Catalyst for synthesis of siloxanes

Patent metadata

Field	Value
Publication number	US-2016347910-A1
Application number	US-201414891803-A
Country	US
Kind code	A1
Filing date	May 16, 2014
Priority date	Feb 15, 2013
Publication date	Dec 1, 2016
Grant date	—

Abstract

Compositions and methods for the production of siloxane materials using an azaphosphatrane as a catalyst. In one embodiment, there is provided a process for the ring opening polymerization of a cyclosiloxane in the presence of an azaphosphatrane. In another embodiment, there is provided a composition and method for condensation curing of a moisture curable composition using an azaphosphatrane.

First claim

1 . A process for the synthesis of a siloxane polymer by ring opening polymerization of a cyclosiloxane comprising contacting a cyclosiloxane with an azaphosphatrane.

2 . The process of claim 1 , wherein the azaphosphatrane is of the formula:

where R 9 , R 10 , and R 11 are independently chosen from hydrogen, a linear or branched alkyl comprising 1 to 10 carbon atoms, and an aromatic group comprising 6 to 12 carbon atoms, and a substituted phosphorous group with or without nitrogen; and A is chosen from hydrogen, R 12 , or (R 13 R 14 P—N=)t, where R 12 , R 13 , and R 14 are independently chosen from hydrogen, a linear or branched alkyl comprising 1 to 10 carbon atoms, and an aromatic group comprising 6 to 12 carbon atoms; and t is 1 to 10.

3 . The process of claim 2 , wherein the azaphosphatrane is chosen from a compound of the formulas:

or a combination of two or more thereof.

4 . The process of claim 1 , comprising an azaphosphatrane compound of the formula:

where R 9 , R 10 , and R 11 are independently chosen from methyl, isopropyl, or isobutyl.

5 . The process of claim 1 , wherein the azaphosphatrane is present in an amount of from about 0.025 weight percent to about 5 weight percent based on the total weight of the cyclosiloxane.

6 . The process of claim 1 , wherein the azaphosphatrane is present in an amount of from about 0.1 weight percent to about 0.4 weight percent based on the total weight of the cyclosiloxane.

7 . The process of claim 1 , wherein the cyclosiloxane is of the formula (R 15 R 16 SiO) n , wherein R 15 and R 16 are independently chosen from hydrogen or an optionally substituted alkyl, alkenyl, aryl, alkaryl or aralkyl group having up to 8 carbon atoms, n denotes an integer with a value of from 3 to 12.

8 . The process of claim any of claim 14 , wherein the cyclosiloxene is chosen from octamethyl cyclotetrasiloxane (D4), hexamethylcyclotrisiloxane (D3), octaphenylcyclotetrasiloxane, tetramethylcyclotetrasiloxane, tetramethyltetravinylcyclotetrasiloxane, hexamethyl-1,1-diphenylcyclotetrasiloxane, decamethyl pentacyclosiloxane, cyclopenta (methylvinyl) siloxane, cyclotetra(phenylmethyl) siloxane, cyclopenta methylhydrosiloxane, or a combination of two or more thereof.

9 . The process of claim 1 comprising two or more cyclosiloxanes, along with silanol or methyl terminated poly(dimethylsiloxane) where at least two cyclosiloxanes have a different ring size from each other.

10 . The process of claim 1 , wherein the process comprises adding an endblocker material.

11 . The process of claim 10 , wherein the endblocker material is chosen from hexamethyldisiloxane; octamethyltrisiloxane; decamethyltetrasiloxane; dodecamethylpentasiloxane; tetradecamethylhexasiloxane; hexadecamethylheptasiloxane, or a combination of two or more thereof.

12 . The process of claim 1 further comprising deactivating the catalyst.

13 . The process of claim 12 , wherein deactivating the catalyst comprises: heating the product of the process at a temperature of about 100° C. or greater after the reaction; treating the product with water; bubbling carbon dioxide through the product; treating the product with a material to neutralize the catalyst, or a combination of two or more thereof.

14 . The process of claim 12 further comprising filtering the reaction mixture.

15 . The process of claim 14 further comprising treating the filtered reaction mixture with charcoal.

16 . A composition for forming a cured polymer composition comprising:
(A) a polymer having at least a reactive silyl group; (B) a crosslinker or chain extender; (C) a catalyst comprising an azaphosphatrane compound; and (D) an optional adhesion promoter.

17 . The composition of claim 16 , wherein the azaphosphatrane is of the formula:

where R 9 , R 10 , and R 11 are independently chosen from hydrogen, a linear or branched alkyl comprising 1 to 10 carbon atoms, and an aromatic group comprising 6 to 12 carbon atoms, and a substituted phosphorous group with or without nitrogen; and A is chosen from hydrogen, R 12 , or (R 13 R 14 P—N=)t, where R 12 , R 13 , and R 14 are independently chosen from hydrogen, a linear or branched alkyl comprising 1 to 10 carbon atoms, and an aromatic group comprising 6 to 12 carbon atoms; and t is 1 to 10.

18 . The composition of claim 17 , wherein the azaphosphatrane is chosen from a compound of the formulas:

or a combination of two or more thereof.

19 . The composition of claim 16 comprising from about 0.01 to about 7 parts per weight catalyst (C) per 100 parts per weight of the polymer (A).

20 . The composition of claim 16 , wherein the polymer (A) has the formula
[R 1 a R 2 3-a Si—Z—] n -X—Z—SiR 1 a R 2 3-a .
where X is chosen from a polyurethane; a polyester; a polyether; a polycarbonate; a polyolefin; a polyester ether; and a polyorganosiloxane having units of R 3 SiO 1/2 , R 2 SiO, RSiO 3/2 , and/or SiO 2 ,
n is 0 to 100,
a is 0 to 2,
R and R 1 can be identical or different at the same Si-atom and chosen from a C 1 -C 10 alkyl; a C 1 -C 10 alkyl substituted with one or more of Cl, F, N, O or S; a phenyl; a C 7 -C 16 alkylaryl; a C 7 -C 16 arylalkyl; a C 2 -C 4 polyalkylene ether; or a combination of two or more thereof.
R 2 is chosen from OH, C 1 -C 8 alkoxy, C 2 -C 18 alkoxyalkyl, oximoalkyl, enoxyalkyl, aminoalkyl, carboxyalkyl, amidoalkyl, amidoaryl, carbamatoalkyl, or a combination of two or more thereof, and
Z is a bond, a divalent unit selected from the group of a C 1 -C 8 alkylene, or O.

21 . The composition of claim 16 , wherein the crosslinker component (B) is chosen from tetraethylorthosilicate (TEOS); methyltrimethoxysilane (MTMS); methyltriethoxysilane; vinyltrimethoxysilane; vinyltriethoxysilane; methylphenyldimethoxysilane; 3,3,3-trifluoropropyltrimethoxysilane; methyltriacetoxysilane; vinyltriacetoxysilane; ethyltriacetoxysilane; di-butoxydiacetoxysilane; phenyltripropionoxysilane; methyltris(methylethylketoximo)silane; vinyltris(methylethylketoximo)silane; 3,3,3-trifluoropropyltris(methylethylketoximo)silane; methyltris(isopropenoxy)silane; vinyltris(isopropenoxy)silane; ethylpolysilicate; dimethyltetraacetoxydisiloxane; tetra-n-propylorthosilicate; methyldimethoxy(ethylmethylketoximo)silane; methylmethoxybis(ethylmethylketoximo)silane; methyldimethoxy(acetaldoximo)silane; methyldimethoxy(N-methylcarbamato)silane; ethyldimethoxy(N-methylcarbamato)silane; methyldimethoxyisopropenoxysilane; trimethoxyisopropenoxysilane; methyltriisopropenoxysilane; methyldimethoxy(but-2-en-2-oxy)silane; methyldimethoxy(l-phenylethenoxy)silane; methyldimethoxy-2-(1-carboethoxypropenoxy)silane; methylmethoxydi(N-methylamino)silane; vinyldimethoxy(methylamino)silane; tetra-N,N-diethylaminosilane; methyldimethoxy(methylamino)silane; methyltri(cyclohexylamino)silane; methyldimethoxy(ethylamino)silane; dimethyldi(N,N-dimethylamino)silane; methyldimethoxy(isopropylamino)silane; dimethyldi(N,N-diethylamino)silane;

Assignees

• Momentive Performance Mat Inc
• Momentive Performance Mat Inc

Inventors

• Sivasubramanian Karthikeyan
• Anderson Patricia

Classifications

• C09D5/1637

  Macromolecular compounds · CPC title

• C09D183/08

  containing silicon bound to organic groups containing atoms other than carbon, hydrogen, and oxygen · CPC title

• C08G77/08 Primary

  characterised by the catalysts used · CPC title

• C08G59/3281 Primary

  containing silicon · CPC title

• Y10T428/31663

  As siloxane, silicone or silane · CPC title