Platinum (II) diene complexes for controlled siloxane crosslinking
A process for cross-linking siloxane and organic polymers comprising reacting (a) a silyl hydride with (b) an unsaturated polymeric compound in the presence of (d) a platinum diene compound with a chelating dianionic ligand.
1. A process for producing a crosslinked product comprising reacting (a) an alkenyl silicone, (b) a hydrogen siloxane (c) optionally a cure inhibitor, and (d) a catalyst, optionally in the presence of a solvent, wherein the catalyst comprises a compound of the formula:
wherein R 1 —X 2 —R 2 is a diene that is bonded to platinum in an η 4 -mode and is a branched chain, an unbranched chain, a cyclic system, or a bicyclic system having 4 to 30 carbon atoms;
E 1 and E 2 are independently chosen from monoanionic ligands of O, NR 3 , a carboxyl group [C(O)O], or S;
R 3 is independently hydrogen, or a monovalent hydrocarbon radical having from 1 to 30 carbon atoms;
X 1 is a divalent hydrocarbyl group selected from a substituted or unsubstituted alkylene, or arylene group with the proviso that the E 1 -X 1 -E 2 ligand of Formula (I) does not include ureylene or alpha hydroxy acid ligands;
X 2 is a divalent hydrocarbyl selected from a substituted or unsubstituted alkylene, arylene, or cycloalkylene group, whereby the bonding olefin moieties are terminal and/or internal and X 2 represents bridges between the olefinic groups; and
n is 0, 1, 2, 3, or 4.
2. The process of claim 1 , wherein E 1 and E 2 are O.
3. The process of claim 1 , wherein R 1 —X 2 —R 2 is chosen from 1,5-cyclooctadiene, norbornadiene, dicyclopentadiene, or 1,5-hexadiene.
4. The process of claim 1 , wherein E 1 -X 1 -E 2 is chosen from amidophenolate, phenylenediamide, benzenedithiolate, mercaptophenolate, mercaptoethanolate, pinacolate, ethylene diolate, propandiolate, catecholate, substituted catecholate, salicylate, oxalate, or malonate.
5. The process of claim 4 , wherein R 1 —X 2 —R 2 is 1,5-cyclooctadiene.
6. The process of claim 1 , wherein E 1 -X 1 -E 2 is pinacolate, and R 1 —X 2 —R 2 is 1,5-cyclooctadiene.
7. The process of claim 1 , wherein E 1 -X 1 -E 2 is represented by the formula:
where R 4 , R 5 , R 6 , and R 7 are independently chosen from hydrogen, a C1-C20 alkyl, and a C6-C10 aryl.
8. The process of claim 7 , wherein E 1 and E 2 are each O.
9. The process of claim 1 , wherein E 1 -X 1 -E 2 is represented by the formula:
where R 8 , R 9 , R 10 , and R 11 are independently chosen from hydrogen and a C1-C20 alkyl.
10. The process of claim 9 , wherein R 8 , R 9 , R 10 , and R 11 are each hydrogen.
11. The process of claim 9 , wherein R 8 and R 10 are independently chosen from a C1-C20 alkyl, and R 9 and R 11 are each hydrogen.
12. The process of claim 11 , wherein R 8 and R 10 are each tert-butyl.
13. The process of claim 9 , wherein E 1 and E 2 are independently chosen from 0 and S.
14. 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 12 2 R 13 SiO 1/2 , T b =R 14 SiO 3/2 where R 14 is chosen from R 12 or R 13 ; D c =R 12 R 14 SiO 2/2 where R 14 is chosen from R 12 or R 13 ; M d =R 12 3 SiO 1/2 ; and Q e =SiO 4/2 ; R 12 is independently selected from a monovalent hydrocarbon radical having one to forty carbon, optionally containing at least one heteroatom; and R 13 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; and a+b+c+d+e is in the range of 50-20,000.
15. 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 hydrogen siloxane is between 100 and 100,000 Dalton; M is a monofunctional group of formula R 15 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 15 SiO 3/2 , and Q is a tetrafunctional group of formula SiO 4/2 , M H is HR 15 2 SiO 1/2 , T H is HSiO 3/2 , and D H is R 15 HSiO 2/2 , where each occurrence of R 15 is independently chosen from a C1-C40 alkyl, a C1-C40 substituted alkyl, a C6-C14 aryl or substituted aryl, wherein R 15 optionally contains at least one heteroatom.
16. The process of claim 1 , wherein the inhibitor is chosen from ethylenically unsaturated amides, aromatically unsaturated amides, acetylenic compounds, ethylenically unsaturated isocyanates, olefinic siloxanes, unsaturated hydrocarbon diesters, unsaturated hydrocarbon mono-esters of unsaturated acids, conjugated or isolated ene-ynes, hydroperoxides, ketones, sulfoxides, amine, phosphines, phosphites, nitrites, diaziridines, or a combination of two or more thereof.
17. The process of claim 1 , wherein the concentration of platinum is from about 100 parts per billion (ppb) to about 100 ppm.
18. The process of claim 1 , wherein component (c) is present in an amount of from about 0 to about 10 weight percent.
19. The process of claim 1 , wherein components (a)-(d) are provided in a single composition.
20. The process of claim 1 , wherein the reaction is completed in about 10 seconds or less.
21. The process of claim 1 , wherein the reaction is completed in 2-5 seconds.
22. The process of claim 1 , wherein the process is conducted by heating at a temperature above room temperature.
23. The process of claim 1 , wherein the a composition of components (a)-(d) has a working life of at least 2 hours when the concentration of inhibitor (c) is about 0.25 weight percent or less.
24. A composition comprising (a) an alkenyl silicone, (b) a hydrogen siloxane, (c) optionally a cure inhibitor, and (d) a catalyst, optionally in the presence of a solvent, wherein the catalyst comprises a compound of the formula:
wherein R 1 —X 2 —R 2 is a diene that is bonded to platinum in an η 4 -mode and is a branched chain, an unbranched chain, a cyclic system, or a bicyclic system having 4 to 30 carbon atoms;
E 1 and E 2 are independently chosen from monoanionic ligands of O, NR 3 , a carboxyl group [C(O)O], or S;
R 3 are each independently hydrogen, or a monovalent hydrocarbon radical having from 1 to 30 carbon atoms;
X 1 is a divalent hydrocarbyl group selected from a substituted or unsubstituted alkylene, or arylene group with the proviso that the E 1 -X 1 -E 2 ligand of Formula (I) does not include urelyene or alpha hydroxy acid ligands;
X 2 is a divalent hydrocarbyl selected from a substituted or unsubstituted alkylene, arylene, or cycloalkylene group, whereby the bonding olefin moieties are terminal and/or internal and X 2 represents bridges between the olefinic groups; and
n is 0, 1, 2, 3, or 4.
25. The composition of claim 24 , wherein E 1 and E 2 are 0.
26. The composition of claim 24 , wherein R 1 —X 2 —R 2 is chosen from 1,5-cyclooctadiene, norbornadiene, dicyclopentadiene, or 1,5-hexadiene.
27. The composition of claim 24 , wherein E 1 -X 1 -E 2 is chosen from amidophenolate, phenylenediamide, benzenedithiolate, mercaptophenolate, mercaptoethanolate, pinacolate, ethanediolate, propanediolate, catecholate, substituted catecholate, salicylate, oxalate, or malonate.
28. The composition of claim 27 , wherein R 1 —X 2 —R 2 is 1,5-cyclooctadiene.
29. The composition of claim 24 , wherein the catalyst (c) is chosen from pinacolate-Pt-cycloooctadiene; propanediolate-Pt-cyclooctadiene; salicylate-Pt-cyclooctadiene, or a combination of two or more thereof.
30. The composition of claim 24 , 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 12 2 R 13 SiO 1/2 ; T b =R 14 SiO 3/2 where R 14 is chosen from R 12 or R 13 ; D c =R 12 R 14 SiO 2/2 where R 14 is chosen from R 12 or R 13 ; M d =R 12 3 SiO 1/2 ; and Q e =SiO 4/2 ; R 12 is independently selected from a monovalent hydrocarbon radical having one to forty carbon, optionally containing at least one heteroatom; and R 13 is selected from a terminal olefinic monovalent hydrocarbon radical having two to forty carbon atoms, optionally containing at least one heteroatom, where the alkenyl silicone comprises at least two unsaturated groups reactive to hydrosilylation per chain; a≥0, b≥0, d≥0, e≥0; and a+b+c+d+e is in the range of 50-20,000.
31. The composition of claim 24 , 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 15 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 15 SiO 3/2 , and Q is a tetrafunctional group of formula SiO 4/2 , M H is HR 15 2 SiO 1/2 , T H is HSiO 3/2 , and D H is R 15 HSiO 2/2 , and each occurrence of R 15 is independently chosen from a C1-C40 alkyl, a C1-C40 substituted alkyl, a C6-C14 aryl or substituted aryl, wherein R 15 optionally contains at least one heteroatom.
32. The composition of claim 24 , wherein the inhibitor is chosen from ethylenically unsaturated amides, aromatically unsaturated amides, acetylenic compounds, ethylenically unsaturated isocyanates, olefinic siloxanes, unsaturated hydrocarbon diesters, unsaturated hydrocarbon mono-esters of unsaturated acids, conjugated or isolated ene-ynes, hydroperoxides, ketones, sulfoxides, amine, phosphines, phosphites, nitrites, diaziridines, or a combination of two or more thereof.
33. The composition of claim 24 , wherein the concentration of platinum is from about 100 parts per billion (ppb) to about 100 ppm.
34. The composition of claim 24 , comprising components (a)-(d) as a single component composition.
35. A cured material prepared from the composition of claim 24 .
36. A coating formed from the composition of claim 24 .
37. A substrate having a surface thereof at least partially coated with the coating of claim 36 .
38. The substrate of claim 37 , wherein the coating is anchored to the surface of the substrate.
39. A compound of the formula:
wherein R 1 —X 2 —R 2 is a diene that is bonded to platinum in an η 4 -mode and is a branched chain, an unbranched chain, a cyclic system, or a bicyclic system having 4 to 30 carbon atoms;
E 1 -(X 1 ) n -E 2 is chosen from mercaptophenolate, pinacolate, propanediolate, or salicylate; and
X 2 is a divalent hydrocarbyl such as substituted or unsubstituted alkylene, arylene, or cycloalkylene group, whereby the bonding olefin moieties are terminal and/or internal and X 2 represents bridges between the olefinic groups.
40. The compound of claim 39 , wherein R 1 —X 2 —R 2 is chosen from 1,5-cyclooctadiene, norbornadiene, dicyclopentadiene, or 1,5-hexadiene.
41. The compound of claim 39 , wherein the compound is chosen from pinacolate-Pt-cyclooctadiene; propanediolate-Pt-cyclooctadiene; or salicylate-Pt-cyclooctadiene.