Siloxane crosslinking processes employing sulfur compounds and platinum catalysts
Provided is a composition and process for producing a crosslinked product. The composition comprises a mixture constituting (a) an alkenyl silicone, (b) a hydrogen siloxane, (c) a cure inhibitor and (d) a hydrosilylation catalyst, optionally in the presence of a solvent, and (e) sulfur compounds in order to produce the crosslinked product, and the process comprises reacting such a composition to form a crosslinked product.
1. A process for producing a crosslinked product comprising reacting a mixture constituting (a) an alkenyl silicone, (b) a hydrogen siloxane, (c) a cure inhibitor chosen from an ethylenically unsaturated amide, an aromatically unsaturated amide, an acetylenic compound, an ethylenically unsaturated isocyanate, an olefinic siloxane, an unsaturated hydrocarbon diester, an unsaturated hydrocarbon mono-ester of an unsaturated acid, a conjugated or isolated ene-yne, a hydroperoxide, a ketones, a sulfoxide, an amine, a phosphine, a phosphite, a nitrite, a diaziridine, or a combination of two or more thereof, and (d) a hydrosilylation catalyst, optionally in the presence of a solvent, and (e) a sulfur compound in order to produce the crosslinked product, the sulfur compound (e) being a compound of the formula:
R 1 —S—R 2
where (i) R 1 and R 2 are independently chosen from a H a C1-C20 hydroxyalkyl, a C1-C20 carboxylic acid, or a combination thereof, or (ii) R 1 is chosen from a C1-C20 alkyl, and R 2 is chosen from a C1-C20 hydroxyalkyl, with the proviso that Formula I is not H 2 S.
2. The process of claim 1 , wherein the hydrosilylation catalyst (d) comprises a metal, and the ratio of total moles of the sulfur compound (e) to moles of the metal in catalyst (d) is from about 1:1 to about 100:1.
3. The process of claim 1 , wherein the hydrosilylation catalyst (d) comprises a metal, and the ratio of total moles of the sulfur compound (e) to moles of the metal in catalyst (d) is from about 1:1 to about 10:1.
4. The process of claim 1 , comprising the inhibitor (c) in an amount of from about 0.001 to about 10% by weight of the mixture.
5. The process of claim 1 comprising the inhibitor (c) in an amount of from about 0.01 to about 0.1% by weight of the mixture.
6. The process of claim 1 , wherein the hydrosilylation catalyst is a platinum-based catalyst, and the platinum is present in an amount of from about 100 parts per billion to about 100 parts per million.
7. The process of claim 6 , wherein the platinum is present in an amount of from about 1 ppm to about 50 ppm.
8. The process of claim 1 , wherein the curable alkenyl silicone is of the formula:
M vi a T b D c M d Q e
wherein M vi a =R 3 2 R 4 SiO 1/2 ; T b =R 5 SiO 3/2 where R 5 is chosen from R 3 or R 4 ; D c =R 3 R 5 SiO 2/2 where R 5 is chosen from R 3 or R 4 ; M d =R 3 3 SiO 1/2 ; and Q e =SiO 4/2 ; R 3 is independently selected from a monovalent hydrocarbon radical having one to forty carbon, optionally containing at least one heteroatom; and R 4 is selected from a terminal olefinic monovalent hydrocarbon radical having two to forty carbon atoms, optionally containing at least one heteroatom, where the composition of the alkenyl silicone comprises at least two unsaturated groups reactive to hydrosilylation per chain; a≥0, b≥0, d≥0, e≥0; values for c in particular are determined by the desired properties and attributes of the cross-linked material so that the sum a+b+c+d+e is in the range 50-20,000.
9. The process of claim 1 , wherein the hydrogen siloxane is chosen from a compound of the formula M a′ M H b′ D c′ D H d′ T e′ T H f′ Q g , where the subscripts a′, b′, c′, d′, e′, f, and g are such that the molar mass of the siloxane-type reactant is between 100 and 100,000 Dalton; M is a monofunctional group of formula R 6 3 SiO 1/2 , D is a difunctional group of formula R 15 2 SiO 2/2 , T is a trifunctional group of formula R 7 SiO 3/2 , and Q is a tetrafunctional group of formula SiO 4/2 , M H is HR 8 2 SiO 1/2 , T H is HSiO 3/2 , and D H is R 10 HSiO 2/2 , where each occurrence of R 6-1 ° is independently chosen from a C1-C40 alkyl, a C1-C40 substituted alkyl, a C6-C14 aryl or substituted aryl, wherein R 6-10 optionally contains at least one heteroatom.
10. The process of claim 1 , wherein the reaction is completed in about 10 seconds or less.
11. The process of claim 1 , wherein the process is conducted by heating at a temperature of from about 0 to about 300° F.
12. The process of claim 1 , wherein components (a)-(d) are provided in a single composition.
13. The process of claim 1 , wherein components (a) and (e) are provided in a first part (i) optionally comprising component (c); component (b) is provided in a second part (ii); and component (d) is provided in a third part (iii), and the process comprises mixing parts (i), (ii), and (iii) to conduct the reaction.
14. The process of claim 1 , wherein component (a) and optionally component (c) is provided in a first part; component (b) is provided in a second part (ii); and components (d) and (e) are provided in a third part (iii).
15. A composition for producing a crosslinked product, the composition comprising (a) an alkenyl silicone, (b) a hydrogen siloxane, (c) a cure inhibitor chosen from an ethylenically unsaturated amide, an aromatically unsaturated amide, an acetylenic compound, an ethylenically unsaturated isocyanate, an olefinic siloxane, an unsaturated hydrocarbon diester, an unsaturated hydrocarbon mono-ester of an unsaturated add, a conjugated or isolated ene-yne, a hydroperoxide, a ketones, a sulfoxide, an amine, a phosphine, a phosphite, a nitrite, a diaziridine, or a combination of two or more thereof, and (d) a hydrosilylation catalyst, optionally in the presence of a solvent, and (e) a sulfur compound in order to produce the crosslinked product, the sulfur compound (e) being a compound of the formula:
R 1 —S—R 2
where (i) R 1 and R 2 are independently chosen from a H a C1-C20 hydroxyalkyl, a C1-C20 carboxylic acid, or a combination thereof, or (ii) R 1 is chosen from a C1-C20 alkyl, and R 2 is chosen from a C1-C20 hydroxyalkyl, with the proviso that Formula I is not H 2 S.
16. The composition of claim 15 , wherein the hydrosilylation catalyst (d) comprises a metal, and the ratio of total moles of the sulfur compound (e) to moles of the metal in catalyst (d) is from about 1:1 to about 100:1.
17. The composition of claim 15 , wherein the hydrosilylation catalyst (d) comprises a metal, and the ratio of total moles of the sulfur compound (e) to moles of the metal in catalyst (d) is from about 1:1 to about 10:1.
18. The composition of claim 15 , comprising the inhibitor (c) in an amount of from about 0.001 to about 10% by weight of the mixture.
19. The composition of claim 15 comprising the inhibitor (c) in an amount of from about 0.01 to about 0.1% by weight of the mixture.
20. The composition of claim 15 , wherein the hydrosilylation catalyst is a platinum-based catalyst, and the platinum is present in an amount of from about 100 parts per billion to about 100 parts per million.
21. The composition of claim 20 , wherein the platinum is present in an amount of from about 1 ppm to about 50 ppm.
22. The composition of claim 15 , wherein the curable alkenyl silicone is of the formula:
M vi a T b D c M d Q e
wherein M vi a =R 3 2 R 4 SiO 1/2 ; T b =R 5 SiO 3/2 where R 5 is chosen from R 3 or R 4 ; D c =R 3 R 5 SiO 2/2 where R 5 is chosen from R 3 or R 4 ; M d =R 3 3 SiO 1/2 ; and Q e =SiO 4/2 ; R 3 is independently selected from a monovalent hydrocarbon radical having one to forty carbon, optionally containing at least one heteroatom; and R 4 is selected from a terminal olefinic monovalent hydrocarbon radical having two to forty carbon atoms, optionally containing at least one heteroatom, where the composition of the alkenyl silicone comprises at least two unsaturated groups reactive to hydrosilylation per chain; a≥0, b≥0, d≥0, e≥0; values for c in particular are determined by the desired properties and attributes of the cross-linked material so that the sum a+b+c+d+e is in the range 50-20,000.
23. The composition of claim 15 , wherein the hydrogen siloxane is chosen from a compound of the formula M a′ M H b′ D c′ D H d′ T e′ T H f Q g , where the subscripts a′, b′, c′, d′, e′, f, and g are such that the molar mass of the siloxane-type reactant is between 100 and 100,000 Dalton; M is a monofunctional group of formula R 6 3 SiO 1/2 , D is a difunctional group of formula R 15 2 SiO 2/2 , T is a trifunctional group of formula R 7 SiO 3/2 , and Q is a tetrafunctional group of formula SiO 4/2 , M H is HR 8 2 SiO 1/2 , T H is HSiO 3/2 , and D H is R 10 HSiO 2/2 , where each occurrence of R 6-10 is independently chosen from a C1-C40 alkyl, a C1-C40 substituted alkyl, a C6-C14 aryl or substituted aryl, wherein R 6-10 optionally contains at least one heteroatom.
24. A cured material prepared from the process of claim 1 .
25. The cured material of claim 24 , wherein the cured material is a coating.
26. A substrate having a surface thereof at least partially coated with the coating of claim 25 .
27. The substrate of claim 26 , wherein the coating is a release coating.
28. A cured material formed from the composition of claim 14 .