Granted Patent B2

US 12,746,537 · App. 18/469,546 · Granted Sep 29, 2026

Inventor: Aroop Kumar Roy (Mechanicville, NY)

B01J31/2295C07F7/21B01J2231/32B01J2531/004B01J2531/828

Abstract

Claims (81)

1 . A complex according to Formula VIII, selected individually or in any mixture:

wherein:

the ligand 1 CR 2 ═CR 3 -E-X-E-CR 4 ═CR 5 R is dienic,

R 1 and R 6 are independently an alkyl or aryl group, or H if CR 2 ═CR 3 or CR 4 ═CR 5 is part of a cyclic structure such as a cyclic monoolefin;

R 2 , R 3 , R 4 , and R 5 are independently H, an alkyl group, or an aryl group, or

R 2 and R 3 and/or R 4 and R 5 taken together form part of a cyclic monoolefin;

both occurrences of E are either SiR 13 R 14 where R 13 and R 14 are independently alkyl or aryl, or CR 15 R 16 where R 15 and R 16 are independently H, alkyl or aryl;

X is selected from oxygen (O) and nitrogen (N), preferably oxygen, or X is a divalent hydrocarbyl group;

L is a monodentate or bidentate neutral ligand selected from organophosphines or CO, and p=0-1;

wherein, if p=1, the ratio min is 1:1;

wherein, if p=0, the ratio min is from 2:1 to 3:2;

wherein each said alkyl or aryl group either within the internal alkenyl group or on the organophosphine independently contains 1-20 carbon atoms;

wherein said alkyl or aryl group optionally and independently contains heteroatoms selected from N, O, P, Si, S; and

wherein said alkyl or aryl group optionally and independently is substituted with halogen.

2 . A complex according to Formula VIII, selected individually or in any mixture:

wherein:

the ligand 1 CR 2 ═CR 3 -E-X-E-CR 4 ═CR 5 R is dienic,

R 1 and R 6 are independently an alkyl or aryl group, or H if CR 2 —CR 3 or CR 4 ═CR 5 is part of a cyclic monoolefin;

R 2 , R 3 , R 4 , and R 5 are independently H, an alkyl group, or an aryl group, or R 2 and R 3 and/or R 4 and R 5 taken together form part of a cyclic monoolefin structure;

both occurrences of E are either SiR 13 R 14 where R 13 and R 14 are independently alkyl or aryl, or CR 15 R 16 where R 15 and R 16 are independently H, alkyl or aryl;

X is selected from oxygen (O) and nitrogen (N), or X is a divalent hydrocarbyl group;

L is a monodentate or bidentate neutral ligand selected from organophosphines, organophosphine oxides, CO, internal monoolefins, cyclodienes, or 2-methyl-1,4-naphthoquinone, and p=0-1;

wherein, if p=1, the ratio min is 1:1;

wherein, if p=0, the ratio min is from 2:1 to 3:2;

wherein each said alkyl or aryl group either within the internal alkenyl group or on the organophosphine or organophosphine oxide independently contains 1-20 carbon atoms;

wherein said alkyl or aryl group optionally and independently contains heteroatoms selected from N, O, P, Si, S; and

wherein said alkyl or aryl group optionally and independently is substituted with halogen.

3 . The complex according to claim 1 that is an in-situ complex wherein a Pt atom of the complex is coordinated to one or both internal olefin groups of the dienic ligand 1 CR 2 ═CR 3 -E-X-E-CR 4 ═CR 5 R .

4 . The complex according to claim 2 that is an in-situ complex wherein a Pt atom of the complex is coordinated to one or both internal olefin groups of the dienic ligand 1 CR 2 ═CR 3 -E-X-E-CR 4 ═CR 5 R .

5 . The complex according to claim 1 wherein X is oxygen (O).

6 . The complex according to claim 1 , wherein X is a divalent hydrocarbyl group and the divalent hydrocarbyl group is —CH 2 —.

7 . The complex according to claim 1 , wherein the organophosphine is a triorganophosphine.

8 . The complex according to claim 7 wherein the triorganophosphine is a triarylphosphine.

9 . The complex according to claim 1 , wherein p=0, and the ratio min is 3:2, or wherein p=1, and the ratio min is 1:1.

10 . The complex according to claim 2 wherein X is oxygen (O).

11 . The complex according to claim 2 , wherein X is a divalent hydrocarbyl group and the divalent hydrocarbyl group is —CH 2 —.

12 . The complex according to claim 2 , wherein the organophosphine is a triorganophosphine.

13 . The complex according to claim 12 wherein the triorganophosphine is a triarylphosphine.

14 . The complex according to claim 2 , wherein p=0, and the ratio min is 3:2, or wherein p=1, and the ratio min is 1:1.

15 . The complex according to claim 2 wherein the internal monoolefin is 2 butene, dimethyl maleate, dimethyl fumarate, diallyl maleate, fumaronitrile, tetracyanoethylene, or maleic anhydride.

16 . The complex according to claim 2 , wherein the cyclodiene is 1,5-cyclooctadiene.

17 . A process for hydrosilylation of unsaturated compounds, comprising:

reacting a silyl or siloxy hydride with an unsaturated compound having one or more unsaturations in a reaction mixture comprising a complex according to claim 1 ,

wherein the one or more unsaturations are, independently, a double bond or triple bond.

18 . The process according to claim 17 , wherein the reaction is conducted under one or more conditions of:

(a) the concentration of Pt in the reaction mixture is between 0.1-100 ppm by weight;

(b) the reaction is conducted at a temperature is between −50° C. to 250° C.;

(c) the reaction is conducted neat or the reaction mixture further comprises a solvent selected from a hydrocarbon, a halogenated hydrocarbon, an ether, an alcohol, or a combination of two or more thereof;

(d) the reaction is conducted under ambient, sub-ambient or super-ambient pressure;

(e) the reaction mixture further comprises a cure inhibitor; and

(f) the reaction mixture comprises excess of the dienic ligand 1 CR 2 ═CR 3 -E-X-E-CR 4 ═CR 5 R such that the dienic ligand to platinum ratio in the reaction mixture is less than or equal to 1000:1.

19 . A process for hydrosilylation of unsaturated compounds, comprising:

reacting a silyl or siloxy hydride with an unsaturated compound having one or more unsaturations in a reaction mixture comprising a complex according to claim 2 ,

wherein the one or more unsaturations are, independently, a double bond or triple bond.

20 . The process according to claim 18 , wherein the reaction is conducted under one or more conditions of:

(a) the concentration of Pt in the reaction mixture is between 0.1-100 ppm by weight;

(b) the reaction is conducted at a temperature is between −50° C. to 250° C.;

(c) the reaction is conducted neat or the reaction mixture further comprises a solvent selected from a hydrocarbon, a halogenated hydrocarbon, an ether, an alcohol, or a combination of two or more thereof; and

(d) the reaction is conducted under ambient, sub-ambient or super-ambient pressure;

(e) the reaction mixture further comprises a cure inhibitor; and

(f) the reaction mixture comprises excess of the dienic ligand 1 CR 2 ═CR 3 -E-X-E-CR 4 ═CR 5 R such that the dienic ligand to platinum ratio in the reaction mixture is less than or equal to 1000:1.

21 . A process for hydrosilylation of unsaturated compounds, comprising:

reacting a silyl or siloxy hydride with an unsaturated compound having one or more unsaturations in a reaction mixture comprising a complex according to claim 3 ,

wherein the one or more unsaturations are, independently, a double bond or triple bond.

22 . The process according to claim 21 , wherein the reaction is conducted under one or more conditions of:

(a) the concentration of Pt in the reaction mixture is between 0.1-100 ppm by weight;

(b) the reaction is conducted at a temperature is between −50° C. to 250° C.;

(c) the reaction is conducted neat or the reaction mixture further comprises a solvent selected from a hydrocarbon, a halogenated hydrocarbon, an ether, an alcohol, or a combination of two or more thereof;

(d) the reaction is conducted under ambient, sub-ambient or super-ambient pressure;

(e) the reaction mixture further comprises a cure inhibitor; and

(f) the reaction mixture comprises excess of the dienic ligand 1 CR 2 ═CR 3 -E-X-E-CR 4 ═CR 5 R such that the dienic ligand to platinum ratio in the reaction mixture is less than or equal to 1000:1.

23 . A process for hydrosilylation of unsaturated compounds, comprising:

reacting a silyl or siloxy hydride with an unsaturated compound having one or more unsaturations in a reaction mixture comprising a complex according to claim 4 ,

wherein the one or more unsaturations are, independently, a double bond or triple bond.

24 . The process according to claim 23 , wherein the reaction is conducted under one or more conditions of:

(a) the concentration of Pt in the reaction mixture is between 0.1-100 ppm by weight;

(b) the reaction is conducted at a temperature is between −50° C. to 250° C.;

(c) the reaction is conducted neat or the reaction mixture further comprises a solvent selected from a hydrocarbon, a halogenated hydrocarbon, an ether, an alcohol, or a combination of two or more thereof; and

(d) the reaction is conducted under ambient, sub-ambient or super-ambient pressure;

(e) the reaction mixture further comprises a cure inhibitor; and

(f) the reaction mixture comprises excess of the dienic ligand 1 CR 2 ═CR 3 -E-X-E-CR 4 ═CR 5 R such that the dienic ligand to platinum ratio in the reaction mixture is less than or equal to 1000:1.

Continuity (3)

References Cited (48)