Thermally stable, high refractive index curable silicone compositions

Patent metadata

Field	Value
Publication number	US-9834679-B2
Application number	US-201514814965-A
Country	US
Kind code	B2
Filing date	Jul 31, 2015
Priority date	Aug 1, 2014
Publication date	Dec 5, 2017
Grant date	Dec 5, 2017

Abstract

A curable composition comprises (a) a mercapto-functional siloxane; (b) a siloxane comprising unsaturated functional groups; (c) a photoinitiator; and (d) an antioxidant compound. In one embodiment, the antioxidant is chosen from a hindered phenolic compound. The curable compositions can be utilized to form a cured article, which may be useful in a variety of applications including, but not limited to, optical applications. The cured articles from the cured compositions may exhibit good physical properties including, for example, high refractive index. The articles may also exhibit good thermal stability.

First claim

What is claimed is:

1. A curable composition comprising:
(a) a mercapto-functional siloxane;
(b) a siloxane comprising an unsaturated hydrocarbon group;
(c) a photoinitiator; and
(d) an antioxidant compound comprising a hindered phenol; wherein (a) and (b) are provided such that the composition has a molar equivalent ratio of mercapto groups to unsaturated groups of about 2.5:1 to about 6:1.

2. The curable composition of claim 1 , wherein the mercapto-functional siloxane is a siloxane of the formula:
M 1 a M 2 b D 1 c D 2 d T 1 e T 2 f Q g   (1)

where the M-units are of the formula R 1 R 2 R 3 SiO 1/2 ; the D-units are of the formula: R 4 R 5 SiO 2/2 ; the T-units have three Si—O bonds are of the formula: R 6 SiO 3/2 ; the Q-units are of the formula SiO 4/2 ; R 1 -R 6 are independently chosen from hydrogen, a hydroxyl, a linear or branched alkyl group, an alcohol, a linear or branched alkoxy group, an aryl group, an alkylvinyl group, an amide, an amino-group, an acryloyl group, a carbonyl group, a silyloxy group, an isocyanyl group, a mercapto group, an epoxy-containing group, where one or more of R 1 -R 6 is a mercapto group; a is from 0-1000, b is from 0-1000; c is from 0-500; d is from 0-500; e is from 0-100; f is from 0-100; and g is from 0 to 200, where at least two subscripts on any particular embodiment are positive integers.

3. The curable composition of claim 2 , wherein the mercapto group is of the formula —(CH 2 ) h SH, where h is 0-10.

4. The curable composition of claim 3 , wherein the mercapto group is chosen from mercaptomethyl, 2-mercaptoethyl, 3-mercaptopropyl, 4-mercaptobutyl, or a combination of two or more thereof.

5. The curable composition of claim 1 , wherein the siloxane (b) is of the formula:
M 3 i M 4 j D 3 k D 4 l T 3 m T 4 n Q o   (2)

where the M-units are of the formula R 7 R 8 R 9 SiO 1/2 ; the D-units are of the formula R 10 R 11 SiO 2/2 ; the T-units have three Si—O bonds are of the formula R 12 SiO 3/2 ; the Q-units are of the formula SiO 4/2 ; R 7 -R 12 are independently chosen from hydrogen, a hydroxyl, a linear or branched alkyl group, an alcohol, a linear or branched alkoxy group, an aryl group, an alkylvinyl group, an amide, an amino group, an acryloyl group, a carbonyl groups, a silyloxy group, an isocyanyl group, a mercapto group, an epoxy-containing group, where one or more of R 7 -R 12 comprises an unsaturated group; i is from 0-1000, j is from 0-1000, k is from 0-500, l is from 0-100, m is from 0-100, n is from 0-100, and o is from 0 to 200, where at least two subscripts on any particular embodiment are positive integers.

6. The curable composition of claim 5 , wherein the unsaturated group comprises an alkenyl group of the formula CH 2 ═CH—R 13 x — where R 13 is a C1-C20 alkyl, a C1-C20 branched alkyl, a C1-C10 cyclic alkyl, or a C6-C10 aryl group.

7. The curable composition of claim 5 , wherein the unsaturated group is chosen from vinyl, allyl, styryl, butenyl, pentenyl, hexenyl, or a combination of two or more thereof.

8. The curable composition of claim 1 , wherein the photoinitiator is an acylphosphine compound.

9. The curable composition of claim 8 , wherein the acylphosphine compound is chosen from a mono-acylphosphine compound, a bis-acylphosphine compound, or a combination of two or more thereof.

10. The curable composition of claim 8 , wherein the acylphosphine compound is chosen from diphenyl(2,4,6-trimethylbenzoyl)phosphine oxide and bis(2,6-di-methoxybenzoyl)-2,4,4-trimethylpentylphosphine oxide.

11. The curable composition of claim 1 , wherein the hindered phenol is chosen from 2,6-di-t-butyl-p-cresol; 2-t-butyl-4-methoxyphenol; 3-t-butyl-4-methoxyphenol; 2,6-t-butyl-4-ethylphenol; 2,2′-methylene-bis(4-methyl-6-t-butylphenol); 4,4′-thiobis(3-methyl-6-t-butylphenol); 4,4′-butylidene-bis(3-methyl-6-t-butylphenol); 1,1,3-tris(2-methyl-4-hydroxy-5-t-butylphenyl)butane; 1,3,5-trimethyl-2,4,6-tris(3,5-di-t-butyl-4-hydroxybenzyl)benzene; tetrakis[methylene-3-(3′,5′-di-t-butyl-4′-hydroxyphenyl)propionate]methane; bis[3,3′-bis(4′-hydroxy-3-t-butylphenyl)butyric acid glycol ester; tocopherol; or a combination of two or more thereof.

12. The curable composition of claim 1 comprising the photoinitiator in an amount of from about 200 ppm to about 1500 ppm.

13. The curable composition of claim 1 comprising the hindered phenol in an amount of from about 200 ppm to about 2000 ppm.

14. A cured article formed from a curable composition comprising:
(a) a mercapto-functional siloxane comprising;
(b) a siloxane comprising an unsaturated hydrocarbon group;
(c) a photoinitiator; and
(d) an antioxidant compound comprising a hindered phenol; wherein (a) and (b) are provided such that the composition has a molar equivalent ratio of mercapto groups to unsaturated groups of about 2.5:1 to about 6:1.

15. The cured article of claim 14 , wherein the cured article has a refractive index of from about 1.41 to about 1.53.

16. The cured article of claim 15 , wherein the cured article has a yellowing index of from about 0 to about 10 after ageing for 350 hours.

17. The cured article of claim 15 , wherein the article has a transparency of about 85% or greater.

18. A method of forming a cured article comprising exposing a curable composition to UV light, visible light, or a combination of two or more thereof, the composition comprising: (a) a mercapto-functional siloxane; (b) a siloxane comprising an unsaturated hydrocarbon group; (c) a photoinitiator; and (d) an antioxidant compound comprising a hindered phenol, wherein (a) and (b) are provided such that the composition has a molar equivalent ratio of mercapto groups to unsaturated groups of about 2.5:1 to about 6:1.

19. The method of claim 18 further comprising heating the curable composition by exposing the composition to a temperature of from about 70° C. to about 150° C.

Assignees

• Srikanth Abirami
• Dukes Douglas M
• Momentive Performance Mat Inc

Inventors

• Srikanth Abirami
• Dukes Douglas M

Classifications

• C08G77/20

  containing silicon bound to unsaturated aliphatic groups · CPC title

• C08L83/04

  Polysiloxanes · CPC title

• C08K5/005

  Stabilisers against oxidation, heat, light, ozone · CPC title

• C08G77/28

  sulfur-containing groups · CPC title

• C08L83/08 Primary

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