Vulcanizable organopolysiloxane composition

• US 5,371,116 A
• Filed: 07/13/1993
• Issued: 12/06/1994
• Est. Priority Date: 07/14/1992
• Status: Expired due to Term

• Current Assignee: Shin-Etsu Chemical Company Limited
• Original Assignee: Shin-Etsu Chemical Company Limited
• Inventors: Arai, Masatoshi, Miyoshi, Kei, Sakamoto, Takafumi
• Primary Examiner(s): Marquis, Melvyn I.
• Application Number:
  US08/090,374
• Time in Patent Office: 511 Days
• Field of Search: 528/18, 528/17, 528/41, 522/33, 522/35, 522/41, 522/43, 522/44, 522/46, 522/48, 522/47, 522/65, 522/68, 522/63, 522/70, 522/148, 522/172
• US Class Current: 522/33
• CPC Class Codes: C08G 77/16 to hydroxyl groups
• CPC Class Codes: C08K 5/5419 containing at least one Si—C bond
• CPC Class Codes: C08K 5/5425 containing at least one C=C bond
• CPC Class Codes: C08K 5/57 Organo-tin compounds
• CPC Class Codes: C08L 2666/44 Silicon-containing compounds
• CPC Class Codes: C08L 83/04 Polysiloxanes

Abstract

Vulcanizable organopolysiloxane compositions comprise a hydroxy-terminated organopolysiloxane, an acrylic or methacryllc functional alkoxy silane, a divalent tin compound, an alkoxy-α-silyl ester, a photopolymerization initiator, and a curing catalyst whereby the composition is cured by UV irradiation and/or by the action of moisture in air. The composition has good shelf stability and can yield rubber elastomers having good physical properties.

Claims

1. A vulcanizable organopolysiloxane composition which comprises:

(A) a hydroxy-terminated organopolysiloxane of the following general formula (1) ##STR12## wherein each R¹ independently represents an unsubstituted or substituted monovalent organic group, and n is an integer of from 1 to 10,000;

(B) an acrylic or methacrylic functional alkoxysilane of the following general formula (27) ##STR13## wherein R² represents a hydrogen atom or a methyl group, R³ represents an unsubstituted or substituted divalent organic group, R⁴ and R⁵ independently represent an unsubstituted or substituted monovalent organic group, and a is a value of 0, 1 or 2;

(C) a divalent tin compound of the following general formula (3)

space="preserve" listing-type="equation">SnX.sub.2 (

     3)

wherein each X independently E represents a halogen atom, an OR⁶ or an ##STR14## group in which R⁶ and R⁷ independently represent an unsubstituted or substituted monovalent organic group;

(D) an alkoxy-α

-silyl ester of the following general formula (4) ##STR15## wherein R⁸ and R⁹ independently represent a methyl group or an ethyl group, R¹⁰ and R¹¹ independently represent a hydrogen atom or an unsubstituted or substituted monovalent organic group, R¹² represents an unsubstituted or substituted monovalent organic group, and b is a value of 0, 1 or 2;

(E) an effective amount of a photopolymerization initiator for photopolymerization of said alkoxysilane (B), said photopolymerization initiator being selected from the group consisting of acetophenone, propiophenone, benzophenone, xanthol, fluorene, benzaldehyde, anthraquinone, triphenylamine, 4-methylacetophenone, 3-pentylacetophenone, 4-methoxyacetophenone, 3-bromoacetophenone, 4-allylacetophenone, p-diacetylbenzene, 3-methoxybenzophenone, 4-methylbenzophenone, 4-chlorobenzophenone, 4,4-dimethoxybenzophenone, 4-chloro-4-benzylbenzophenone, 3-chloroxanthone, 3,9-dichloroxanthone, 3-chloro-8-nonylxanthone, benzoin, benzoin methyl ether, benzoin butyl ether, bis(4-dimethylaminophenyl)ketone, benzyl methoxyketal, 2-chloroxanthone, diethylacetophenone, 1-hydroxycyclohexyl phenyl ketone, 2-methyl[4-(methylthio)phenyl]2-morpholino-1-1-propanone, 2,2-dimethoxy-2-phenylacetophenone, and diethoxyacetophenone; and

(F) an effective amount of a catalyst for vulcanization of said alkoxysilane (B) and said alkoxy-α

-ester (D) whereby the composition is vulcanizable by the action of moisture in air at room temperature and/or by application of UV light, said catalyst for vulcanization being selected from the group consisting of dibutyltin diacetate, dibutyltin dioctoate, dibutyltin dilaurate, dibutyltin dioleate, diphenyltin diacetate, dibutyltin dioxide, dibutyltin dimethoxide, dibutylbis(triethoxysiloxy)tin, dibutyltinbenzyl maleate, tetraisopropoxy, titanium, tetra-n-butoxy titantium, tetrabis (2-ethylhexoxy) titanium, dipropoxybis (acetylacetona) titanium and titanium isopropoxyoctylene glycol.

2. A vulcanizable organopolysiloxane composition according to claim 1, wherein each R¹ independently represents an unsubstituted or substituted monovalent hydrocarbon group having from 1 to 10 carbon atoms.

3. A vulcanizable organopolysiloxane composition according to claim 1, wherein said organopolysiloxane has viscosity of not smaller than 25 centipoises at 25°

C.

4. A vulcanizable organopolysiloxane composition according to claim 1, wherein R³ is a divalent hydrocarbon group having from 1 to 10 carbon atoms and R⁴ and R⁵ independently represent a monovalent hydrocarbon group having from 1 to 10 carbon atoms.

5. A vulcanizable organopolysiloxane composition according to claim 1, wherein X of the ingredient (C) is a halogen atom.

6. A vulcanizable organopolysiloxane composition according to claim 1, wherein X of the ingredient (C) is a group of OR⁶ or OCOR⁷ wherein R⁶ and R⁷, respectively, represent an unsubstituted or substituted monovalent hydrocarbon group having from 1 to 15 carbon atoms.

7. A vulcanizable organopolysiloxane composition according to claim 1, wherein R¹⁰ and R¹ 1 of the ingredient (D), respectively, represent an unsubstituted or substituted monovalent hydrocarbon group having from 1 to 10 carbon atoms.

8. A vulcanizable organopolysiloxane composition according to claim 1, wherein said composition comprises 100 parts by weight of said hydroxy-terminated organopolysiloxane, from 0.1 to 10 parts by weight of said acrylic or methacrylic functional alkoxysilane, from 0.01 to 5 parts by weight of said divalent tin compound, from 0.1 to 10 parts by weight of said alkoxy-α

-silyl ester, from 0.01 to 10 parts by weight of said photopolymerization initiator, and from 0.01 to 10 parts by weight of said catalyst for vulcanization.

9. A vulcanized product obtained from the composition of claim 1.

10. A vulcanizable organopolysiloxane composition which comprises:

(A) a hydroxy-terminated organopolysiloxane of the following general formula (1) ##STR16## wherein each R¹ independently represents an unsubstituted or substituted monovalent organic group, and n is an integer of from to 10,000;

(B) an acrylic or methacrylic functional alkoxysilane of the following general formula (2) ##STR17## wherein R² represents a hydrogen atom or a methyl group, R³ represents an unsubstituted or substituted divalent organic group, R⁴ and R⁵ independently represent an unsubstituted or substituted monovalent organic group, and a is a value of 0, 1 or 2;

(C) a divalent tin compound of the following general formula (3)

space="preserve" listing-type="equation">SnX.sub.2 (

     3)

wherein each X independently represents a halogen atom, an OR⁶ or an ##STR18## group in which R⁶ and R⁷ independently represent an unsubstituted or substituted monovalent organic group;

(D) an alkoxy-α

-silyl ester of the following general formula (4) ##STR19## wherein R⁸ and R⁹ independently represent a methyl group or an ethyl group, R¹⁰ and R¹¹ independently represent a hydrogen atom or an unsubstituted or substituted monovalent organic group, R¹² represents an unsubstituted or substituted monovalent organic group, and b is a value of 0, 1 or 2;

(E) an effective amount of a photopolymerization initiator for photopolymerization of said alkoxysilane (B); and

(F) an effective amount of a catalyst for vulcanization of said alkoxysilane (B) and said alkoxy-α

-ester (D) whereby the composition is vulcanizable by the action of moisture in air at room temperature and/or by application of UV light, said catalyst for vulcanization being selected from the group consisting of dibutyltin diacetate, dibutyltin dioctoate, dibutyltin dilaurate, dibutyltin dioleate, diphenyltin diacetate, dibutyltin dioxide, dibutyltin dimethoxide, dibutylbis(triethoxysiloxy) tin, dibutyltinbenzyl maleate, tetraisopropoxy titanium, tetra-n-butoxy titantium, tetrabis (2-ethylhexoxy) titanium, dipropoxybis (acetylacetona) titanium and titanium isopropoxyoctylene glycol.