Platinum (II) diene complexes with chelating dianionic ligands and their use in hydrosilylation reactions
A process for the hydrosilylation of an unsaturated compound comprising reacting (a) a silyl hydride with (b) an unsaturated compound in the presence of (c) a platinum based hydrosilylation catalyst comprising a platinum-diene complex with chelating anions. The use of the present catalysts in the process provides silylated products in good yields and allows for using lower platinum loadings than conventional catalysts, reduced cycle times, and may reduce yellowing in the product.
1. A process for the hydrosilylation of an unsaturated compound comprising reacting (a) a silyl hydride with (b) an unsaturated compound in the presence of (c) a hydrosilylation catalyst, optionally in the presence of a solvent, to produce a hydrosilylated product, wherein the hydrosilylation catalyst is a complex of Formula (I):
where R 1 —X 2 —R 2 is a diene that is bonded to platinum in an η 4 -mode and is chosen from a branched or unbranched chain, a cyclic structure, or a bicyclic system having 4 to 30 carbon atoms, whereby R 1 and R 2 are olefinic groups comprising terminal and/or internal bonding olefin moieties, and X 2 is a divalent hydrocarbyl group chosen from an alkylene, an arylene, or a cycloalkylene group;
E 1 and E 2 are independently chosen from a mono-anionic group of O, NR 3 carboxyl group (C(O)O), and S; R 3 is independently hydrogen, or a monovalent hydrocarbon radical having from 1 to 30 carbon atoms;
X 1 is a divalent hydrocarbyl chosen from an alkylene, or an arylene; and
n is 0, 1, 2, 3, or 4
with the proviso that E 1 -X 1 -E 2 is not an alpha hydroxy acid.
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 1,5-cyclooctadiene.
4. The process of claim 1 , wherein E 1 -X 1 -E 2 is chosen from an amidophenolate, a phenylenediamide, a benzenedithiolate, a mercaptophenolate, a mercaptoethanolate, a pinacolate, an ethylene diolate, a propandiolate, a catecholate, a catecholate, a salicylate, an 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 4 , wherein E 1 -X 1 -E 2 is chosen from:
where R 4 , R 5 , R 6 , and R 7 are independently chosen from hydrogen, a C1-C20 alkyl, and a C6-C10 aryl, and R 8 , R 9 , R 10 , and R 11 are independently chosen from hydrogen and a C1-C20 alkyl.
7. The process of claim 6 , wherein R 8 , R 9 , R 10 , and R 11 are each hydrogen.
8. The process of claim 7 , wherein R 8 and R 10 are independently chosen from a C1-C20 alkyl, and R 9 and R 11 are each hydrogen.
9. The process of claim 8 , wherein R 8 and R 10 are each tert-butyl.
10. The process of claim 6 , wherein E 1 and E 2 are each O.
11. The process of claim 6 , wherein E 1 and E 2 are independently chosen from O and S.
12. The process of claim 1 , wherein E 1 -X 1 -E 2 is 3,5-dibutylcatecholate, and R 1 —X 2 —R 2 is 1,5-cyclooctadiene.
13. The process of claim 1 , wherein the unsaturated compound is chosen from an unsaturated polyether; an alkyl capped allyl polyether; a methylallyl polyether; a terminally unsaturated amine; an alkyne; a C2-C45 linear or branched olefin; an unsaturated epoxide; a terminally unsaturated acrylate; a terminally unsaturated methacrylate; a terminally unsaturated diene; an aliphatically unsaturated aryl ether; an aliphatically unsaturated aromatic hydrocarbon; an unsaturated cycloalkane; a vinyl-functionalized polymer or oligomer; a vinyl-functionalized and/or terminally unsaturated allyl-functionalized or alkenyl-functionalized silane or siloxane; an unsaturated fatty acid; an unsaturated fatty ester; or a combination of two or more thereof.
14. The process of claim 1 , wherein the unsaturated compound is chosen from a polyoxyalkylene having the formula:
R 28 (OCH 2 CH 2 ) z (OCH 2 CHR 30 ) w —OR 29 ;
R 29 O(CHR 30 CH 2 O) w (CH 2 CH 2 O) z —CR 31 2 —C≡C—CR 31 2 (OCH 2 CH 2 ) z (OCH 2 CHR 30 ) w OR 29 ;
H 2 C═CR 31 CH 2 O(CH 2 CH 2 O) z (CH 2 CHR 30 O) w CH 2 CR 31 ═CH 2 ;
or a combination of two ore thereof, wherein R 28 is independently an unsaturated organic group containing from 2 to 10 carbon atoms; R 29 is independently hydrogen, an acyl group, or an alkyl group having from 1 to 8 carbon atoms; R 30 is independently a monovalent hydrocarbon group; R 31 independently chosen from hydrogen and a monovalent hydrocarbon group having 1-20 carbon atoms; each occurrence of z is 0 to 100 inclusive; and each occurrence of w is 0 to 100 inclusive.
15. The process of claim 1 , wherein the silylhydride is chosen from a compound of the formula R 12 m SiH p X 4−(m+p) and/or M a M H b D c D H d T e T H f Q g , where each R 12 is independently an aliphatic or aromatic hydrocarbyl group, X is alkoxy, acyloxy, halogen, or silazane, m is 1-3, p is 1-3 the subscripts a, b, c, d, e, f, and g are such that the molar mass of the silylhydride is between 100 and 100,000 Dalton; M is a monofunctional group of formula R 13 3 SiO 1/2 , D is a difunctional group of formula R 14 2 SiO 2/2 , a T is a trifunctional group of formula R 15 SiO 3/2 , Q is a tetrafunctional group of formula SiO 4/2 , M H is HR 16 2 SiO 1/2 , T H represents HSiO 3/2 , and D H is R 17 HSiO 2/2 ; each occurrence of R 13-17 is independently C1-C18 alkyl, C6-C14 aryl, wherein R 13-17 optionally contains at least one heteroatom.
16. The process according to claim 1 , wherein the silylhydride is a chlorosilane, R 12 m SiH p X 4−(m+p) , M a D H d M a , where R12 is a C1-C10 alkoxy, m is 1-3, and p is 1-3, M is a monofunctional group of formula R 13 3 SiO 1/2 , D H is R 17 HSiO 2/2 ; each occurrence of R 13 and R 17 is independently C1-C18 alkyl, C6-C14 aryl, wherein R 13 and R 17 optionally contains at least one heteroatom, and a and d are such that the molar mass of the silylhydride is between 100 and 100,000 Dalton.
17. The process of claim 1 , wherein the silylhydride is a compound of the formula R 18 R 19 R 20 Si(CH 2 R 21 ) x SiOSiR 22 R 23 (OSiR 24 R 25 ) y OSiR 26 R 27 H, where R 18 -R 27 are independently chosen from hydrogen, a monovalent alkyl group, a cycloalkyl group, and an aryl group; x has a value of 1-8, and y has a value from zero to 10.
18. The process according to claim 1 where the unsaturated compound is allyl methacrylate.
19. The process of claim 1 , wherein the unsaturated compound is allyl glycidyl ether.
20. The process of claim 1 where the unsaturated compound is an allyl or methallyl polyether.
21. The process of claim 1 where the reaction is carried out at a temperature of −50 ° C. to 250 ° C.
22. The process of claim 1 where the reaction is conducted in the presence of a solvent chosen from a hydrocarbon, a halogenated hydrocarbon, an ether, an alcohol, or a combination of two or more thereof.
23. The process of claim 1 , wherein the platinum concentration is from about 100 parts per billion to about 100 parts per million.