CA1270973A - Self-bonding precious metal catalyzed silicone rubber compositions - Google Patents
Self-bonding precious metal catalyzed silicone rubber compositionsInfo
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- CA1270973A CA1270973A CA000498347A CA498347A CA1270973A CA 1270973 A CA1270973 A CA 1270973A CA 000498347 A CA000498347 A CA 000498347A CA 498347 A CA498347 A CA 498347A CA 1270973 A CA1270973 A CA 1270973A
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- olefin
- polydiorganosiloxane
- bis
- varies
- adhesion promoter
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Abstract
SELF-BONDING PRECIOUS METAL CATALYZED
SILICONE RUBBER COMPOSITIONS
Abstract There is provided SiH-olefin precious metal catalyzed self-bonding silicone rubber compositions wherein the self-bonding additive is selected from silyl maleates, silyl fumarates, maleate-functional polysiloxanes, and fumarate-functional polysiloxanes.
SILICONE RUBBER COMPOSITIONS
Abstract There is provided SiH-olefin precious metal catalyzed self-bonding silicone rubber compositions wherein the self-bonding additive is selected from silyl maleates, silyl fumarates, maleate-functional polysiloxanes, and fumarate-functional polysiloxanes.
Description
SELF-BONDING PRECIOUS METAL CATALYZED
SILICONE RUBBER COMPOSITIONS
Background of the Invention The present invention relates to self-bonding silicone rubber compositions. More particularly, the present invention relates to SiH-olefin precious metal catalyzed self-bonding silicone rubber compositions wherein the self-bonding additive is selected from silyl maleates, silyl fumarates, maleate-functional polysiloxanes and fumarate-functional polysiloxanes.
SiH-olefin precious metal catalyzed compositions are well known in the artO Such compositions generally comprise a vinyl-containing polydiorganosiloxane, an oxganohydrogenpolysiloxane crosslinking agent and a precious metal or precious metal-containing catalyst.
In a particularly preferred embodiment there is also included in the composition a filler, which may be a reinforcing filler such as fumed silica or an extending filler such as ground quartz, and an inhibitor such as that described in U.S. Patent No. 4,061,509, issued December 6, 1977 to Bobear.
~0 The aforesaid compositions are generally sold in two packages but they can be sold in three or more packages as described in U.S. Patent No. 4,322,320, issued ~arch 30, 1982 to Caprino~ Those skilled in the art recognize that these types of compositions can be cured at room temperature, in the absence of an inhibitor, over a period of time, for example, from ~7a~'73
SILICONE RUBBER COMPOSITIONS
Background of the Invention The present invention relates to self-bonding silicone rubber compositions. More particularly, the present invention relates to SiH-olefin precious metal catalyzed self-bonding silicone rubber compositions wherein the self-bonding additive is selected from silyl maleates, silyl fumarates, maleate-functional polysiloxanes and fumarate-functional polysiloxanes.
SiH-olefin precious metal catalyzed compositions are well known in the artO Such compositions generally comprise a vinyl-containing polydiorganosiloxane, an oxganohydrogenpolysiloxane crosslinking agent and a precious metal or precious metal-containing catalyst.
In a particularly preferred embodiment there is also included in the composition a filler, which may be a reinforcing filler such as fumed silica or an extending filler such as ground quartz, and an inhibitor such as that described in U.S. Patent No. 4,061,509, issued December 6, 1977 to Bobear.
~0 The aforesaid compositions are generally sold in two packages but they can be sold in three or more packages as described in U.S. Patent No. 4,322,320, issued ~arch 30, 1982 to Caprino~ Those skilled in the art recognize that these types of compositions can be cured at room temperature, in the absence of an inhibitor, over a period of time, for example, from ~7a~'73
- 2 - 60SI 00785 several minutes to 10 hours after the components have been mixed together. If an inhibitor is present in the composition or if it is desired to increase the rate of curing, the mixed components can be cured in a s relatively short time by exposing the composition to elevated temperatures.
Such Si~-olefin precious metal catalyzed com-positions are particularly useful in preparing silicone molds, encapsulants and heat curable molded, extruded, and calendered rubber articles. However, one dis-advantage of these compositions is that they typically form a poor bond between the silicone rubber and a substrate, for example, glass, aluminum, copper, steel or the like. To solve this problem primers were developed which allowed the cured silicone rubber to stronyly adhere to the substrate. Inasmuch as the application of a primer to the substrate increases both labor and material costs, it is desirable to have available self-bonding silicone rubber compositions.
~0 Various attempts have been made to provide self-bonding SiH-olefin precious metal catalyzed silicone rubber compositions, but most such attempts failed for one reason or another~ The most common reason that prospective self-bonding additives failed ~5 to accomplish their intended purpose has been that the additive would poison the precious metal catalyst.
Moreover, it has often been found that additives known to promote adhesion in other types of systems, for example, condensation curing room temperature vulcanizable compositions, simply did not work in SiH-olefin precious metal catalyzed systems.
One successful self-bonding SiH-olefin precious metal catalyzed silicone rubber composition is described in U.S. Patent No. 3,527,655, issued September 8, 1970 to ~5 Ballard, which patent is assigned to -the same assiynee as the present invention. Briefly, the self-bonding .. . ..
,, :.
.. , ., . :, .
. , ~ :. . .
: : . .
7~3
Such Si~-olefin precious metal catalyzed com-positions are particularly useful in preparing silicone molds, encapsulants and heat curable molded, extruded, and calendered rubber articles. However, one dis-advantage of these compositions is that they typically form a poor bond between the silicone rubber and a substrate, for example, glass, aluminum, copper, steel or the like. To solve this problem primers were developed which allowed the cured silicone rubber to stronyly adhere to the substrate. Inasmuch as the application of a primer to the substrate increases both labor and material costs, it is desirable to have available self-bonding silicone rubber compositions.
~0 Various attempts have been made to provide self-bonding SiH-olefin precious metal catalyzed silicone rubber compositions, but most such attempts failed for one reason or another~ The most common reason that prospective self-bonding additives failed ~5 to accomplish their intended purpose has been that the additive would poison the precious metal catalyst.
Moreover, it has often been found that additives known to promote adhesion in other types of systems, for example, condensation curing room temperature vulcanizable compositions, simply did not work in SiH-olefin precious metal catalyzed systems.
One successful self-bonding SiH-olefin precious metal catalyzed silicone rubber composition is described in U.S. Patent No. 3,527,655, issued September 8, 1970 to ~5 Ballard, which patent is assigned to -the same assiynee as the present invention. Briefly, the self-bonding .. . ..
,, :.
.. , ., . :, .
. , ~ :. . .
: : . .
7~3
- 3 - 60SI 00785 additive of Barrard ls a fluid vinyl siloxane hydrolyzate of the formula ( ~HO)z (RO)y (CH2 = CH) SiO~y~ ) x ~here R is a lower alkyl radical, ~ is a number greater than 3, y has a value from 0.01 to 0.4 and z has a value of from 0.1 to 0.4.
Another successful self-bonding SiH-olefin precious metal catalyzed silicone rubber composition is described in U.S. Patent No. 4,329,273, issued May 11, 1~2 to Hardman et al, which patent is assigned to the same assignee as the present invention. Briefly, the self-bonding additive of Hardman et al is the partial hydrolysis product of a compound of the formula (R)a Si (OR )4-a ~here R is an unsaturated aliphatic radical having from ~ to S carbon atoms, Rl is an alkyl radical having from 1 to 8 carbon atoms, and a is 1, and wherein the partial hydrolysis product is such that on the average 16 to 49 mole percent of the hydrocarbonoxy groups of said silane 0 are hydrolyzed.
`'Summ'ar'y'o'f-the-'I'nve'ntion It is an object of the present invention to provide self-bonding Si~I-olefin precious metal catalyzed silicone rubber compositions.
~5 It is another object of the present invention to provide a process for producing such self-bondin~ SiH-olefin precious metal catalyzed silicone rubber compositions.
Another object of the present invention is to ' provide articles of manufacture having the self-bonding SiH-olefin precious metal catalyzed silicone rubber compositions bonded thereto.
Still another object of the present invention is to provide a process for making articles of ` ~
. . .-, . -... ,. , :, .~ . :, ,, :
.. : :......... : :
~2 ~ 3
Another successful self-bonding SiH-olefin precious metal catalyzed silicone rubber composition is described in U.S. Patent No. 4,329,273, issued May 11, 1~2 to Hardman et al, which patent is assigned to the same assignee as the present invention. Briefly, the self-bonding additive of Hardman et al is the partial hydrolysis product of a compound of the formula (R)a Si (OR )4-a ~here R is an unsaturated aliphatic radical having from ~ to S carbon atoms, Rl is an alkyl radical having from 1 to 8 carbon atoms, and a is 1, and wherein the partial hydrolysis product is such that on the average 16 to 49 mole percent of the hydrocarbonoxy groups of said silane 0 are hydrolyzed.
`'Summ'ar'y'o'f-the-'I'nve'ntion It is an object of the present invention to provide self-bonding Si~I-olefin precious metal catalyzed silicone rubber compositions.
~5 It is another object of the present invention to provide a process for producing such self-bondin~ SiH-olefin precious metal catalyzed silicone rubber compositions.
Another object of the present invention is to ' provide articles of manufacture having the self-bonding SiH-olefin precious metal catalyzed silicone rubber compositions bonded thereto.
Still another object of the present invention is to provide a process for making articles of ` ~
. . .-, . -... ,. , :, .~ . :, ,, :
.. : :......... : :
~2 ~ 3
- 4 - 60SI 00785 manufacture which utilize the self-bonding SiH-olefin precious metal catalyzed silieone rubber compositions of the present invention.
In accordance with one aspect of the present
In accordance with one aspect of the present
5 invention there is provided a curable composition, eomprising:
(a) an olefin-containing polydiorganosiloxane having a viscosity of at least about 250,000 centipoise at ~5C;
(b) an organohydrogenpolysiloxane crosslinking agent;
(e) a preeious metal or precious metal eontaining eatalyst; and (d) an effeetive amount of adhesion promoter or self-bonding additive seleeted from the group consisting of silyl maleates, silyl fumarates, maleate-funetional polysiloxanes and fumarate-functional polysiloxanes.
Description o-f 'the' Inve'ntion There is provided in aceordance with one aspect ?~ of the present invention there is provided a curable eomposition, eomprising:
(a) an olefin-eontaining polydiorganosiloxane having a viseosity of at least about 250,000 eentipoise at 25C;
~5 (b) an organohydrogenpolysiloxane erosslinking agent;
(e) a preeious metal or preeious metal containing eatalyst; and (d) an effective amount of adhesion promoter or self-bonding additive selected from the group consisting of silyl maleates, silyl fumarates, maleate-functional polysiloxanes and fumarate-functional polysiloxanes.
Olefin-eontaining polydiorganosiloxane (a) is well known in the art and id described, for example in the aforessaid U.S. Patent Nos. 4,061,609 and 4,329,273.
Basieally, polydiorganosiloxane (a) contains at least 0.005 mole pereent olefinie radieals and more preferably -, :, :-: ~ : ,. ~ , .
. .: : ~ : : ~ ..
contains from about 0.01 to about 1 mole percent olefinic radicals. It is especially preferable that the polymer be substantially linear and that the olefinic radicals be vinyl radicals. The olefinic radicals can be only on the interior of the polymer chain or there can be a mixture of terminal and on-chain olefinic radicals.
The artisan will appreciate that polydiorgano-siloxane (a) can be a single polymeric specie or it can be a blend of olefin-containing polymers. The viscosity of polydiorganosiloxane ~a) can be anywhere from about ~50,000 centipoise at 25C to about 300,000,000 centipoise at ~5~C. More preferably, the viscosity is from about 500,000 centipoise at 25C to about 200,000,000 centipoise at ~5C, and most preferably is from about 1,000,000 centipoise at 25C to about 100,000,000 centipoise at ~5C.
The organo substituents of polydiorganosiloxane ~a), in addition to the olefinic radicals, can be any monovalent hydrocarbon radical or substituted monovalent 2~ hydrocarbon radical. Preferred organo radicals include methyl, phenyl r trifluoropropyl and mixtures thereof.
The second essential component of the present invention is organohydrogenpolysiloxane (b), which is also well known in the art and described in the ~5 aforementioned U.S. Patent Nos. 3,527,65~, 4,061,609 and ~,3~9,~73. Organohydrogenpolysiloxane (b) can be any ~olydiorganosiloxane having silicon-bonded hydrogen atoms which is normally utilized by the artisan as a crosslinking ag0nt. Such organohydrogenpolysiloxanes can 3a be linear polymers or resinous materials.
Processes for producing olefin-containing polydiorganosiloxane (a) and organohydrogenpolysiloxane (b) are well known in the art. Fluoro-containing organohydrogenpolysiloxane crosslinking agents which are intended to be within the scope of the present invention are described in U.S. Patent No. 4,041,010, 3~2~73
(a) an olefin-containing polydiorganosiloxane having a viscosity of at least about 250,000 centipoise at ~5C;
(b) an organohydrogenpolysiloxane crosslinking agent;
(e) a preeious metal or precious metal eontaining eatalyst; and (d) an effeetive amount of adhesion promoter or self-bonding additive seleeted from the group consisting of silyl maleates, silyl fumarates, maleate-funetional polysiloxanes and fumarate-functional polysiloxanes.
Description o-f 'the' Inve'ntion There is provided in aceordance with one aspect ?~ of the present invention there is provided a curable eomposition, eomprising:
(a) an olefin-eontaining polydiorganosiloxane having a viseosity of at least about 250,000 eentipoise at 25C;
~5 (b) an organohydrogenpolysiloxane erosslinking agent;
(e) a preeious metal or preeious metal containing eatalyst; and (d) an effective amount of adhesion promoter or self-bonding additive selected from the group consisting of silyl maleates, silyl fumarates, maleate-functional polysiloxanes and fumarate-functional polysiloxanes.
Olefin-eontaining polydiorganosiloxane (a) is well known in the art and id described, for example in the aforessaid U.S. Patent Nos. 4,061,609 and 4,329,273.
Basieally, polydiorganosiloxane (a) contains at least 0.005 mole pereent olefinie radieals and more preferably -, :, :-: ~ : ,. ~ , .
. .: : ~ : : ~ ..
contains from about 0.01 to about 1 mole percent olefinic radicals. It is especially preferable that the polymer be substantially linear and that the olefinic radicals be vinyl radicals. The olefinic radicals can be only on the interior of the polymer chain or there can be a mixture of terminal and on-chain olefinic radicals.
The artisan will appreciate that polydiorgano-siloxane (a) can be a single polymeric specie or it can be a blend of olefin-containing polymers. The viscosity of polydiorganosiloxane ~a) can be anywhere from about ~50,000 centipoise at 25C to about 300,000,000 centipoise at ~5~C. More preferably, the viscosity is from about 500,000 centipoise at 25C to about 200,000,000 centipoise at ~5C, and most preferably is from about 1,000,000 centipoise at 25C to about 100,000,000 centipoise at ~5C.
The organo substituents of polydiorganosiloxane ~a), in addition to the olefinic radicals, can be any monovalent hydrocarbon radical or substituted monovalent 2~ hydrocarbon radical. Preferred organo radicals include methyl, phenyl r trifluoropropyl and mixtures thereof.
The second essential component of the present invention is organohydrogenpolysiloxane (b), which is also well known in the art and described in the ~5 aforementioned U.S. Patent Nos. 3,527,65~, 4,061,609 and ~,3~9,~73. Organohydrogenpolysiloxane (b) can be any ~olydiorganosiloxane having silicon-bonded hydrogen atoms which is normally utilized by the artisan as a crosslinking ag0nt. Such organohydrogenpolysiloxanes can 3a be linear polymers or resinous materials.
Processes for producing olefin-containing polydiorganosiloxane (a) and organohydrogenpolysiloxane (b) are well known in the art. Fluoro-containing organohydrogenpolysiloxane crosslinking agents which are intended to be within the scope of the present invention are described in U.S. Patent No. 4,041,010, 3~2~73
- 6 - 60SI 00785 issued Au~ust 9, 1977 to Jeram, assigned to -the same assignee as the present invention.
Precious metal or precious metal-containing catalyst (c) includes all of the well known platinum and rhodium based catalysts which are effective for promoting the reaction between silicon-bonded olefinic radicals of polydiorganosiloxane (a) and silicon-bonded hydrogen atoms of organohydrogenpolysiloxane (b). These materials especially include ~he platinum hydrocarbon 1~ complexes described in U.S. Patent Nos. 3,159,601 and 3,159,662, both issued December 1, 1964 to Ashby and the platinum alcoholate complexes described in U.S.
Patent No. 3,220,972, issued November 30, 1965 to Lamoreaux, as well as the platinum complex catalysts of U.S. Patent No. 3,184,730, issued June 4, 1974 to ~arstedt. Additionally, the platinum chloride-olefin comple~es described in U.S. Patent No. 3,516,946 issued ~une 23, 1970 to Modic are also useful herein.
Other metal or metal complex catalysts which ~0 can be used to practice the present invention include those which are based on ruthenium, palladium, osmium and irridium.
The precious metal or precious metal containing catalyst is employed in an amount effective for promoting ~5 crosslinking of the aforesaid polydiorganosiloxane (a) and organohydrogenpolysiloxane ~b). Generally, an effective amount of hydrosilation catalyst ranges from about 1 to about 500 parts per million, as platinum metal, based on the weight of polydiorganosiloxane (a) and or~anohydrogenpolysiloxane (b). Of course more or less catalyst may be utilized without departing from the spirit or intended scope of the invention.
The final essential ingredient of the curable composition of the present invention is adhesion promoter (d). For purposes of the present invention, the terms `'adhesion promoter" and "self-bonding additive`' are : , : -, . . :: -: . , ~ :
- . ,.. - ~ . . : - :
.:
. . ...
, ~: : ~ : , . . , . :
:, .
. . .
Precious metal or precious metal-containing catalyst (c) includes all of the well known platinum and rhodium based catalysts which are effective for promoting the reaction between silicon-bonded olefinic radicals of polydiorganosiloxane (a) and silicon-bonded hydrogen atoms of organohydrogenpolysiloxane (b). These materials especially include ~he platinum hydrocarbon 1~ complexes described in U.S. Patent Nos. 3,159,601 and 3,159,662, both issued December 1, 1964 to Ashby and the platinum alcoholate complexes described in U.S.
Patent No. 3,220,972, issued November 30, 1965 to Lamoreaux, as well as the platinum complex catalysts of U.S. Patent No. 3,184,730, issued June 4, 1974 to ~arstedt. Additionally, the platinum chloride-olefin comple~es described in U.S. Patent No. 3,516,946 issued ~une 23, 1970 to Modic are also useful herein.
Other metal or metal complex catalysts which ~0 can be used to practice the present invention include those which are based on ruthenium, palladium, osmium and irridium.
The precious metal or precious metal containing catalyst is employed in an amount effective for promoting ~5 crosslinking of the aforesaid polydiorganosiloxane (a) and organohydrogenpolysiloxane ~b). Generally, an effective amount of hydrosilation catalyst ranges from about 1 to about 500 parts per million, as platinum metal, based on the weight of polydiorganosiloxane (a) and or~anohydrogenpolysiloxane (b). Of course more or less catalyst may be utilized without departing from the spirit or intended scope of the invention.
The final essential ingredient of the curable composition of the present invention is adhesion promoter (d). For purposes of the present invention, the terms `'adhesion promoter" and "self-bonding additive`' are : , : -, . . :: -: . , ~ :
- . ,.. - ~ . . : - :
.:
. . ...
, ~: : ~ : , . . , . :
:, .
. . .
- 7 - 60SI 00785 intended to be synonymous and, therefore, are u~ed interchangeably. Adhesion promoter (d) can generally be described as a silyl maleate, silyl fumarate, a maleate-functional polysiloxane, fumarate-functional polysiloxane, or mixture thereof. These compounds and their methods of preparation are described in U.S.
Patent No. 3,759,968, issued September 18, 1973 to Berger et al, which patent is assigned to the same assignee as the present invention.
1~ Generally, adhesion promoters within the intended scope of the present invention are within the scope of the following formulas:
(1) R2 C - Z - R - Si (R )n (M)3-n R - C - Z - G
(2) R - C - Z - R - Si (R )n (M)3-n f 2 15 (3) ( R - C - Z - R ~ ~2 ~
R - C - Z - GJ a ~ J SiO 4-a-b and ~ 2 (4) ~ R - C - Z - R 2 ~G _ n _ C - R2 a R b 4-a-b O O
where Z is selected from C - O, C, phenylene, CONH, and CONRl, G is selected from hydrogen, R3 and R4HC(Rl)dSio3 c d~
where R is selected from monovalent hydrocarbon 2 radicals and monovalent halogenated hydrocarbon radicals, where R and R4 are divalent hydrocarbon radicals, R is selected from monovalent hydrocarbon radicals and monovalent halogenated hydrocarbon radicals, a varies from 0.005 to 2.0, b varies from 1.0 to 2.5, the sum of ,: ;, . ,. . ; .::,.: : : .: .:
~7~ 73
Patent No. 3,759,968, issued September 18, 1973 to Berger et al, which patent is assigned to the same assignee as the present invention.
1~ Generally, adhesion promoters within the intended scope of the present invention are within the scope of the following formulas:
(1) R2 C - Z - R - Si (R )n (M)3-n R - C - Z - G
(2) R - C - Z - R - Si (R )n (M)3-n f 2 15 (3) ( R - C - Z - R ~ ~2 ~
R - C - Z - GJ a ~ J SiO 4-a-b and ~ 2 (4) ~ R - C - Z - R 2 ~G _ n _ C - R2 a R b 4-a-b O O
where Z is selected from C - O, C, phenylene, CONH, and CONRl, G is selected from hydrogen, R3 and R4HC(Rl)dSio3 c d~
where R is selected from monovalent hydrocarbon 2 radicals and monovalent halogenated hydrocarbon radicals, where R and R4 are divalent hydrocarbon radicals, R is selected from monovalent hydrocarbon radicals and monovalent halogenated hydrocarbon radicals, a varies from 0.005 to 2.0, b varies from 1.0 to 2.5, the sum of ,: ;, . ,. . ; .::,.: : : .: .:
~7~ 73
- 8 - 60SI 00785 a and b varies from 1.005 to 3.0, c varies from 0 to 1.0, d varies from l.0 to 2.5, the sum of c and d varies from l.o to 3.0, M is selected from R3O and o radicals, R3Co R~ is selected from hydrogen and alkyl radicals having from 1 to about 15 carbon atoms, and n is a whole number from l to 3, inclusive.
Especially preferable adhesion promoters for practicing the present invention are:
bis-(trimethoxysilylpropyl) maleate, l~ bis-~trimethoxysilylpropyl) fumarate, bis-(dimethoxymethylsilylpropyl) maleate, bis-(dimethoxymethylsilylpropyl) fumarate, trimethoxysilylpropyl allyl maleate, and trimethoxysilylpropyl allyl fumarate.
The most preferred adhesion promoters for practicing the present invention are bis-(trimethoxysilylpropyl) maleate and bis-(trimethoxysilylpropyl) fumarate, or a mixture thereof.
The artisan can readily determine which compounds ~0 within the foregoing general formulas (1) to (4) are most effective for a particular purpose without undue experimentation.
In practicing the present invention it has been found that an effective amount of adhesion promoter ~5 ~an~es from about 0.1 to about 5 parts by weight per 100 parts by weight of olefin-containing polydiorganosiloxane (a).
Methods for preparing such silyl maleates, silyl fumarates, maleate-functional polysiloxanes and fumarate-functional polysiloxanes are described in the aforesaid ~.S. Patent No. 3,759,968.
In a preferred embodiment of the present invention there is also included a hydroperoxide inhibitor as described in aforesaid U.S. Patent No. 4,061,609.
The artisan will appreciate that the inclusion of such an inhibitor will extend the work iife of the heat curable compositions of the present in~ention. For most ~ , . , i ",,~ , .:: ,i,;, ,,; , , "
-. . . ~ ., - . :-:
~ 9 ~ 60SI 007~5 applications there should be present from about 0.01 to 10 parts by weight inhibitor per 100 parts by weight olefin-containing polydiorganosiloxane (a). Suitable hydroperoxy inhibitors are described in the aforementioned Bobear U.S. Patent 4,061,609 and the interested reader is referred thereto for further information.
Another additive that can be employed to provide a preferred embodiment of the present invention is a filler.
O course, the filler can be included in the composition 1~ whether or not the inhibitor is included. Generally, the amount of filler can be as small as 5 parts by weight per 100 parts by weight olefin-containing polydiorgano-siloxane (a) to as much as 250 parts or more by weight of filler per 100 parts by weight of olefin-containing polydiorganosiloxane (a). The preferred fillers are reinforcing fillers such as fumed silica and precipitated silica, however, extending fillers can be used in addition to or in place of such reinforclng fillers. Examples of suitable extending fillers include iron oxide, diatomaceous earth, calcium carbonate, ground quartz, cork and the like.
Other additives known in the art may also be included in the self-bonding curable compositions of the present invention, for example, flame retardants, plast-~5 icizers, pigments and the like.
In order to better enable the artisan to practice the present invention the following examples are provided by way of illustration and not by way of limitation. All parts are by weight unless otherwise indicated.
EXAMPLES
Ex-ampl`e ]
A precious metal catalyzed heat curable silicone rubber composition was prepared by mixing the following components:
vinyl chainstopped polydimethylsiloxane 40 parts having a viscosity of 20,000,000 cps. at 25C
:~ . ,: ,., ~ ., . . , : , :
~27~97~
vinyl chainstopped methylvinylpolysiloxane 40 parts having 0.05 mole % vinyl on the polymer chain and a viscosity of 20,000,000 cps. at 25C
vinyl chainstopped methylvinylpolysiloxane 20 parts having 0.6 mole % vinyl on the polymer chain and a viscosity of 20,000,000 cps. at 25C
silanol-containing polydimethylsiloxane2 parts process aid having a viscosity of 20 centipoise at 25C
octanlethylcyclotetrasiloxane treated fumed silica 53 parts linear methylhydrogenpolysiloxane 2 parts crosslinking agent platinum complex catalyst 1 parts This composition, designated as Composition I, is illustrative of prior art compositions.
Example 2 A composition, designated as Composition II, was prepared as in Example I except that it also included 1 weight percent bis-(trimethoxysilylpropyl) maleate in ~0 accordance with the present invention.
Example 3 A composition, designated as Composition III, was prepared as in Example 1 except that it also included 2 weight percent bis-(-trimethoxysilylpropyl) maleate in ~5 accordance with the present invention.
Example` 4 A 60 mil sheet of each of Composition I, Composition II, and Composition III was pressed onto each side of untreated fiberglass cloth and vulcanized at 350F for 15 minutes. One inch by four inch sprips of the resultant laminates were tested for peel strength in a Monsanto Tensometer at a jaw speed of two inches per minute. The results are set forth in Table I.
Table I
Composition I Composition II Composition III
peel strength 1 6 14*
tpounds/inch~
*Rubber tore before adhesive bond failed.
-- . ,: ~:: ,:: ~. : . :
.... . .. ,;. , .
., ." . ,., .. .. :: . , . ~ -7~
- 11 ~ 60SI 00785 These results thus illustrate the improved results obtained by incorporating an adhesion promoter of the present invention into heat curable silicone rubber compositions.
Example 5 In this example lap shear tests were conducted on one inch by six inch strips of Composition III
vulcanized directly on galvanized steel and anodized aluminum, respectively. Each metallic surface was wiped with toluene prior to assembling the metal/rubber/metal lap shear construction. The rubber thickness was appro~imately 20 mils and the overlap distance was one inch. After curing at 350F for 15 minutes, lap shear values were obtained on a Tinius Olsen tensometer at a jaw speed of 0.5 inch per minute as set forth in Table II.
Table II
` Anodized Aluminum Galvanized Steel Lap Shear Strength 538 689 ~0 (psi) . j
Especially preferable adhesion promoters for practicing the present invention are:
bis-(trimethoxysilylpropyl) maleate, l~ bis-~trimethoxysilylpropyl) fumarate, bis-(dimethoxymethylsilylpropyl) maleate, bis-(dimethoxymethylsilylpropyl) fumarate, trimethoxysilylpropyl allyl maleate, and trimethoxysilylpropyl allyl fumarate.
The most preferred adhesion promoters for practicing the present invention are bis-(trimethoxysilylpropyl) maleate and bis-(trimethoxysilylpropyl) fumarate, or a mixture thereof.
The artisan can readily determine which compounds ~0 within the foregoing general formulas (1) to (4) are most effective for a particular purpose without undue experimentation.
In practicing the present invention it has been found that an effective amount of adhesion promoter ~5 ~an~es from about 0.1 to about 5 parts by weight per 100 parts by weight of olefin-containing polydiorganosiloxane (a).
Methods for preparing such silyl maleates, silyl fumarates, maleate-functional polysiloxanes and fumarate-functional polysiloxanes are described in the aforesaid ~.S. Patent No. 3,759,968.
In a preferred embodiment of the present invention there is also included a hydroperoxide inhibitor as described in aforesaid U.S. Patent No. 4,061,609.
The artisan will appreciate that the inclusion of such an inhibitor will extend the work iife of the heat curable compositions of the present in~ention. For most ~ , . , i ",,~ , .:: ,i,;, ,,; , , "
-. . . ~ ., - . :-:
~ 9 ~ 60SI 007~5 applications there should be present from about 0.01 to 10 parts by weight inhibitor per 100 parts by weight olefin-containing polydiorganosiloxane (a). Suitable hydroperoxy inhibitors are described in the aforementioned Bobear U.S. Patent 4,061,609 and the interested reader is referred thereto for further information.
Another additive that can be employed to provide a preferred embodiment of the present invention is a filler.
O course, the filler can be included in the composition 1~ whether or not the inhibitor is included. Generally, the amount of filler can be as small as 5 parts by weight per 100 parts by weight olefin-containing polydiorgano-siloxane (a) to as much as 250 parts or more by weight of filler per 100 parts by weight of olefin-containing polydiorganosiloxane (a). The preferred fillers are reinforcing fillers such as fumed silica and precipitated silica, however, extending fillers can be used in addition to or in place of such reinforclng fillers. Examples of suitable extending fillers include iron oxide, diatomaceous earth, calcium carbonate, ground quartz, cork and the like.
Other additives known in the art may also be included in the self-bonding curable compositions of the present invention, for example, flame retardants, plast-~5 icizers, pigments and the like.
In order to better enable the artisan to practice the present invention the following examples are provided by way of illustration and not by way of limitation. All parts are by weight unless otherwise indicated.
EXAMPLES
Ex-ampl`e ]
A precious metal catalyzed heat curable silicone rubber composition was prepared by mixing the following components:
vinyl chainstopped polydimethylsiloxane 40 parts having a viscosity of 20,000,000 cps. at 25C
:~ . ,: ,., ~ ., . . , : , :
~27~97~
vinyl chainstopped methylvinylpolysiloxane 40 parts having 0.05 mole % vinyl on the polymer chain and a viscosity of 20,000,000 cps. at 25C
vinyl chainstopped methylvinylpolysiloxane 20 parts having 0.6 mole % vinyl on the polymer chain and a viscosity of 20,000,000 cps. at 25C
silanol-containing polydimethylsiloxane2 parts process aid having a viscosity of 20 centipoise at 25C
octanlethylcyclotetrasiloxane treated fumed silica 53 parts linear methylhydrogenpolysiloxane 2 parts crosslinking agent platinum complex catalyst 1 parts This composition, designated as Composition I, is illustrative of prior art compositions.
Example 2 A composition, designated as Composition II, was prepared as in Example I except that it also included 1 weight percent bis-(trimethoxysilylpropyl) maleate in ~0 accordance with the present invention.
Example 3 A composition, designated as Composition III, was prepared as in Example 1 except that it also included 2 weight percent bis-(-trimethoxysilylpropyl) maleate in ~5 accordance with the present invention.
Example` 4 A 60 mil sheet of each of Composition I, Composition II, and Composition III was pressed onto each side of untreated fiberglass cloth and vulcanized at 350F for 15 minutes. One inch by four inch sprips of the resultant laminates were tested for peel strength in a Monsanto Tensometer at a jaw speed of two inches per minute. The results are set forth in Table I.
Table I
Composition I Composition II Composition III
peel strength 1 6 14*
tpounds/inch~
*Rubber tore before adhesive bond failed.
-- . ,: ~:: ,:: ~. : . :
.... . .. ,;. , .
., ." . ,., .. .. :: . , . ~ -7~
- 11 ~ 60SI 00785 These results thus illustrate the improved results obtained by incorporating an adhesion promoter of the present invention into heat curable silicone rubber compositions.
Example 5 In this example lap shear tests were conducted on one inch by six inch strips of Composition III
vulcanized directly on galvanized steel and anodized aluminum, respectively. Each metallic surface was wiped with toluene prior to assembling the metal/rubber/metal lap shear construction. The rubber thickness was appro~imately 20 mils and the overlap distance was one inch. After curing at 350F for 15 minutes, lap shear values were obtained on a Tinius Olsen tensometer at a jaw speed of 0.5 inch per minute as set forth in Table II.
Table II
` Anodized Aluminum Galvanized Steel Lap Shear Strength 538 689 ~0 (psi) . j
Claims (37)
1. A curable composition, comprising:
(a) an olefin-containing polydiorganosiloxane comprising a polydiorganosiloxane having silicon-bonded olefin radicals and a viscosity of at least about 250,000 centipoise at 25°C;
(b) a crosslinking agent comprising polydiorganosiloxane having silicon-bonded hydrogen atoms;
(c) an amount of a platinum metal or a platinum metal complex catalyst effective for promoting crosslinking of olefin-containing polydiorganosiloxane (a) and crosslinking agent (b);
and (d) an effective amount of adhesion promoter selected from the group consisting of silyl maleates, silyl fumarates, maleate-functional polysiloxanes and fumarate-functional polysiloxanes.
(a) an olefin-containing polydiorganosiloxane comprising a polydiorganosiloxane having silicon-bonded olefin radicals and a viscosity of at least about 250,000 centipoise at 25°C;
(b) a crosslinking agent comprising polydiorganosiloxane having silicon-bonded hydrogen atoms;
(c) an amount of a platinum metal or a platinum metal complex catalyst effective for promoting crosslinking of olefin-containing polydiorganosiloxane (a) and crosslinking agent (b);
and (d) an effective amount of adhesion promoter selected from the group consisting of silyl maleates, silyl fumarates, maleate-functional polysiloxanes and fumarate-functional polysiloxanes.
2. The composition of claim 1 wherein the viscosity of olefin-containing polydiorganosiloxane (a) having a viscosity of from about 500,000 centipoise to about 200,000,000 centipoise at 25°C.
3. The composition of claim 1 wherein the viscosity of olefin-containing polydiorganosiloxane (a) has a viscosity of from about 1,000,000 centipoise to about 100,000,000 centipoise at 25°C.
4. The composition of claim 1 wherein the platinum metal or platinum metal complex catalyst is present in an amount of from about 1 to about 500 parts per million, as platinum metal, based on the weight of polydiorganosiloxane (a) and crosslinking agent (b).
5. The composition of claim 1 wherein the
5. The composition of claim 1 wherein the
Claim 5 continued:
adhesion promoter is selected from the group consisting of compounds having the formulas:
(1) (2) (3) (4) ;
where Z is selected from ? - O, ?, phenylene, CONH, and CONR1, G is selected from hydrogen, R3 and R4HC(R1)d SiO3-c-d, where R3 is selected from monovalent hydrocarbon radicals and monovalent halogenated hydrocarbon radicals, where R and R4 are divalent hydrocarbon radicals, R1 is selected from monovalent hydrocarbon radicals and monovalent halogenated hydrocarbon radicals, a varies from 0.005 to 2.0, b varies from 1.0 to 2.5, the sum of a and b varies from 1.005 to 3.0, c varies from 0 to 1.0, d varies from 1.0 to 2.5, the sum of c and d varies from 1.0 to 3.0, M is selected from R3O and radicals, R2 is selected from hydrogen and alkyl radicals having from 1 to about 15 carbon atoms, and n is a whole number from 1 to 3, inclusive.
adhesion promoter is selected from the group consisting of compounds having the formulas:
(1) (2) (3) (4) ;
where Z is selected from ? - O, ?, phenylene, CONH, and CONR1, G is selected from hydrogen, R3 and R4HC(R1)d SiO3-c-d, where R3 is selected from monovalent hydrocarbon radicals and monovalent halogenated hydrocarbon radicals, where R and R4 are divalent hydrocarbon radicals, R1 is selected from monovalent hydrocarbon radicals and monovalent halogenated hydrocarbon radicals, a varies from 0.005 to 2.0, b varies from 1.0 to 2.5, the sum of a and b varies from 1.005 to 3.0, c varies from 0 to 1.0, d varies from 1.0 to 2.5, the sum of c and d varies from 1.0 to 3.0, M is selected from R3O and radicals, R2 is selected from hydrogen and alkyl radicals having from 1 to about 15 carbon atoms, and n is a whole number from 1 to 3, inclusive.
6. The composition of claim 1 wherein the adhesion promoter is selected from the group consisting of silyl maleates and silyl fumarates.
7. The composition of claim 6 wherein the adhesion promoter is selected from the group consisting of bis-(trimethoxysilylpropyl) maleate, bis-(trimethoxysilylpropyl) fumarate, bis-(dimethoxymethylsilylpropyl) maleate, bis-(dimethoxymethylsilylpropyl) fumarate, trimethoxyislylpropyl allyl maleate, and trimethoxysilylpropyl allyl fumarate.
8. The composition of claim 7 wherein the adhesion promoter is bis-(trimethoxysilylpropyl) maleate, bis-(trimethoxysilylpropyl) fumarate, or a mixture thereof.
9. The composition of claim 1 wherein the adhesion promoter is present in an amount of from about 0.1 part by weight to about 5 parts by weight per 100 parts by weight of olefin-containing polydiorganosiloxane (a).
10. The composition of claim 1, further comprising an effective amount of hydroperoxide inhibitor.
11. The composition of claim 1, further comprising an effective amount of filler.
12. The composition of claim 10, further comprising an effective amount of filler.
13. A method for making a curable composition comprising:
(I) mixing:
(a) an olefin-containing polydiorgano-siloxane comprising a polydiorganosiloxane having silicon-bonded olefin radicals and a viscosity of at least 250,000 centipoise at 25°C;
(b) a crosslinking agent comprising polydiorganosiloxane having silicon-bonded olefin radicals;
(c) C platinum metal or a platinum metal complex catalyst; and (d) an effective amount of adhesion promoter selected from the group consisting of silyl maleates, silyl fumarates, maleate-functional polysiloxanes and fumarate-functional polysiloxanes.
(I) mixing:
(a) an olefin-containing polydiorgano-siloxane comprising a polydiorganosiloxane having silicon-bonded olefin radicals and a viscosity of at least 250,000 centipoise at 25°C;
(b) a crosslinking agent comprising polydiorganosiloxane having silicon-bonded olefin radicals;
(c) C platinum metal or a platinum metal complex catalyst; and (d) an effective amount of adhesion promoter selected from the group consisting of silyl maleates, silyl fumarates, maleate-functional polysiloxanes and fumarate-functional polysiloxanes.
14. The method of claim 13 wherein the viscosity of olefin-containing polydiorganosiloxane (a) has a viscosity of from about 500,000 centipoise to about 200,000,000 centipoise at 25°C.
15. The method of claim 13 wherein the viscosity of olefin-containing polydiorganosiloxane (a) has a viscosity of from about 1,000,000 centipoise to about 100,000,000 centipoise at 25°C.
16. The method of claim 13 wherein the platinum metal or platinum metal complex catalyst is present in an amount of from about 1 to about 500 parts per million, as platinum metal, based on the weight of polydiorganosiloxane (a) and crosslinking agent (b).
17. The method of claim 13 wherein the adhesion promoter is selected from the group consisting of compounds having the formulas (1) , (2) ,
17. The method of claim 13 wherein the adhesion promoter is selected from the group consisting of compounds having the formulas (1) , (2) ,
Claim 17 continued:
(3) and (4) ;
where Z is selected from , ?, phenylene, CONH, and CONR1, G is selected from hydrogen, R3 and R4Hc(R1)d SiO3-c-d, where R3 is selected from monovalent hydrocarbon radicals and monovalent halogenated hydrocarbon radicals, where R and R4 are divalent hydrocarbon radicals, R1 is selected from monovalent hydrocarbon radicals and monovalent halogenated hydrocarbon radicals, a varies from 0.005 to 2.0, b varies from 1.0 to 2.5, the sum of a and b varies from 1.005 to 3.0, c varies from 0 to 1.0, d varies from 1.0 to 2.5, the sum of c and d varies from 1.0 to 3.0, M is selected from R3O and radicals, R2 is selected from hydrogen and alkyl radicals having from 1 to about 15 carbon atoms, and n is a whole number from 1 to 3, inclusive.
(3) and (4) ;
where Z is selected from , ?, phenylene, CONH, and CONR1, G is selected from hydrogen, R3 and R4Hc(R1)d SiO3-c-d, where R3 is selected from monovalent hydrocarbon radicals and monovalent halogenated hydrocarbon radicals, where R and R4 are divalent hydrocarbon radicals, R1 is selected from monovalent hydrocarbon radicals and monovalent halogenated hydrocarbon radicals, a varies from 0.005 to 2.0, b varies from 1.0 to 2.5, the sum of a and b varies from 1.005 to 3.0, c varies from 0 to 1.0, d varies from 1.0 to 2.5, the sum of c and d varies from 1.0 to 3.0, M is selected from R3O and radicals, R2 is selected from hydrogen and alkyl radicals having from 1 to about 15 carbon atoms, and n is a whole number from 1 to 3, inclusive.
18. The method of claim 13 wherein the adhesion promoter is selected from the group consisting of silyl maleates and silyl fumarates.
19. The method of claim 18 wherein the adhesion promoter is selected from the group consisting of bis-(trimethoxysilylpropyl) maleate, bis-(trimethoxysilylpropyl) fumarate, bis-(dimethoxymethylsilylpropylj maleate, bis-(dimethoxymethylsilylpropyl) fumarate, trimethoxyislylpropyl allyl maleate, and trimethoxysilylpropyl allyl fumarate.
20. The method of claim 19 wherein the adhesion promoter is bis-(trimethoxysilylpropyl) maleate, bis-(trimethoxysilylpropyl) fumarate, or a mixture thereof.
21. The method of claim 13 wherein the adhesion promoter is present in an amount of from about 0.1 part by weight to about 5 parts by weight per 100 parts by weight of olefin-containing polydiorganosiloxane (a).
22. The method of claim 13, further comprising mixing an effective amount of hydroperoxide inhibitor.
23. The method of claim 13, further comprising mixing an effective amount of filler.
24. The method of claim 22, further comprising mixing an effective amount of filler.
25. An article of manufacture, comprising:
(a) 100 parts by weight of component A and (b) 1 to 100 parts by weight of component B, wherein component A comprises a mixture of (i) one or more polydiorganosiloxanes having silicon-bonded i olefinic radicals and a viscosity of at least about 250,000 centipoise at 25°C and (ii) an amount of platinum metal or platinum metal containing catalyst;
and component B comprises a polydiorganosiloxane having silicon-bonded hydrogen atoms, with the proviso that component A, component B or both component A and component B also include an adhesion promoter selected from the group consisting of silyl maleates, silyl fumarates, maleate-functional polysiloxanes and fumarate-functional polysiloxanes.
(a) 100 parts by weight of component A and (b) 1 to 100 parts by weight of component B, wherein component A comprises a mixture of (i) one or more polydiorganosiloxanes having silicon-bonded i olefinic radicals and a viscosity of at least about 250,000 centipoise at 25°C and (ii) an amount of platinum metal or platinum metal containing catalyst;
and component B comprises a polydiorganosiloxane having silicon-bonded hydrogen atoms, with the proviso that component A, component B or both component A and component B also include an adhesion promoter selected from the group consisting of silyl maleates, silyl fumarates, maleate-functional polysiloxanes and fumarate-functional polysiloxanes.
26. An article of manufacture prepared by the steps comprising:
(I) mixing, so as to form a curable composition comprising:
(a) an olefin-containing polydiorganosiloxane comprising a polydiorganosiloxane having silicon-bonded olefin radicals and a viscosity of at least about 250,000 centipoise at 25°C;
(b) a crosslinking agent comprising polydiorganosiloxane having silicon-bonded hydrogen atoms;
(c) a platinum metal or a platinum metal complex catalyst; and (d) an effective amount of adhesion promoter selected from the group consisting of silyl maleates, silyl fumarates, maleate-functional polysiloxanes and fumarate-functional polysiloxanes;
(II) applying said curable composition to a substrate; and (III) curing said curable composition.
(I) mixing, so as to form a curable composition comprising:
(a) an olefin-containing polydiorganosiloxane comprising a polydiorganosiloxane having silicon-bonded olefin radicals and a viscosity of at least about 250,000 centipoise at 25°C;
(b) a crosslinking agent comprising polydiorganosiloxane having silicon-bonded hydrogen atoms;
(c) a platinum metal or a platinum metal complex catalyst; and (d) an effective amount of adhesion promoter selected from the group consisting of silyl maleates, silyl fumarates, maleate-functional polysiloxanes and fumarate-functional polysiloxanes;
(II) applying said curable composition to a substrate; and (III) curing said curable composition.
27. The article of claim 26 wherein the viscosity of olefin-containing polydiorganosiloxane (a) has a viscosity of from about 500,000 centipoise to about 200,000,000 centipoise at 25°C.
28. The article of claim 26 wherein the viscosity of olefin-containing polydiorganosiloxane (a) has a viscosity of from about 1,000,000 centipoise to about 100,000,000 centipoise at 25°C.
29. The article of claim 28 wherein the platinum metal or platinum metal complex catalyst is present in an amount of from about 1 to about 500 parts per million, as platinum metal, based on the weight of polydiorganosiloxane (a) and crosslinking agent (b).
30. The article of claim 26 wherein the adhesion promoter is selected from the group consisting of compounds having the formulas:
(1) , (2) , (3) and (4) ;
where Z is selected from , ?, phenylene, CONH, and CONR1, G is selected from hydrogen, R3 and R4Hc(R1)d SiO3-c-d, where R3 is selected from monovalent hydrocarbon radicals and monovalent halogenated hydrocarbon radicals, where R and R4 are divalent hydrocarbon radicals, R1 is selected from monovalent hydrocarbon radicals and monovalent halogenated hydrocarbon radicals, a varies from 0.005 to 2.0, b varies from 1.0 to 2.5, the sum of a and b varies from 1.005 to 3.0, c varies from 0 to 1.0, d varies from 1.0 to 2.5, the sum of c and d varies from 1.0 to 3 . 0, M is selected from R3O and radicals, R2 is selected from hydrogen and alkyl radicals having from 1 to about 15 carbon atoms, and n is a whole number from 1 to 3, inclusive.
(1) , (2) , (3) and (4) ;
where Z is selected from , ?, phenylene, CONH, and CONR1, G is selected from hydrogen, R3 and R4Hc(R1)d SiO3-c-d, where R3 is selected from monovalent hydrocarbon radicals and monovalent halogenated hydrocarbon radicals, where R and R4 are divalent hydrocarbon radicals, R1 is selected from monovalent hydrocarbon radicals and monovalent halogenated hydrocarbon radicals, a varies from 0.005 to 2.0, b varies from 1.0 to 2.5, the sum of a and b varies from 1.005 to 3.0, c varies from 0 to 1.0, d varies from 1.0 to 2.5, the sum of c and d varies from 1.0 to 3 . 0, M is selected from R3O and radicals, R2 is selected from hydrogen and alkyl radicals having from 1 to about 15 carbon atoms, and n is a whole number from 1 to 3, inclusive.
31. The article of claim 26 wherein the adhesion promoter is selected from the group consisting of silyl maleates and silyl fumarates.
32. The article of claim 31 wherein the adhesion promoter is selected from the group consisting of bis-(trimethoxysilylpropyl) maleate, bis-(trimethoxysilylpropyl) fumarate, bis-(dimethoxymethylsilylpropyl) maleate, bis-(dimethoxymethylsilylpropyl) fumarate, trimethoxyislylpropyl allyl maleate, and trimethoxysilylpropyl allyl fumarate.
33. The article of claim 32 wherein the adhesion promoter is bis-(trimethoxysilylpropyl) maleate, bis-(trimethoxysilylpropyl) fumarate, or a mixture thereof.
34. The article of claim 26 wherein the adhesion promoter is present in an amount of from about 0.1 part by weight to about 5 parts by weight per 100 parts by weight of olefin-containing polydiorganosiloxane (a).
35. The article of claim 26 wherein the curable composition further comprises an effective amount of hydroperoxide inhibitor.
36. The article of claim 26 wherein the curable composition further comprises an effective amount of filler.
37. The article of claim 35 wherein the curable composition further comprises an effective amount of filler.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US68848885A | 1985-01-03 | 1985-01-03 | |
| US688,488 | 1985-01-03 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1270973A true CA1270973A (en) | 1990-06-26 |
Family
ID=24764629
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000498347A Expired - Fee Related CA1270973A (en) | 1985-01-03 | 1985-12-20 | Self-bonding precious metal catalyzed silicone rubber compositions |
Country Status (2)
| Country | Link |
|---|---|
| JP (1) | JPH0672206B2 (en) |
| CA (1) | CA1270973A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE102006016321A1 (en) * | 2006-04-06 | 2007-11-29 | Wacker Chemie Ag | New organosilicon compound containing maleate group and other functional groups, useful for the preparation of cross-linkable mass, which is useful to prepare molded articles and for coating paper and foil substrates |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3631125A1 (en) * | 1986-09-12 | 1988-03-24 | Wacker Chemie Gmbh | METHOD FOR PRODUCING ORGANOPOLYSILOXANELASTOMERS AND NEW ORGANOSILICIUM COMPOUNDS |
| US5998515A (en) * | 1997-12-29 | 1999-12-07 | General Electric Company | Liquid injection molding silicone elastomers having primerless adhesion |
| US6040366A (en) * | 1998-02-27 | 2000-03-21 | General Electric Company | Liquid injection molding silicone elastomers having primerless adhesion |
| US7767754B2 (en) | 2005-11-08 | 2010-08-03 | Momentive Performance Materials Inc. | Silicone composition and process of making same |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4308372A (en) * | 1979-06-25 | 1981-12-29 | General Electric Company | Shelf-stable one-part room temperature vulcanizable silicone rubber compositions |
-
1985
- 1985-12-20 CA CA000498347A patent/CA1270973A/en not_active Expired - Fee Related
- 1985-12-27 JP JP60293396A patent/JPH0672206B2/en not_active Expired - Lifetime
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE102006016321A1 (en) * | 2006-04-06 | 2007-11-29 | Wacker Chemie Ag | New organosilicon compound containing maleate group and other functional groups, useful for the preparation of cross-linkable mass, which is useful to prepare molded articles and for coating paper and foil substrates |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0672206B2 (en) | 1994-09-14 |
| JPS61181863A (en) | 1986-08-14 |
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