Granted Patent B2

US 9,035,009 · App. 13/770,089 · Granted May 19, 2015

Inventors: Takao Manabe (Osaka, JP); Makoto Seino (Osaka, JP); Shinya Mizuta (Osaka, JP)

Assignee: KANEKA CORPORATION

C07F7/21C08F230/08C08G77/04C08G77/045C08G77/12C08G77/14C08G77/20C08G77/50C08K5/56C09D183/04

Abstract

Claims (71)

1. A modified polyhedral polysiloxane,

which is obtained by modifying a polyhedral polysiloxane compound (a) having an alkenyl group with a cyclic siloxane compound (b) having a hydrosilyl group capable of hydrosilylation with the compound (a),

wherein the modified polyhedral polysiloxane is obtained by:

adding the cyclic siloxane compound (b) to the polyhedral polysiloxane compound (a) to allow the compound (a) to be modified by the compound (b), wherein the number of a hydrogen atom directly bonded to a Si atom of the compound (b) is 2.5 to 20 per alkenyl group of the compound (a); and

distilling off an unreacted portion of the compound (b), and

wherein the modified polyhedral polysiloxane is in a liquid state at 20° C.

2. The modified polyhedral polysiloxane according to claim 1 ,

wherein a molecule of the modified polyhedral polysiloxane contains at least three hydrosilyl groups.

3. The modified polyhedral polysiloxane according to claim 1 ,

wherein the cyclic siloxane compound (b) further has a reactive functional group other than a hydrosilyl group.

4. The modified polyhedral polysiloxane according to claim 1 , comprising a siloxane unit represented by the formula:

[XR 1 2 SiO—SiO 3/2 ] a [HO—SiO 3/2 ] b [R 2 3 SiO—SiO 3/2 ] c

wherein

a+b+c is an integer of 6 to 24, a is an integer of 1 or more, and b and c are each 0 or an integer of 1 or more;

X is a reactive functional group-containing group;

R 1 is an alkyl group or an aryl group; and

R 2 is an alkyl group, an aryl group, an alkenyl group, a hydrogen atom, or a group bonded to another polyhedral polysiloxane.

5. The modified polyhedral polysiloxane according to claim 4 ,

wherein b is an integer of 1 or more.

6. The modified polyhedral polysiloxane according to claim 4 ,

wherein the reactive functional group-containing group X has at least one functional group selected from the group consisting of an epoxy group, a hydrolyzable silyl group, an oxetanyl group, a (meth)acryloyl group, and a thiol group.

7. The modified polyhedral polysiloxane according to claim 6 ,

wherein the reactive functional group-containing group X has at least one functional group selected from the group consisting of an epoxy group, a hydrolyzable silyl group, and an oxetanyl group.

8. The modified polyhedral polysiloxane according to claim 6 ,

wherein the hydrolyzable silyl group is an alkoxysilyl group.

9. The modified polyhedral polysiloxane according to claim 6 ,

wherein the reactive functional group-containing group X is an alkoxysilylethyl group.

10. The modified polyhedral polysiloxane according to claim 1 ,

wherein the modified polyhedral polysiloxane is soluble in an alkaline aqueous solution.

11. The modified polyhedral polysiloxane according to claim 5 , which is produced by a process comprising:

synthesizing a polyhedral polysiloxane intermediate containing a siloxane unit having a dialkylsilyl group represented by the formula:

[XR 1 2 SiO—SiO 3/2 ] a [HR 1 2 SiO—SiO 3/2 ] b [R 2 3 SiO—SiO 3/2 ] c ; and

treating the polyhedral polysiloxane intermediate with a polar solvent to eliminate the dialkylsilyl group, which results in generation of a silanol group.

12. The modified polyhedral polysiloxane according to claim 4 ,

wherein at least one X contains a constitutional unit represented by the formula (2):

wherein

l is an integer of 2 or more;

n is an integer of 2 or more;

Z is a hydrogen atom, an alkenyl group, an aryl group, or a moiety bonded to a polyhedral polysiloxane via an alkylene chain, and the Zs may be the same as or different from each other, provided that at least one of the Zs is a hydrogen atom; and

R is an alkyl group or an aryl group,

wherein in the case where there are a plurality of Xs, the structures of the formula (2) may be different from each other.

13. The modified polyhedral polysiloxane according to claim 1 , which is obtained by:

adding an excessive amount of the cyclic siloxane compound (b) to the polyhedral polysiloxane compound (a) to allow the compound (a) to be modified with the compound (b) by a hydrosilylation reaction, wherein the number of a hydrogen atom directly bonded to a Si atom is 2.5 to 20 per one alkenyl group; and

distilling off an unreacted portion of the cyclic siloxane compound (b),

the polyhedral polysiloxane compound (a) containing a siloxane unit represented by the formula:

[AR 1 2 SiO—SiO 3/2 ] a [R 4 3 SiO—SiO 3/2 ] b

wherein

a+b is an integer of 6 to 24, a is an integer of 1 or more, and b is 0 or an integer of 1 or more;

As are alkenyl group(s) and/or hydrogen atom(s), provided that at least one of the As is an alkenyl group;

R 1 is an alkyl group or an aryl group; and

R 4 is a substituent group other than an alkenyl group and a hydrogen atom.

14. A polysiloxane composition, comprising:

the modified polyhedral polysiloxane according to claim 1 ; and

a curing initiator.

15. A polysiloxane composition, comprising:

the modified polyhedral polysiloxane according to claim 1 ; and

a curing agent.

16. The polysiloxane composition according to claim 14 , further comprising

a hydrosilylation catalyst.

17. The polysiloxane composition according to claim 14 , further comprising

a curing retardant.

18. The polysiloxane composition according to claim 14 , further comprising

an adhesion promoter.

19. The polysiloxane composition according to claim 15 ,

wherein the curing agent comprises an alkenyl group-containing polysiloxane with a molecular weight less than 3000 and an alkenyl group-containing polysiloxane with a molecular weight of 5000 or more.

20. A cured product, which is obtained by curing the polysiloxane composition according to claim 14 .

21. A cured product, which is obtained by curing the polysiloxane composition according to claim 15 .

22. The modified polyhedral polysiloxane according to claim 13 ,

wherein R 4 is a substituent group selected from the group consisting of an alkyl group, an aryl group and a group bonded to another polyhedral polysiloxane or siloxane compound.

23. The modified polyhedral polysiloxane according to claim 1 ,

wherein the polyhedral polysiloxane compound (a) contains at most eight alkenyl groups.

Priority Claims (10)

Continuity (2)