Curable cage-type silicone copolymer and process for production thereof and curable resin composition comprising curable cage-type silicone copolymer and cured product thereof

A process for producing a cage-type curable silicone copolymer characterized by having a constituent unit represented by the following general formula (1):

• Y—[Z—(O1/2—R22SiO1/2)a—(R1SiO3/2)n—(O1/2)b]m—Z—Y (1)
• wherein R1 and R2 each is a vinyl group, an alkyl group, a phenyl group, a (meth)acryloyl group, an allyl group, or an oxirane ring-containing group;
• the substituents selected for R1 and R2 may be identical with or different from one another and at least one of the substituents selected for R1 contained in a molecule is a vinyl group, a (meth)acryloyl group, an allyl group, or an oxirane ring-containing group;
• a and b each is a number of 0-3 and satisfies the relationship 1≦a+b≦4 and n denotes a number of 8-14;
• in the case where n is an odd number, a and b are a combination of an even number and an odd number including 0;
• in the case where n is an even number, a and b are a combination of even numbers including 0;
• m denotes a number of 1-2,000;
• Z is a divalent group represented by the following general formula (2)
• wherein R3 is a hydrogen atom, a vinyl group, an alkyl group, a phenyl group, a (meth)acryloyl group, an allyl group, or an oxirane ring-containing group, the substituents selected for R3 may be identical with or different from one another, and p denotes a number of 0-30;
• and Y is a monovalent group selected from the following general formulas (3) to (6)
• [(R4O)R22SiO1/2]a—[R1SiO3/2]n—[O1/2]— (3)
• [R4O1/2]b—[R1SiO3/2]n—[O1/2—R22SiO1/2]— (4)
• (R4O1/2)— (5)
• (R23SiO1/2)— (6)
• wherein R1 and R2 each is a vinyl group, an alkyl group, a phenyl group, a (meth)acryloyl group, an allyl group, or an oxirane ring-containing group;
• the substituents selected for R1 or R2 may be identical with or different from one another;
• R4 is selected from a hydrogen atom, a methyl group, and an ethyl group;
• a and b each is a number of 0-3 and n denotes a number of 8-14;
• in the case where n is an odd number, a and b each is independently 0 or 2;
• in the case where n is an even number, a and b each is independently 1 or 3:
• the said process comprising condensing a cage-type siloxane compound containing an alkoxyl group or silanol group represented by the following general formula (7)
• [(R4O)R22SiO1/2]a—[R1SiO3/2]n—[O1/2R4]b (7)
• wherein R1 and R2 each is selected from a vinyl group, an alkyl group, a phenyl group, a (meth)acryloyl group, an allyl group, and an oxirane ring-containing group;
• R4 is selected from a hydrogen atom, a methyl group, and an ethyl group;
• the substituents selected for R1, R2, or R4 may be identical with or different from one another and at least one of the substituents selected for R1 contained in a molecule is a vinyl group, a (meth)acryloyl group, an allyl group, or an oxirane ring-containing group;
• a and b each is a number of 0-3 and satisfies the relationship 1≦a+b≦4;
• further, n is an integer of 8-14;
• in the case where n is an odd number, a and b are a combination of an even number and an odd number including 0;
• in the case where n is an even number, a and b are a combination of even numbers including 0 with a compound represented by the following compound (8)
• wherein R3 is a hydrogen atom, a vinyl group, an alkyl group, a phenyl group, a (meth)acryloyl group, an allyl group, or an oxirane ring-containing group;
• the substituents selected for R3 may be identical with or different from one another;
• X is a hydroxyl group, a hydrogen atom, a chlorine atom, or an alkoxyl group;
• the substituents selected for X may be identical with or different from one another;
• further, p denotes a number of 0-30, and then condensing the said condensation reaction product with a compound represented by the following general formula (9)
• R23Si—X (9)
• wherein R2 is a hydrogen atom, a vinyl group, an alkyl group, a phenyl group, a (meth)acryloyl group, an allyl group, or an oxirane ring-containing group, the substituents selected for R2 may be identical with or different from one another, and X is a hydroxyl group, a hydrogen atom, a chlorine atom, or an alkoxyl group,
• wherein the process further comprises mixing a cage-type siloxane compound represented by the following general formula (19)
• [R1SiO3/2]n (19)
• wherein R1 is selected from a vinyl group, an alkyl group, a phenyl group, a (meth)acryloyl group, an allyl group, and an oxirane ring-containing group, the substituents selected for R1 may be identical with or different from one another, and n is an integer of 8-14;
• with a dialkoxysilane represented by the following general formula (20)
• R22Si(OR5)2 (20)
• wherein R2 is selected from a vinyl group, an alkyl group, a phenyl group, a (meth)acryloyl group, an allyl group, and an oxirane ring-containing group, R5 is selected from a methyl group and an ethyl group, and the substituents selected for R2 or R5 may be identical with or different from one another;
• at a molar ratio [R1SiO3/2]n:
• R22Si(OR5)2 in the range of 1:0.5 to 1:2, and subjecting the mixture to addition reaction in a non-polar solvent in the presence of a basic catalyst to yield a cage-type siloxane compound containing an alkoxyl group represented by general formula (7).