08 0.06 0.04 0.03 0.03 0.01 Specific Gravity 0.95 0.97 0.97 0.97 0.98 0.98 0.98 0.98 0.98 0.98 0.98 0.98 Silicone pressure sensitive adhesives, silicone curable solvent dispersions. One & two part RTVs Uses Polydimethyl Siloxanes Silanol Terminated CAS No. [7013-67-8] Structure control additive for Silicone rubber and cure Moderator for RTV foams

83

Table 20
Other Moisture Cure Prepolymers
Product # [CAS #] PS363.5 [68440-60-8] Viscosity Functionality Weight % 0.30 Specific Gravity 0.98 Uses Polydimethylsiloxane, Dimethylacetoxy Terminated 2500-3500

Polydimethylsiloxane, Methyldiacetoxy Terminated PS368.5 PS375 [67923-13-1] 2500-3500 2-5 0.5-0.6 13-16 0.99 1.00

Polydimethylsiloxane, Dimethylchloro Terminated

Polydimethylsiloxane, Dimethylamino Terminated PS383 [67762-92-9] PS393 [70851-25-1] PS395 PS397 2-5 13-16 0.98

Polydimethylsiloxane, Dimethylethoxy Terminated 2-3 6-11 1000 20-25 7-13 R.I.=1.4040 84 0.92 0.94 0.98

Polydimethylsiloxane, Dimethylmethoxy Terminated

Silanol fluids are curable to elastomers by a wide variety of crosslinkers. Equations listing the most common cure pathways are listed in Figure 22. All of these cure systems result in elimination of a volatile byproduct such as acetic acid, an oxime or alcohol. These systems are thus called condensation cures. Metallic corrosion can result from elimination of acetic acid or to a lesser extent alcohols. Oxime or enoxy cure systems are preferred if metal contact is anticipated. Due to the problems with volatile byproducts or corrosion, the homogeneous platinum catalyzed systems described earlier have replaced silanol based cure systems in many electronic, fiber optic or defense applications. The advantages of the platinum based over the condensation based cure systems are outlined in Table 21.

85

Figure 22
THE MOST COMMON CONDENSATION CURE SYSTEMS ARE:
O O = = Acetoxy Si - OH + CH3CO - Si CH2 Si - O - Si + = Si - O - Si + CH3COH O =

Enoxy

Si - OH + C2H5

CH3CO - Si

CH3CCH3

Oxime

Si - OH + C=NO - Si H 3C Si - OH + CH3O - Si

Si - O - Si

C2H5 + H 3C

C=NOH

Alkoxy

Si - O - Si

CH3OH

Amine

Si - OH +

(CH3)2N- Si

Si - O - Si

+ (CH3) 2NH

86

Table 21
Advantages of Addition Cure (Platinum) Over Condensation Cure (Tin, Zinc) Systems: A) No volatile byproducts. B) Lower catalyst concentrations (5-30 ppm vs 100-300 ppm). C) Less moisture sensitivity D) Smoother reaction profiles.

87

Typical one and two part condensation cure RTV systems are listed in Table 22 and Table 23. For one part moisture cures it is critical that all components be thoroughly dried to prevent premature gelation in a dispensing tube or hot warehouse. Liquid components, if low viscosity, can be dried over molecular sieves. Alternatively, water can be azeotroped off with toluene. Solid fillers should be oven dried if possible. Untreated silica fillers when incorporated into one part systems, often cause viscosity buildup or gelation from active silanols on the surface. Treated fillers, such as UCT number SS0216, cap off these groups and give more stable systems.

88

Table 22 Condensation Cure Silanol System

PART A
PS347.5 SS0216 PS9120 TOTAL: (Silanol) (Filler) (Crosslinker) 70g 28g 2g 100g PS041 SS0216 PC055 TOTAL:

PART B
(Plasticizer) (Filler) (Catalyst) 35g 45g 20g 100g

Procedure
Prepare parts A and B separately. Mix 10 parts A with one part B. Cure at ambient conditions.

89

Table 23
Starting One Part Moisture Cure RTV Formulation
PS347.5 PS043 M9220 A0750 (Silanol) (Plasticizer) (Oxime Crosslinker) (Primer) 65.9g 20.0g 5.0g 1.0 8.0g 0.1g 100g

150m2/g Fumed Silica Dibutyl Tin Dilaurate (Catalyst) TOTAL:

Physical Properties
Shore A Elongation Skin over Scratch time 22 550% 10 min 120 min Tensile Strength 100% Modulus Tack Free Through cure
90

1.9 Mpa 0.4 Mpa 60 min 2.0 mm (24hr)

Figure 23 describes the tin and zinc alkanoate catalysts offered by United Chemical Technologies for condensation cure systems. The catalysts are blended with low viscosity inert silicone to allow easier compounding. The octanoate group is actually 2-ethyl hexanoate, not a linear C8 carboxylic acid. Tin salts are generally more reactive than zinc salts. Typical starting formulations incorporate a minimum of 500 ppm of active metal.

91

Figure 23
Metal Octanoates (Zinc & Tin) and Metal Dilaurate (Tin)Catalysts
Applications
Zinc and Tin Octanoates are catalysts used independently or together in RTV formulations. RTV systems are formulated from silanol terminated polymers with a molecular weight of 26,000 to 200,000. There are several applications for UCT's metal catalysts. They may be cross-linked with small quantities of multifunctional silanes that condense with silanol groups, as in the following equation:

Typical Properties
Product PC040 PC050 PC055 Chemical Description Zinc Octanoate Tin Octanoate Dibutyl Tin Dilaurate Carrier Polydimethyl siloxane Polydimethyl siloxane Polydimethyl siloxane Concentration 50% 50% 25%

Si OH + MeO Si

Catalyst

Si O - Si

These catalysts may also be used to apply silicon elastomers on surface treatments if the surface has an - OH group. Zn and Sn catalysts also catalyze the reaction between a silanol and hydrosilane. Application is from a dilute (0.5 - 2%) hydrocarbon or chlorinated hydrocarbon solution and cured at 110 - 150C.
92

UCT also offers an extensive line of one part heat or moisture curable pre formulated systems under the Glassclad product line. These are described in detail in Figures 24-29. Brief overviews of these coatings are given below. PS252, a one part moisture cure silicone described in Figure 24. Cure generates a clear soft shiny hydrophobic silicone coat. PS200 , a one part coating applied in water to glass or other active substrate to generate a highly hydrophobic deactivated surface. Technically a silane as it is C18 functional. See detailed information in Figures 25 and 26. PS216, described in Figure 27. A one part reactive chloro silicone applied in dry alcohol or aprotic solvent. Generates a permanently bonded hydrophobic silicone surface to glass, with lower critical surface tension than PS200 coatings. PS220,PS225 and PS233, all one part solvent applied thermally cured silicones, described in Figure 28. All generate hard abrasion resistant clear films. PS222 and PS225, are one part neat or solvent applied silicones thermally generating thin silicon dioxide films. For detailed description see Figure 29. PR6772, a water borne protective coating for masonry. Refer to Figure 30.
93

Figure 24 PS252 Glassclad FF

Applications
PETRARCH FF (PS252) is a source of filler-free silicone rubber in a tough bulk film. It exhibits high bond strength to a wide range of substrates including other silicones, silica, metals and solvent compatible plastics and fibers. In biomedical equipment, PETRARCH FF coatings reduce physiological interaction including protein adsorption and clot initiation. In optical devices it provides a clear mechanical barrier that seals and gaskets without scratching or initiation notch failure.

Description
PETRARCH FF (PS252) is a moisture-activated silicone RTV dispersed in a solution of tetrahydrofuran/dioxane. In the presence of atmospheric moisture a condensation of silicone prepolymers to a high molecular weight rubber occurs. The byproduct of the reaction is acetic acid, which imparts a vinegar-like odor. The system is designed for wet out and adhesion to polar substrates.

94

Figure 24 PS252 PETRARCH FF (Contd)

Cured Properties
Tensile Strength Elongation Durometer, Shore A Tear Strength >100psi >150% >8 >5psi

Uncured Properties
Percent Viscosity Specific gravity Skin over time Cure time (10 mls) Flash Point 48-52% 350-400 ctsks 0.97 30-45 min 6-8 hours 0

Application Methods
PETRARCH FF is applied by dipping or brushing. Solvent is allowed to evaporate. Cure is at room temperature.

Caution:
Use in a well ventilated area. Flammable. Keep away from open flame.
95

Figure 25 PS200 Glassclad-18 Hydrophobic Coating = Trademark of Sivento, Inc.

PS200 (Glassclad -18) Imparts the Following Properties to Treated Surfaces Non-adherent, non-oily surfaces Greater scratch resistance Easier cleaning, improved appearance Reduces the number of surface polar sites PS200 = Glassclad 18 Uses Applications where Glassclad 18 has been used successfully include: Laboratory glassware - improves drainage, reduces breakage. Porcelain ware - provides a glide surface and reduces adhesion to other porcelain ware. Optical fibers - provides lubricity and reduces breakage during fabrication and in operational flexing. Clinical analysis - treatment of analytical equipment extends clotting time of blood, reduces hemolysis, reduces protein adsorption. Glassclad 18 is not for food or drug use. Fluorescent light bulbs - increases scratch resistance, reducing breakage, increases surface resistivity.
96

Figure 25 PS200, Glassclad-18 Hydrophobic Coating (Contd)

Properties of Treated Surface
Values reported are for glass slides dipped in 1 % solution of Glassclad 18 (PS200) and cured at 100C. Critical surface tension c =78 dynes/cm Untreated Treated (hydrophobic) c =31 dynes/cm Surface resistivity Untreated Treated 1 x 10 ohms 13 1.2 x 10 ohms
12

Blood protein adsorption (glass slide on glass slide) comparative 100 hour adsorption values for whole human blood on borosilicate glass surfaces 2 Untreated 0.13mg/mm 2 Treated 0.01-0.02mg/mm

Coefficient of friction, static Untreated 0.9-1.0 Treated 0.2-0.3

These results are not meant to suggest in vivo application of Glassclad 18. Glassclad 18 should be used only in treatment of diagnostic apparatus for clinical analysis in outside the human body application.

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Figure 25 PS200, Glassclad-18 Hydrophobic Coating (Contd)

Description

Glassclad 18 (PS200) is a monomeric octadecylsilane derivative in a solution of tbutanol and diacetone alcohol that reacts with water to form a silanol-rich prepolymer and an alcohol. The silanol-rich prepolymer is able to condense with available hydroxy groups of glass or other siliceous materials to form a chemically bound alkylsilicone.

Typical Properties of Glassclad 18 (PS200)

% active Color, Gardner scale Flashpoint Specific gravity Solidification point 20% 8 10C 0.88 -30C

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Glassclad 18 (PS200) is most frequently used as a dilute aqueous solution containing 0.1%-1.0% of reactive silicone prepolymer. A 0.2% solution of active chemical can be easily prepared by adding one part by weight of the product as supplied to 99 parts of water while stirring. The following procedure is frequently employed. 1. Thoroughly clean objects with an alkaline detergent. Used-glass surfaces may require immersion in 2-3% sodium hydroxide. All detergent or alkali should be removed with a final rinse. 2. Prepare a 1% solution of Glassclad 18 in water. Ordinary tap water, but not hard water, is acceptable. 3. Immerse the glass or vitreous surface in the solution for 5-10 seconds, ensuring that all surfaces are wetted by the solution. Agitation of the solution or the part generally results in more uniform deposition. After immersion remove the part and thoroughly rinse with water to remove excess Glassclad 18 from the surface. 4. Cure Glassclad 18 coatings by bringing surface temperature to 100C for 3-5 minutes. Room temperature cure may be accomplished by air drying for 24 hours if relative humidity is 65% or less. Each liter of solution will coat approximately 80 one liter beakers or 600 15cm test tubes. It will coat approximately 250 m2 of surface. Stability of Glassclad 18 and Solutions Aqueous solutions of Glassclad 18 are not stable indefinitely and may turn cloudy and precipitate after standing for several days. The solution stability can be optimized by adjusting the pH of the solution to 4.5-5. PS200 = Glassclad 18
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Figure 26 PS200Application Methods

Figure 27 Glassclad 6C
PS216 = Glassclad 6C Uses
Applications where Glassclad 6C (PS216) has been used successfully include: Laboratory glassware - improves drainage, reduces breakage. Fiberoptics -reduces moisture adsorption and surface fracture. Clinical analysis - reduces protein and lipid adsorption of diagnostic glassware: Glassclad 6C (PS216) is not for food or drug use. Electronic glassware - reduces surface tracking in mercury switches and optical displays.

Properties of Treated Surface

Critical surface tension c =78 dynes/cm Untreated Treated (hydrophobic) c =25 dynes/cm

Values reported are for glass slides dipped in 1 % solution of Glassclad 6C (PS216) and cured at 100C.

Description
Glassclad 6C (PS216) is a chlorine terminated polydimethylsiloxane telomer. The chlorines react with hydroxy and silanol groups of glass or other siliceous surfaces to form a chemically bound polydimethylsiloxane siliconized surface.

Typical Properties of Glassclad 6C (PS216)

% active 100% Flashpoint 5C Specific gravity 0.98-1.00 100

PS216 Application Methods

is a chlorinated polysiloxane and is corrosive. Avoid skin and eye contact. Use in a well ventilated area. 1. Glassclad 6C (PS216) is most frequently applied as a 2-10% solution in dry solvents such as hexane, methylene chloride, or 1, 1,1-trichloroethane. Articles are dipped or wiped. The articles can be cured by air drying for 24 hours at conditions of less than 75% relative humidity. Heat curing at 110C for 15-20 minutes in an exhausted oven provides the most effective surface treatment. 2. A master batch of Glassclad 6C (PS216) in isopropanol or ethanol is desirable when large surfaces are to be treated and the acidic byproducts are difficult to handle. A 0.5 to 2% solution of Glassclad 6C (PS216) in isopropanol is prepared in a well ventilated area. Hydrogen chloride fumes issue during this stage. Acidic character is reduced for subsequent surface treatment. Overtreatment results in a cloudy surface. The concentration of Glassclad 6C (PS216) should be reduced to eliminate this effect.

Glassclad 6C(PS216)

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Figure 28
Protective Hard Coatings
Glassclad HT(PS220) is a high temperature modified phenylsiloxane resin which has a continuous use temperature exceeding 350C. It is used both as a thin film coating and for the production of laminated structures. It has a tensile strength of 3,500 psi and a hardness of 120R (R=Rockwell). Parts are dipped or sprayed with undiluted resin and cured 20 to 30 minutes at 240C. PS220 = Glassclad HT 20% solids in xylene. Glassclad EG (PS225) is a thermally stable resin which forms a moderately flexible film with excellent adhesion and low chloride content. It provides an oxidation and mechanical barrier for resistors and circuit boards. Part application is by spraying or dipping. Cure is 20 minutes at 220C. PS225 = Glassclad EG 20 % solids in xylene. Glassclad RC (PS233) is a methylsilicone resin which forms a coating with high temperature (250C) serviceability. Its high dielectric strength, thermal resistance and mechanical strength make it ideal as an electrical component and circuit board coating. Glassclad RC reacts covalently with glass and siliceous surfaces to form a permanent bond. It has excellent abrasion resistance properties and can be applied to materials as a protective coating. It is typically applied by dipping or brushing followed by air dry and final cure at 150C for one hour. PS233 = Glassclad RC 50% solution in isopropanol

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Figure 29
Silicon Dioxide (SiO2) Sources
Glassclad TF(PS235) is employed as a source of thick film (0.2-0.4 micron) coatings of silicon dioxide. Glassclad TF (PS235) is a polymeric precursor of silicon dioxide. Silica formation begins o o at 110-120 C and is complete by 220 C. The polymer converts to approximately 36% SiO2. Applications for Glassclad TF include dielectric layers, abrasion resistant coatings, and translucent films. Glassclad TF (PS235) can be applied without solvent or in chlorinated hydrocarbon and ester vehicles. Specific gravity is 1.13. It is 100% solids. PS235 = Glassclad TF Glassclad SO (PS222) is specifically formulated for the deposition of silicon dioxide. Undoped films are useful as protective films and as getter layers; doped silicon oxide film as getter layers. Cure is o o accomplished in two steps:1) 2-5 mins at 200 C; 2) final cure at 500 C. S.G=0.84 PS222 = Glassclad SO

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Figure 30
PR6772 Hydrophobic Masonry Coating
Glassclad MS (PR6772) is an alkaline resinous silicone solution that reacts with siliceous substrates including stone and masonry.

Uses
Masonry - renders surface water repellent. Ceramics - increases green strength and green storage life.

Description
Glassclad MS (PR6772) is a 30% sodium methyl siliconate solution in water.

Application
Glassclad MS (PR6772) is diluted 10:1 with water then sprayed or brushed onto surfaces. The solution should be air-dried 24 to 36 hours prior to immersion in water.

Caution
PR6772 = Glassclad MS

Avoid skin contact, Glassclad MS (PR6772) is alkaline.

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Another class of silicones which has found extensive use as photocopy releasing agents or additives for epoxies are the amino functional silicones. The basic structure of a typical amino terminated silicone is illustrated in Figure 31. Typical cure chemistries when used as additives in urethanes or epoxy formulations involve reaction of the amine with an isocyanate group in a curing urethane polymer, or the three membered epoxy ring in a curing epoxy resin. A typical reaction with the isocyanate group is illustrated in Figure 32. Silicone additives impart greater flexibility and lower glass transition temperatures to epoxy and urethane resins.

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Figure 31
Aminofunctional Silicones
CH3 H2NCH2CH2CH2 Si CH3

( )
CH3 Si O CH3
106

CH3 Si CH3 CH2CH2CH2NH2

Figure 32
Reactions of Amino Functional Silicones
Aminopropyl-terminated siloxanes are used to form a variety of block copolymers including polyamides, polyurethanes and polycarbonates. A typical reaction is shown below:

Me Si Me CH2 CH2 CH2 NH2 + RNCO

Me

SiCH2 CH2 CH2 NHCNR Me H

The silicone is employed to produce silicone modified epoxy resins. It also has improved adhesion to both painted and unpainted metal surfaces allowing use in corrosion resistant coatings and polishes. Amino functional silicones are reactive additives to both epoxy and urethane formulations. Aminoalkyl functional T-structure polymers demonstrate the same range of chemical reactivity as the aminopropyl-terminated siloxanes (reactivity with epoxides, isocyanates, carboxylic acids, etc.). The branched polymers are more likely to find application as formulative additives rather than as prepolymers. Typical applications include detergent polishes, leather finishes, and internal mold releases for nylon.
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The UCT product line of aminosilicones is summarized in Table 24. PS509-PS513 are difunctional in primary amine at the polymer terminals. These silicones are useful as photocopy releasing agents or chain extending additives for commercial epoxies or urethanes. PS806-PS810 are copolymeric materials with varying molar amounts of ethylenediamine functionality in the backbone. The PS811-PS820 series is similar except that the amino groups are all primary aminopropyl. All of the PS806-PS820 series are curable with atmospheric oxygen to inert films. The films have excellent adhesion to steel and have found application as syringe needle coatings.

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Table 24 Amino Functional Silicones

Product # [CAS #] PS509 PS510 [106214-84-0] PS511 PS512 PS513 PS804 PS805 PS806 PS807 PS808 PS809 PS810 PS811 Description Viscosity Specific Gravity 0.98 0.98 0.98 0.98 0.98 0.97 0.97 0.96 0.97 0.97 0.97 0.97 1 2.5 3-5 4 4 10 10 2.5 Mole% Comonomer 100 g 1 Kg Polydimethylsiloxane, Aminopropyldimethyl Terminated 10-15 50 100-120 1000 2000 100 2500 50-90 50 100 250 2500 12500 X X X X X X X X X X X X X X X X X X X X X X X X X X

Polydimethylsiloxane, Amino Functional Copolymers COMONOMER = (Aminoethylaminopropyl) Methyl

COMONOMER = (Aminopropyl) Methyl

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Table 24 Amino functional silicones (contd)

Product # [CAS #] PS811.5 PS812 PS813 PS814 PS815 PS816 PS817 PS818 PS819 PS820 PS401 [71750-80-6 Description Viscosity Specific Gravity Mole% Comonomer 2.5 0.98 3-5 3-5 4 4 4 4 4 0.974 0.97 0.97 4 10 100 g 1 Kg

COMONOMER = (Aminopropyl) Methyl 35000 70-110 100-200 250 750 2500 5000 7500 12500 750 200-600 X X X X X X X X X X X X X X X X X X X X X X

Amino Functional T-Structure

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Amino functional T-structures containing both alkoxy and amino functionality are one part moisture curable systems. They self catalyze by the amino groups first promoting hydrolysis to silanols, then also catalyzing crosslinking of these silanols. PS401 is a representative and popular member of this series, represented in Figure 33. Other potential chemistries applicable to aminosilicones are incorporation into polyester or urethane compositions as illustrated in Figure 34. The only drawback to use of aminosilicones is phase incompatibility with many industrial resins. In many cases emulsified mixes still react on heating and impart the desired softening to the resin.

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Figure 33
PS401
CH3 O NH2C2H4NHC3H6Si O CH3 O CH3 Si CH3 n CH3 O CH3 O Si O C3H6NHC2H4NH2

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Figure 34 Reactions of Aminosilicones SiCH2CH2CH2NH2

OCNR CH 3 Si CH3 O O O CH 2CH 2CH 2 NH2 CH 3 Si CH 3 CH 3 Si CH 3 CH 2CH 2CH 2N O O CH 2CH 2CH 2NCNR O

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Amino functional silicones have also found utility in the Rimplast line of thermoplastic interpenetrating network (IPN) composites. Typical physical properties for these composites are listed in Table 25. Figure 25, although now dated, depicts high performance medical devices that have in the past been fabricated with these materials.

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Table 25 Properties of Rimplast silicone-thermoplastic IPNs

Property Tensile strength, MPa Elongation, % Flexural strength, MPa Flexural modulus, MPa Tear strength, kN/m Aliphatic urethane 34.5 350 >60 Nylon 12 35.9 20 55 1380 Nylon 6/6 69.6 5 96.5 2482 SEBS 8.3 1200 400 3.5 at 300% 25

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Figure 35
Intra-aortic balloon pumps, requiring mechanical and fatigue strength along with physiological inertness, are fabricated from silicone-urethanes (courtesy Kontron Cardiovascular)

This artificial heart, a totally implantable, hydraulically driven total cardiac prosthesis, is constructed with silicone-urethanes (courtesy R. Ward, Thoratec Laboratories)
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Other silicone functionalities available in a more limited selection are carbinol (C-OH terminated) and carboxy (COOH terminated) materials. Carbinol silicones are very reactive additives in epoxy or urethane resins while carboxy silicones can react directly into a polyester polymer matrix. Phase incompatibility again limits additive amounts, but low addition levels or emulsification still can allow usage. The UCT offerings include PS555 (carbinol terminated) and PS563 (carboxy terminated) silicones. Contact UCT technical support for more information. The chemical reactions described above are shown in Figure 36.

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Figure 36 Miscellaneous Functionalities

Me
Si R O OCH2 CH 2OH + CH2CHR

Me
Si R

OH OCH2 CH2OCH2CHR

Me

Me

Carbinol Terminated
Me
O

Me

SiCH 2CH 2CH2COH + HOR

Me

SiCH 2 CH 2 CH 2 COR + H O H

Me

Carboxypropyl Dimethyl Terminated

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The wide range of curable silicone functionality available is summarized in Figure 37. Certain functionalities such as mercapto have not been covered here due to space limitations. See the UCT product catalog or contact technical service for more informationon these silicone materials.

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Figure 37 Functional Silicone Reactivity Guide

Class Vinyl Reactivity / Product Class
peroxide activated cure (heat cured rubber) vinyl addition (platinum cure)

Hydride
dehydrogenative coupling (metal salt cure) (foamed silicones, water repellent coatings)

Silanol

moisture cure 1-part RTVs condensation cure 2-part RTVs

Alkoxy/Polymeric Alkoxide

sol-gel (ceramics, ormosil)

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Figure 37 Functional Silicone Reactivity Guide (Contd)

Class Amine Epoxy Carbinol Methacrylate/Acrylate Mercapto Acetoxy/Chlorine/Dimethylamine
121

Reactivity / Product Class

polyureas, polyimides epoxy addition cationic UV polyester polyurethane radical (including UV) cure thiol-ene UV cure thermal cure

moisture cure

In summary, this article has attempted to give the scientist, industrial chemist and formulator a basic understanding of silicone functionality, curing chemistries, catalysts and formulation techniques. The overview has used the extensive line of United Chemical Technologies silicones as reference points. UCT is a major manufacturer of the complete line of curable and non curable silicone fluids, gums, T-resins and curing catalysts. Contact UCT at 800-5410559 for ordering, pricing and technical support on these materials.

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REFERENCES 1) Kirk Othmer, Encyclopedia of Chemical Technology, Third Edition, Volume 20, John Wiley and Sons, 1982. 2) Michael A. Brook, Silicon in Organic,Organometallic and Polymer Chemistry, Wiley Interscience, 2000, ISBN 0-471-19658-4. 3) I. Koga, Reductions Using Hydrosilanes, Silicon Compounds Registry and Review, Second Edition, 1982, 36-45. Paper available from United Chemical Technologies. 4) Bruce D. Karstedt, Platinum-Vinyl Siloxanes, U.S. Patent 3,715,334, Feb 6, 1973.

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