Process for production of cyclic polyorganosiloxane, curing agent, curable composition, and cured product of the curable composition
View Patent ↗An object of the invention is to provide a curing agent and a curable composition capable of forming a cured product, which is applicable for optical material and which has excellent heat and light transparency and crack resistance, and a cured product obtained by curing the same. Moreover, an object of the invention is to provide a method for producing with use of the components of the curing agent a cyclic polyorganosiloxane having a specific structure, in a selective manner and in high yield. In order to attain the objects, a curable composition including, as essential components, (A) an organic compound including at least two carbon-carbon double bonds that are reactive with a SiH group, (B) a compound having at least two SiH groups per molecule, and (C) a hydrosilylation catalyst, uses a modified polyorganosiloxane compound having at least two SiH groups per molecule as the compound having at least two SiH groups, which modified polyorganosiloxane compound is a reaction product of a specific cyclic polyorganosiloxane.
1. A method for producing a cyclic polyorganosiloxane comprising:
decomposing a polyorganosiloxane by heating the polyorganosiloxane in the presence of a catalyst, the polyorganosiloxane having a main chain skeleton represented by the following general formula (I):
wherein R 1 to R 3 are identical or different monovalent substituted or unsubstituted hydrocarbon groups; and m and n satisfy:
0.3 ≦n /( m+n )<0.9.
2. The method for producing the cyclic polyorganosiloxane according to claim 1 , wherein:
the polyorganosiloxane is a chain polyorganosiloxane represented by the following general formula (II):
wherein R 1 to R 3 are identical or different monovalent substituted or unsubstituted hydrocarbon groups, R 4 is a monovalent substituted or unsubstituted hydrocarbon group, R 5 is a hydroxyl group or a monovalent substituted or unsubstituted hydrocarbon group, and R 6 is a hydrogen atom or a monovalent substituted or unsubstituted hydrocarbon group; m is 1 to 1000, n is 2 to 1000, m and n satisfy:
4 <m+n< 2000,
and/or, is a cyclic polyorganosiloxane represented by the following general formula (III):
wherein R 1 to R 3 are identical or different monovalent substituted or unsubstituted hydrocarbon groups; m is 1 to 1000, n is 2 to 1000, m and n satisfy:
4 <m+n< 2000.
3. The method for producing the cyclic polyorganosiloxane according to claim 1 , wherein:
the R 1 to R 3 in the general formulae (I) to (III) are a methyl group.
4. The method for producing the cyclic polyorganosiloxane according to claim 1 , wherein:
the catalyst has a metal-oxygen bond, and the metal is at least one selected from the group consisting of: aluminum, titanium, zirconium, tin, and zinc.
5. A cyclic polyorganosiloxane obtained by a method recited in claim 1 having the following general formula (IV):
wherein R 1 to R 3 are identical or different monovalent substituted or unsubstituted hydrocarbon groups; p is an integer of 1 to 8, q is an integer of 2 to 6, p and q being integers that satisfy:
3≦ p+q≦ 10.
6. The cyclic polyorganosiloxane according to claim 5 , comprising the following compounds (β1) and (β2):
7. A modified polyorganosiloxane compound having at least two SiH groups per molecule, the modified polyorganosiloxane compound being a hydrosilylation reaction product of the following compounds:
(α) an organic compound having two to six carbon-carbon double bonds per molecule, the carbon-carbon double bonds being reactive with an SiH group, and
(β) a cyclic polyorganosiloxane recited in claim 5 .
8. A modified polyorganosiloxane compound having at least two SiH groups per molecule, the modified polyorganosiloxane compound being a hydrosilylation reaction product of the following compounds:
(α) an organic compound having two to six carbon-carbon double bonds per molecule, the carbon-carbon double bonds being reactive with an SiH group, and
(β) a cyclic polyorganosiloxane including the following compounds (β1) and (β2):
9. The modified polyorganosiloxane compound according to claim 7 , wherein:
the (β) cyclic polyorganosiloxane includes the compounds (β1) and (β2) by at least 50 wt % with respect to the total weight of the (β) cyclic polyorganosiloxane.
10. The modified polyorganosiloxane compound according to claim 7 , wherein:
the (α) organic compound is at least one cyclic organic compound selected from the group consisting of: an aromatic compound, an aliphatic cyclic compound, a substituted aliphatic cyclic compound, and a heterocyclic compound.
11. The modified polyorganosiloxane compound according to claim 10 , wherein:
the aromatic compound is divinylbenzene, divinylnaphthalene, divinylbiphenyl, bisphenol-A diallyl ether or bisphenol-S diallyl ether, the aliphatic cyclic compound is cyclopentadiene, cyclohexadiene, cyclooctadiene, dicyclopentadiene, tricyclopentadiene or norbornadiene, the substituted aliphatic cyclic organic compound is vinylcyclopentene, vinylcyclohexene, trivinylcyclohexane, 1,3-bis(allyloxy)adamantane or 1,3,5-tris(allyloxy)adamantane.
12. The modified polyorganosiloxane compound according to claim 7 , wherein:
the (α) organic compound includes a compound represented by the following general formula (VI):
wherein R 7 is a hydrogen atom or a monovalent organic group having a carbon number of 1 to 50, and at least two R 7 groups contain a carbon-carbon double bond, the carbon-carbon double bond being reactive with a SiH group.
13. The modified polyorganosiloxane compound according to claim 7 , wherein:
the (α) organic compound includes at least one type thereof selected from the group consisting of: triallyl isocyanurate, monoglycidyl diallyl isocyanurate, and diallyl isocyanurate.
14. A curable composition comprising:
(A) an organic compound having at least two carbon-carbon double bonds per molecule, the carbon-carbon double bond being reactive with a SiH group;
(B) a modified polyorganosiloxane compound; and
(C) a hydrosilylation catalyst, wherein:
the (B) modified polyorganosiloxane compound having at least two SiH groups per molecule and being a hydrosilylation reaction product of the following compounds (α) and (β):
(α) an organic compound having two to six carbon-carbon double bonds per molecule, the carbon-carbon double bonds being reactive with an SiH group, and
(β) a cyclic polyorganosiloxane comprising the following general formula (IV):
wherein R 1 to R 3 are identical or different monovalent substituted or unsubstituted hydrocarbon groups; p is an integer of 1 to 8, q is an integer of 2 to 6, p and q being integers that satisfy:
3≦ p+q≦ 10;
the cyclic polyorganosiloxane produced by a method comprising:
decomposing a polyorganosiloxane by heating the polyorganosiloxane in the presence of a catalyst, the polyorganosiloxane having a main chain skeleton represented by the following general formula (I):
wherein R 1 to R 3 are identical or different monovalent substituted or unsubstituted hydrocarbon groups; m and n satisfy:
0.3 ≦n /( m+n )<0.9.
15. The curable composition according to claim 14 , wherein:
the (A) organic compound is at least one cyclic organic compound selected from the group consisting of: an aromatic compound, an aliphatic cyclic compound, a substituted aliphatic cyclic compound, and a heterocyclic compound.
16. The curable composition according to claim 15 , wherein:
the aromatic compound is divinylbenzene, divinylnaphthalene, divinylbiphenyl, bisphenol-A diallyl ether or bisphenol-S diallyl ether; the aliphatic cyclic compound is cyclopentadiene, cyclohexadiene, cyclooctadiene, dicyclopentadiene, tricyclopentadiene or norbornadiene; and the substituted aliphatic cyclic organic compound is vinylcyclopentene, vinylcyclohexene, trivinylcyclohexane, 1,3-bis(allyloxy)adamantane or 1,3,5-tris(allyloxy)adamantane.
17. The curable composition according to claim 14 , wherein:
the (A) organic compound includes a compound represented by the following general formula (VI):
wherein R 7 is a hydrogen atom or a monovalent organic group having a carbon number of 1 to 50, a plurality of R 7 being different or identical to each other, and at least two R 7 groups contain a carbon-carbon double bond, the carbon-carbon double bond being reactive with a SiH group.
18. A cured product produced by curing a curable composition recited in claim 14 .
19. The curable composition according to claim 14 , wherein:
the polyorganosiloxane is a chain polyorganosiloxane represented by the following general formula (II):
wherein R 1 to R 3 are identical or different monovalent substituted or unsubstituted hydrocarbon groups, R 4 is a monovalent substituted or unsubstituted hydrocarbon group, R 5 is a hydroxyl group or a monovalent substituted or unsubstituted hydrocarbon group, and R 6 is a hydrogen atom or a monovalent substituted or unsubstituted hydrocarbon group; m is 1 to 1000, n is 2 to 1000, m and n satisfy:
4 <m+n< 2000,
and/or, is a cyclic polyorganosiloxane represented by the following general formula (III):
wherein R 1 to R 3 are identical or different monovalent substituted or unsubstituted hydrocarbon groups; m is 1 to 1000, n is 2 to 1000, m and n satisfy:
4 <m+n< 2000.
20. The curable composition according to claim 19 , wherein:
R 1 to R 3 in the general formulae (I) to (III) are a methyl group.
21. The curable composition according to claim 14 , wherein:
the catalyst has a metal-oxygen bond, and the metal is at least one selected from the group consisting of: aluminum, titanium, zirconium, tin, and zinc.
22. The curable composition according to claim 14 , comprising the following compounds (β1) and (β2):
23. The curable composition according to claim 14 , wherein:
the modified polyorganosiloxane compound having at least two SiH groups per molecule and being a hydrosilylation reaction product of the following compounds:
(α) an organic compound having two to six carbon-carbon double bonds per molecule, the carbon-carbon double bonds being reactive with an SiH group, and
(β) a cyclic polyorganosiloxane including the following compounds (β1) and (β2):
24. The curable composition according to claim 23 , wherein:
the (β) cyclic polyorganosiloxane includes the compounds (β1) and (β2) by at least 50 wt % with respect to the total weight of the (β) cyclic polyorganosiloxane.
25. The curable composition according to claim 14 , wherein:
the (α) organic compound is at least one cyclic organic compound selected from the group consisting of: an aromatic compound, an aliphatic cyclic compound, a substituted aliphatic cyclic compound, and a heterocyclic compound.
26. The curable composition according to claim 25 , wherein:
the aromatic compound is divinylbenzene, divinylnaphthalene, divinylbiphenyl, bisphenol-A diallyl ether or bisphenol-S diallyl ether; the aliphatic cyclic compound is cyclopentadiene, cyclohexadiene, cyclooctadiene, dicyclopentadiene, tricyclopentadiene or norbornadiene; and the substituted aliphatic cyclic organic compound is vinylcyclopentene, vinylcyclohexene, trivinylcyclohexane, 1,3-bis(allyloxy)adamantane or 1,3,5-tris(allyloxy)adamantane.
27. The curable composition according to claim 14 , wherein:
the (α) organic compound includes a compound represented by the following general formula (VI):
wherein R 7 is a hydrogen atom or a monovalent organic group having a carbon number of 1 to 50, a plurality of R 7 being different or identical to each other, and at least two R 7 groups contain a carbon-carbon double bond, the carbon-carbon double bond being reactive with a SiH group.
28. The curable composition according to claim 14 , wherein:
the (α) organic compound includes at least one type thereof selected from the group consisting of: triallyl isocyanurate, monoglycidyl diallyl isocyanurate, and diallyl isocyanurate.