Organo-Functional Polymers & Copolymers

Functionally terminated polydimethylsiloxanes describe a class of silicones generally of low or intermediate molecular weight which contain a reactive functionality that is not readily affected by water. They are generally employed as reactive prepolymers either in building high molecular weight silicone elastomers or block copolymers with non-siloxane materials. Polymers of this type are generally of the structure:

Me Y Si Me O

Me Si Me O n

Me Si Me Y

where Y is the organo-functional group. Functional group copolymers provide avenues to high molecular weight and crosslinked materials with silicone-like properties by unconventional cure systems. They also allow the formation of hybrid polymer systems by offering sites for copolymerization and crosslinking. Copolymers of this type are generally of the form:

Me Me Si Me O

Me Si Me O m

R Si Me O n

Me Si Me Me

Organofunctional T-structure polymers contain 2-3 branch points. Their rheology is significantly different from linear materials. These polymers are generally of the form:

Me Me3Si O Si Me n O

R Si O Me3Si O SiMe3
n

Me O Si Me O n SiMe3

250

AMINO FUNCTIONAL POLYMERS

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 CH 2CH2 CH2 NH2 + RNCO Me O

SiCH2CH 2CH 2NHCNR 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 additive rather than as prepolymers. Typical applications include detergent polishes, leather finishes, and an internal mold release for nylon.

Product # Description [CAS #] Polydimethylsiloxane, Aminopropyldimethyl Terminated PS509 [106214-84-0] PS510 PS511 PS512 PS513 Polydimethylsiloxane Amino Functional Copolymers Comonomer [71750-79-3] (AminoethylaminoPS804 propyl)Methyl PS805 PS806 PS807 PS808 PS809 PS810 PS811 PS811.5 PS812 PS813 PS814 PS815 PS816 PS817 PS818 PS819 PS820 PS401 [71750-80-6] " " " " " " (Aminopropyl)Methyl " " " " " " " " " " Aminoalkyl 251

Viscosity 20-30 50 100-120 1000 2000

SG 0.98 0.98 0.98 0.98 0.98

Mole % Comonomer

100 2500 50-90 50 100 250 2500 12500 35000 70-110 100-200 250 750 2500 5000 7500 12500 750 200-600

0.97 0.97 0.96 0.97 0.97 0.97 0.97 CAS No. 99363-37-8 0.97

1 2.5 3-5 4 4 10 10 2.5 2.5 3-5 3-5 4 4 4 4 4 4 10

0.974 0.97 0.97

Amino Functional T-Structure

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.

Viscosity SG Description Polydimethyl siloxane 10 Monomethacryloxypropyl terminated 2000 PS583 1.00 Polydimethyl siloxane Methacryloxypropyl terminated Polydimethyl Siloxane, Methacrylate & Acrylate Functional Copolymers Product # PS560 Comonomer (Acryloxypropyl)Methyl (Methacryloxypropyl)Methyl PS852 (Methacryloxypropyl)Methyl PS853 (Methacryloxypropyl)Methyl PS854 (Methacryloxypropyl)Methyl Methacrylate Functional T-structure PS406 Methacryloxy Propyl Acrylate Homopolymers PS 901 Poly(Methacryloxypropylmethyl)Siloxane (Includes Cyclics) PS 901.5 Poly(Acryloxypropylmethyl)-Siloxane (Includes Cyclics) PS802 PS851 80-120 1000-2000 10000 2500 0.98 0.98 0.982 0.991 0.98 25-50 0.97 25-125

Mole % Comonomer

15-20 2-3 5 8 16

100

1.10-1.12

252

MERCAPTO FUNCTIONAL POLYMERS

Mercapto functional siloxanes strongly adsorb onto fibers and painted surfaces. As components in car polish they are effective rust preventatives. They act as internal mold release agents for rubber and semipermanent lubricants for automotive weather stripping. Mercapto polymers are valuable additives into cosmetic and hair care products. They also will undergo radical initiated (including UV) addition to unsaturated resins.

Viscosity Description Mercapto Functional, Polydimethyl Siloxane Copolymers CAS No. [102783-03-9] 0.954 PS848 25 (Mercaptopropyl)Methyl 0.973 PS849 200 (Mercaptopropyl)Methyl 0.974 PS849.5 25000 (Mercaptopropyl)Methyl PS850 100-200 (Mercaptopropyl)Methyl 0.991 PS850.5 75 (Mercaptopropyl)Methyl PS855 Dimethoxy Mercapto Propyl Terminated Product # Mercapto Methyl Homopolymer Polymercaptopropyl PS927 Methyl Siloxane Mercapto Functional, T-Structure, Mercapto at branch point PS405 Mercaptopropyl 75-150 1.06

SG

Mole % Comonomer 2 2 2 5-10 14

100-200

0.97

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MISCELLANEOUS FUNCTIONALITIES
Chlorinated aromatic siloxanes typically have high refractive indices. The chloromethylaromatic groups often decompose at temperatures greater than 150 C to give radicals capable of inserting into carbon-hydrogen bonds. Exposure to electron beam radiation also induces radical formation. Chloromethyl terminated polydimethylsiloxanes can be used as intermediates for the production of hydrolytically stable polyether-polysiloxane copolymers. They display reduced overall activity when compared to other functionally terminated polydimethylsiloxanes. Reaction will occur with amines, alkoxides, and sulfides. Chloropropylmethylsiloxane-dimethylsiloxane copolymers provide a high density, moderately stable fluid which is reactive with polysulfides and durable press fabrics. The material is an excellent internal lubricant where flammability resistance is a factor.

Me Si Me

O R OCH 2CH 2OH + CH2CHR

Me Si Me

OH R OCH 2CH 2OCH 2CHR

Carboxypropylsilicones are employed in polyester and polyamide copolymers. The esterification reaction is probably the most important because it allows reaction with cellulosic materials. Such materials can be used in copolymerization with polyols and as a durable softening agent for textiles. Carboxylic acid functional fluids, when reacted with inorganic bases or amines, perform as antistatic surfactants and lubricants. They are excellent rheology and wetting modifiers for polyesters.
Me O Me O

SiCH2CH 2CH 2COH + HOR Me

SiCH2CH 2CH 2COR + H2O Me

They also serve as dispersing agents for metal powders. Carbinol terminated siloxanes contain primary hydroxyl groups which may be reacted into such systems as polyurethanes, epoxies, polyesters, and phenolics. A typical reaction is shown below: The material is used as a reactive additive for urethane leather finishes and as a reactive internal lubricant for polyester fiber melt processing. Epoxy functional siloxanes are used predominantly in self-crosslinking acrylic latexes. They are also used to treat textiles to increase wrinkle recovery, reduce needle damage and improve water repellency.

254

MISCELLANEOUS FUNCTIONAL POLYMERS

Prod. # HOMOPOLYMERS PS902 PS906 PS914 PS932 COPOLYMERS PS823 Description [CAS #] Polybis(Cyanopropyl)Siloxane PolycyanopropylmethylSiloxane [67762-86-1] Polydiethylsiloxane [63148-61-8] Poly(Chlorophenethyl)Methylsiloxane (Chloromethylphenethyl)methyl, Dimethyl Siloxane Copolymer (Chloropropyl)MethylDimethyl Siloxane Copolymer [70900-20-81] (Cyanopropyl)Methyl Dimethylsiloxane Copolymer [68938-51-2] (Cyanopropyl)Methyl (48-50%)-MethylphenylSiloxane Copolymer (45-55%)Glycidoxypropyl Methyl-Dimethyl Siloxane Copolymer Viscosity SG Nominal Mole %

4000-5000 1500-2500 1.0 1.09

250-350

5-10

PS826

300-400

1.1

14-16

PS908

10-12

PS910

2000

PS922

FUNCTIONALLY TERMINATED Carbinol Terminated PS555 Polydimethyl Siloxane [68037-63-8] PS556 Monocarbinol Terminated PS558 Polydimethyl Siloxane Monocarbinol Terminated PS559 Polydimethyl Siloxane Carboxypropyl Dimethyl PS563 Terminated Polydimethyl Siloxane Chloromethyldimethyl PS573 Terminated Polydimethylsiloxane Dimethoxyglycidoxy Propyl PS620 Terminated Polydimethylsiloxane Mono-Epoxy Terminated PS628 Polydimethyl Siloxane T-STRUCTURE PS402
252

300-800 250-350 1000 1.06

800-1200

.98

1500-2500

1.0

110

0.97 0.97

72 0.97 125-50 0.98

Polydimethylsiloxane, Carboxypropyl T-Structure

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Silanes and Silicones for Creative Chemists

CATALYSTS

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UCT provides a variety of catalyst concentrates predispersed as pastes or solution in appropriate siloxanes. These materials allow uniform compounding in gum or other vulcanizeable compositions. While a variety of peroxides are used in silicone rubber compounding the most widely employed is dichlorobenzoyl peroxide. It has a low vulcanization temperature and a high rate of vulcanization. It is particularly favored in hot air vulcanization. Benzoyl peroxide is another general purpose peroxide with less tendency to scorch than dichlorobenzoyl peroxide and is favored for thin sections. Zinc and tin octoates are the usual catalysts used independently or together in condensation cure RTV formulations. Divinyl siloxane/platinum catalysts are utilized in addition cure systems. Neutralized divinylsiloxane complexes in xylene are generally hotter catalysts. Cyclic vinylsiloxane solutions give moderated cures. Relative reactivitys PC072 > PC075 > PC085. Prod.# PC010 PC020 PC040 PC050 PC055 PC072 PC073 Platinum Platinum Type Peroxide Peroxide Zinc & Tin Salts Description 2,4-Dichlorobenzoyl Peroxide,50% in polydimethylsiloxane, paste consistency Benzoyl Peroxide, 50% in polydimethylsiloxane, paste consistency Zinc Octoate, 50% in polydimethylsiloxane/hydrocarbon blend Tin Octoate, 50% in polydimethylsiloxane Dibutyl Tin Dilaurate, 25% in polydimethylsiloxane Platinum Divinyl Complex, 2-3% platinum concentration in xylene, neutral Platinum Divinyl Complex, 1% platinum Concentration in Xylene, Neutral Platinum Divinyl Complex, 2% platinum Concentration in Xylene, Neutral, Colorless Platinum Divinyl Complex, 2-3% platinum concentration in vinyl terminated polydimethylsiloxane, Neutral Platinum Divinyl Complex, 5% platinum concentration in vinyl terminated polydimethylsiloxane, Neutral Platinum Divinyl Complex, 1% platinum concentration in vinyl terminated polydimethylsiloxane, Neutral Platinum Cyclovinyl Complex, 2-3% platinum concentration in cyclic vinylmethylsiloxanes, Neutral Platinum Cyclovinyl Complex, 1% platinum concentration in cyclic vinylmethylsiloxanes, Neutral Tetramethylammonium Siloxanolate 256 Cure Type Si-Vinyl Free Radical Si-Vinyl Free Radical Si-Hydride/Si-Hydroxide Si-Hydride/Si-Hydroxide Si-Hydride/Si-Hydroxide Si-Hydride/Si-Vinyl Si-Hydride/Si-Vinyl

PC074

Platinum

Si-Hydride/Si-Vinyl

PC075

Platinum

Si-Hydride/Si-Vinyl

PC075.5 Platinum

Si-Hydride/Si-Vinyl

PC076

Platinum

Si-Hydride/Si-Vinyl

PC085

Nitrogen

Si-Hydride/Si-Vinyl

PC086

Platinum

Si-Hydride/Si-Vinyl

PC090

Nitregen

Siloxy Equilibrium

The following inhibitors can be used in conjunction with the above catalysts.
Product # D6210 Name 1,3-Divinyltetramethyldisiloxane C8H18OSi2 1,3,5-Trivinyl-1,1,3,5,5-Pentamethyltrisiloxane C11H24OSi3 Tetravinyltetramethylcyclotetrasiloxane C12H24O9Si Structure
Me Me Me CH 2 Me H2C CH Si O Si CH CH 2 Me CH Me H2C CHSi OSi OSiCH Me Me Me H2C CH SiO H3C
4

T4290

CH 2

T2160

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MODIFIERS
Crosslinkers and Chain Extenders Name [CAS #] I. ACETOXY Methyltriacetoxysilane [4253-34-3] Ethyltriacetoxysilane [17689-77-9] Vinyltriacetoxysilane [4130-0809] Silicon Tetraacetate [562-90-3] Code M8980 E6345 Structure O MeSi(OCCH3 )3 O CH3 CH2 Si(OCCH3) 3 V4800 O H2 C CHSi(OCCH 3)3 S1570 O Si(OCCH3) 4 two part + one part one part one part one part Used in RTV System

II. ALKOXY 1,3-Dimethyltetramethoxydisiloxane (95%) [18186-97-5] Methyltriethoxysilane [2031-67-6]

OMe D5775 Me Si OMe M9050 CH3Si(OEt)3 O

2

one part non-corrosive + two part one part

Tetraethoxysilane (TEOS) [78-10-4]

T1807

EtO Si EtO

OEt OEt OMe Si OMe OC3H 7 Si OC3H 7 OEt Si OEt

two part

Tetramethoxysilane (TMOS) can cause blindness [681-84-5] Tetra-n-propoxysilane [682-01-9]

T1980

MeO MeO

T2090

C3 H7O C3 H7O

two part because of toxicity (specialties) two part

Dimethyldiethoxysilane [78-62-6]

D5600

Me Me

two part

III. AMIDE Bis-(N-methylbenzylamide)Ethoxymethysilane (90%) [16230-35-6]

B2409.5 (PhCONMe)2Si

OEt Me

one part non corrosive

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Crosslinkers and Chain Extenders (part 2) Code IV. AMINE Tris-(dimethylamino)Methylsilane [3768-57-8] Tris-(cyclohexylamino)Methylsilane (95%) [15901-40-3] Bis-(dimethylamino) Dimethylsilane T4050 Structure Me2N
3 SiMe

Used in RTV System one part non corrosive one part non corrosive one part

T4008 NH B2100 Me2Si NMe2 Me Si(NMe2) 2 H2 C CH SiMe

3

NMe2

Bis-(dimethylamino) Methylvinylsilane

B2300

one part

V. KETOXIME Methyltris-(methylethylKetoxime) Silane (95%) [22984-54-9] Vinyltris-(methylethylketoximine) Silane [2224-33-1]

M9220

CH3 C C2 H5 N O SiMe
3

one part non corrosive

V5050 Et C Me N O SiCH
3

one part non corrosive CH2

VI. HYDROGEN 1,1,3,3-Tetramethyldisiloxane

T2030

Me H Si Me O HMeSi O

Me O Si H Me MeH O Si O SiMeH Si MeH O Si

two part non corrosive

1,3,5,7-Tetramethylcyclotetrasiloxane

T2000

two part non corrosive

Methylhydrocyclosiloxanes

M8830

Me H

two part non corrosive

259