# US 11,306,205 B2 · Addition-curable silicone rubber composition

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- Number: US 11,306,205 B2
- Document ID: US11306205B2
- Status: Granted
- Kind: B2
- Application number: 16/472,282
- Filed: 2017-12-20
- Published: 2019-12-12
- Granted: 2022-04-19
- Earliest claimed: 2016-12-23
- Assignees: Momentive Performance Materials Inc.
- Applicants: Momentive Performance Materials Inc.
- Inventors: Huiping Zhang; Srividhya Marimuthu; Gunnar Hoffmueller; John Mitchell Huggins; Enise Michalski
- Web page: https://patentgrep.com/patent/US11306205B2

## CPC

- C08L 83/04: Polysiloxanes
- C09D 183/04: Polysiloxanes
- C08J 5/121: {by heating}
- C08G 77/12: containing silicon bound to hydrogen
- C08G 77/20: containing silicon bound to unsaturated aliphatic groups
- C08J 2383/07: containing silicon bound to unsaturated aliphatic groups
- C08L 2205/025: containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
- C08L 2205/16: Fibres; Fibrils
- C08L: COMPOSITIONS OF MACROMOLECULAR COMPOUNDS (compositions based on polymerisable monomers C08F, C08G; artificial filaments or fibres D01F; textile treating compositions D06)
- C09D: COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR (cosmetics A61K; processes for applying liquids or other fluent materials to surfaces, in general, B05D; staining wood B27K5/02; glazes or vitreous enamels C03C; natural resins, French polish, drying-oils, driers, turpentine, per se, C09F; polishing compositions other than French polish, ski waxes C09G; adhesives or use of materials as adhesives C09J; materials for sealing or packing joints or covers C09K3/10; materials for stopping leaks C09K3/12; processes for the electrolytic or electrophoretic production of coatings C25D)
- C08J: WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H (working, e.g. shaping, of plastics B29)
- C08G: MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS

## Abstract

The present invention relates to an addition-curable silicone rubber composition having self-bonding capability. The addition-curable silicone rubber composition exhibits self-bonding capability in particular to substrates that contain residual hydroxyl groups or other residual hydrosilyl-reacting groups on their surface, including polycarbonate, polyester, polyamide, polysulfone, polyurethane, phenolic resin, epoxy resin, cellulose, glass and the mixture thereof.

## Claims

### Claim 1

An addition-curable silicone rubber composition, comprising:
(A) at least one polyorganosiloxane having at least two unsaturated hydrocarbyl residues,
(B) at least one polyorganohydrogensiloxane selected from one or more polyorganohydrogensiloxanes of the general formula (2):
[M1a2D1b2T1c2Qd2Ze2]m2 (2)
wherein the siloxy units
M=R3SiO1/2, or M**
D=R2SiO2/2, or D**
T=RSiO3/2, or T**
Q=SiO4/2,
M**=HR2SiO1/2, D**=HRSiO2/2, T**=HSiO3/2,
Z is a divalent optionally substituted hydrocarbyl bridging group with up to 14 carbon atoms between two siloxy groups as defined before,
wherein R is selected from optionally substituted hydrocarbyl groups with up to 30 carbon atoms and poly(C2-C4)-alkylene ether groups with up to 1000 alkylene oxy units. the groups R being free of aliphatic unsaturation, and wherein
a2=2-10
b2=0-1000
c2=0-50
d2=0-5
m2=1-1000,
with the proviso that there are at least two groups selected from M**, D** and T**,
(C) at least one hydrosilylation catalyst, comprising a transition metal,
(D) at least one organosilicon compound containing at least one polyvalent aromatic group, which is not directly attached to a silicon atom, and at least one Si-H group, different from compound B),
(E) at least one aromatic compound with at least two unsaturated hydrocarbyl groups, which aromatic compound does not contain a siloxane group, and does not contain an ester group,
(F) optionally one or more reinforcing fillers,
(G) optionally one or more auxiliary additives.

### Claim 2 (depends on 1)

The addition-curable silicone rubber composition, according to claim 1, wherein component (A) is selected from one or more polyorganosiloxanes of the general formula (1):
[MaDbTcQdZe]m (1)
wherein
a=0-10
b=0-2000,
c=0-50
d=0-10
e=0-300
m=1-1000, with
a+b+c+d+e>2, and
M=R3SiO1/2, or M*
D=R2SiO2/2, or D*
T=RSiO3/2, or T*
Q=SiO4/2,
Z is a divalent optionally substituted hydrocarbyl bridging group with up to 14 carbon atoms between two siloxy groups as defined before,
wherein R is selected from optionally substituted hydrocarbyl groups with up to 30 carbon atoms and poly(C2-C4)-alkylene ether groups with up to 1000 alkylene oxy units. the groups R being free of aliphatic unsaturation, and wherein
M*=R1pR3-pSiO1/2,
D*=R1qR2-qSiO2/2,
T*=R1SiO3/2, wherein
p=1-3,
q=1-2, and
R1 is selected from unsaturated optionally substituted hydrocarbyl groups with up to 30 carbon atoms,
with the proviso that there are at least two groups selected from M*, D* and T*.

### Claim 3 (depends on 1)

The addition-curable silicone rubber composition, according to claim 1, wherein component (C) is selected from hydrosilylation catalysts comprising platinum.

### Claim 4 (depends on 1)

The addition-curable silicone rubber composition, according to claim 1, wherein component (D) is an organosilicon compound comprising one or more straight-chain or cyclic optionally substituted organosiloxane moieties containing 1 to 30 silicon atoms, at least one Si-H group, and at least one polyvalent aromatic group, which is not directly attached to a silicon atom.

### Claim 5 (depends on 1)

The addition-curable silicone rubber composition, according to claim 1, wherein the compound (E) is selected from the group consisting of an aromatic compound of the formula (3):
wherein R2 to R7 are the same or different from each other and are selected from the group consisting of hydrogen, hydroxy, halogen, —R8, wherein R8 is a saturated or unsaturated, optionally substituted hydrocarbyl group with up to 20 carbon atoms, —O—R9, wherein R9 is a saturated or unsaturated optionally substituted hydrocarbyl group with up to 20 carbon atoms,
with the proviso that the compound of formula (3) comprises at least two unsaturated hydrocarbyl groups, and
an aromatic compound of the formula (4):
wherein R11 to R20 are the same or different from each other and are selected from the group consisting of hydrogen, hydroxy, halogen, —R21, wherein R21 is a saturated or unsaturated optionally substituted hydrocarbyl group with up to 20 carbon atoms, —O—R22, wherein R22 is a saturated or unsaturated optionally substituted hydrocarbyl group with up to 20 carbon atoms, and a silyloxy group of the formula —OSiR24R25R26, wherein R24, R25, and R26 are independent from each other selected from an optionally substituted hydrocarbyl group with up to 20 carbon atoms,
X is selected from the group consisting of the groups:
single bond,
—R27—, wherein R27 is a divalent linear or cyclic saturated optionally substituted hydrocarbyl group with up to 20 carbon atoms,
—C(O)—,
—S(O)2—,
—S(O)—,
—S—
—O—Si(R28)2—O—, wherein R28 is independently selected from the group of a halogen, and a saturated or unsaturated hydrocarbyl group with up to 6 carbon atoms, and
—O—
with the proviso that the compound of formula (4) comprises at least two unsaturated hydrocarbyl groups.

### Claim 6 (depends on 1)

The addition-curable silicone rubber composition, according to claim 1, wherein the compound (E) is selected from the group consisting of the compounds of the formula:
(2-allyl-4-[1-(3-allyl-4-hydroxy-phenyl)-1-methyl-ethyl]phenol (2,2′-diallyl bisphenol A))
(1-allyloxy-4-[1-(4-allyloxyphenyl)-1-methyl-ethyl]benzene (bisphenol A diallyl ether)))
([2-allyl-4-[1-(3-allyl-4-trimethylsilyloxy-phenyl)-1-methyl-ethyl]phenoxy]-trimethyl-silane)),
([2-allyl-4-[1-[3-allyl-4-[dimethyl(vinyl)silyl]oxy-phenyl]-1-methyl-ethyl]phenoxy]-dimethyl-vinyl-silane).

### Claim 7 (depends on 1)

The addition-curable silicone rubber composition according to claim 1, wherein component (F) is selected from reinforcing fillers having a BET surface area of 50 m2/g or more.

### Claim 8 (depends on 1)

The addition-curable silicone rubber composition according to claim 1, wherein component (G) is selected from the group of an inhibitor; a plasticizer or softener; non-reinforcing fillers; and/or a fiber material chosen from a polyester fiber, cellulose fiber, polyamide fiber, polyurethane fiber, and/or a glass fiber.

### Claim 9 (depends on 1)

The addition-curable silicone rubber composition according to claim 1, comprising:
100 parts by weight of component (A),
0.01 to 100 parts by weight of component (B)
0.5 to 1000 ppm of component (C) based on the weight amount of the transition metal and based on the total weight of components (A) and (B),
0.01 to 10 parts by weight of component (D)
0.01 to 10 parts by weight of component (E),
0 to 100 parts by weight of component (F), and
0 to 100 parts by weight of component (G).

### Claim 10 (depends on 1)

The addition-curable silicone rubber composition according to claim 1, comprising per 100 parts by weight of the component (A):
0.05 to 2 parts by weight of component (D), and/or
0.02 to 1 parts by weight of component (E).

### Claim 11 (depends on 1)

A cured silicone rubber composition, obtained by curing the addition-curable silicone rubber composition as defined in claim 1.

### Claim 12 (depends on 1)

The use of the addition-curable silicone rubber composition as defined in claim 1 for the manufacture of a composite material, comprising a substrate and the cured silicone rubber composition on at least one part of the surface of the substrate.

### Claim 13 (depends on 11)

A composite material comprising a substrate and the cured silicone rubber composition as defined in claim 11 on the surface of such substrate.

### Claim 14 (depends on 1, 13)

A method of manufacturing a composite material according to claim 13, wherein a substrate that contains residual hydrosilyl-reaction groups is coated with the addition-curable silicone rubber composition as defined in claim 1 and thereafter the addition-curable silicone rubber composition is cured on the surface of said substrate.

### Claim 15 (depends on 13)

The composite of claim 13, wherein the substrate is selected from the group consisting of acrylonitrile-butadiene-styrene resins, styrene resins, polyethylene resins, polypropylene resins, polyacetal resins, acrylic resins, polyethylene terephthalate, polybutylene terephthalate, polyphenylene sulfide resins, polyimide resins, polycarbonate, polyester, polyurethane, poly(phenylene oxide), polysulfone, polyvinylalcohol, phenolic resin, epoxy resin, polyamide, polyetherimide, cellulose, glass and the mixture thereof.

### Claim 16 (depends on 14)

The method of claim 14, wherein the substrate is a thermoplastic resin, and the method comprises molding the thermoplastic resin and thereafter over-molding and curing the addition-curable silicone rubber composition onto the thermoplastic part in the same molding equipment.

### Claim 17 (depends on 1)

The addition-curable silicone composition of claim 1, wherein the at least one polyorganohydrogensiloxane is selected from a siloxane of the formula (2a):
Ha1(R)3-a1Si[RHSiO]x[R2SiO]y[RR1SiO]zSi(R)3-a1Ha1 (2a)
wherein R and R1are as defined above,
a1 is 0-1,
x=2-1000,
y=0-650,
z=0-65, and
2<x+y+z<1000.