Silicone-compatible photoinitiators

Patent metadata

Field	Value
Publication number	US-9409932-B2
Application number	US-201514729229-A
Country	US
Kind code	B2
Filing date	Jun 3, 2015
Priority date	Dec 5, 2012
Publication date	Aug 9, 2016
Grant date	Aug 9, 2016

Abstract

Compounds useful as a photoinitiator and/or photosensitizer represented by the following formula (I):

wherein
R 1 and R 2 each independently designates an alkyl group of 1 to 12 carbon atoms or a cycloalkyl group of 5 or 6 carbon atoms or R 1 and R 2 form together with the carbon atom to which they are attached a cycloaliphatic ring of 5 or 6 carbon atoms, Si* represents an organopolysiloxane residue bonded via a silicon atom of this residue to the oxygen shown in formula (I), or a silane group SiR 4 R 5 R 6 , wherein R 4 , R 5 and R 6 each independently designates an alkyl group of 1 to 12 carbon atoms, a cycloalkyl group of 5 or 6 carbon atoms or an aryl group of 6 to 10 carbon atoms, and R 3 designates a hydrogen atom or a group represented by the following formula (II)

wherein
R 7 and R 8 each independently designates an alkyl group of 1 to 12 carbon atoms or a cycloalkyl group of 5 or 6 carbon atoms or R 7 and R 8 form together with the carbon atom to which they are attached a cycloaliphatic ring of 5 or 6 carbon atoms, and Si** represents an organopolysiloxane residue bonded via a silicon atom of this residue to the oxygen shown in formula (II), or a silane group SiR 9 R 10 R 11 , wherein R 9 , R 10 and R 11 each independently designates an alkyl group of 1 to 12 carbon atoms, a cycloalkyl group of 5 or 6 carbon atoms or an aryl group of 6 to 10 carbon atoms.

First claim

What is claimed is:

1. A compound represented by the following formula (I):

wherein
R 1 and R 2 each independently designates an alkyl group of 1 to 12 carbon atoms or a cycloalkyl group of 5 or 6 carbon atoms or R 1 and R 2 form together with the carbon atom to which they are attached a cycloaliphatic ring of 5 or 6 carbon atoms,
Si* represents an organopolysiloxane residue bonded via a silicon atom of this residue to the oxygen shown in formula (I), or a silane group SiR 4 R 5 R 6 , wherein R 4 , R 5 and R 6 each independently designates a cycloalkyl group of 5 or 6 carbon atoms or an aryl group of 6 to 10 carbon atoms, and
R 3 designates a hydrogen atom or a group represented by the following formula (II)

wherein
R 7 and R 8 each independently designates an alkyl group of 1 to 12 carbon atoms or a cycloalkyl group of 5 or 6 carbon atoms or R 7 and R 8 form together with the carbon atom to which they are attached a cycloaliphatic ring of 5 or 6 carbon atoms, and
Si** represents an organopolysiloxane residue bonded via a silicon atom of this residue to the oxygen shown in formula (II), or a silane group SiR 9 R 10 R 11 , wherein R 9 , R 10 and R 11 each independently designates an alkyl group of 1 to 12 carbon atoms, a cycloalkyl group of 5 or 6 carbon atoms or an aryl group of 6 to 10 carbon atoms.

2. The compound according to claim 1 , wherein R 1 and R 2 each independently designates methyl, ethyl, n-propyl or isopropyl.

3. The compound according to claim 1 , wherein R 1 and R 2 form together with the carbon atom to which they are attached a cyclohexyl ring.

4. The compound according to claim wherein R 3 designates a hydrogen atom.

5. The compound according to claim 1 , wherein R 3 designates a group represented by formula (II), wherein R 7 and R 8 are identical to R 1 and R 2 .

6. The compound according to claim 1 , wherein R 3 designates a group represented by formula (II), wherein Si** is identical to Si*.

7. The compound according to claim 1 , wherein R 1 and R 2 each designates methyl and R 3 designates a hydrogen atom.

8. The compound according to claim 1 wherein R 1 and R 2 form together with the carbon atom to which they are attached a cyclohexyl ring and R 3 designates a hydrogen atom.

9. The compound according to claim 1 , wherein R 1 and R 2 each designates methyl and R 3 designates a group represented by formula (II), wherein R 7 and R 8 each designate methyl.

10. A method to produce a compound according to claim 1 , reacting at least one α-hydroxy ketone of formula (I′)

wherein
R 1 and R 2 each independently designates an alkyl group of 1 to 12 carbon atoms or a cycloalkyl group of 5 or 6 carbon atoms or R 1 and R 2 form together with the carbon atom to which they are attached a cycloaliphatic ring of 5 or 6 carbon atoms, and
R 3 designates a hydrogen atom or a group represented by the following formula (II′)

wherein
R 7 and R 8 each independently designates an alkyl group of 1 to 12 carbon atoms or a cycloalkyl group of 5 or 6 carbon atoms or R 7 and R 8 form together with the carbon atom to which they are attached a cycloaliphatic ring of 5 or 6 carbon atoms,
and at least one organopolysiloxane having at least one SiH group per molecule or at least one silane HSiR 4 R 5 R 6 , wherein R 4 , R 5 and R 6 each independently designates a cycloalkyl group of 5 or 6 carbon atoms or an aryl group of 6 to 10 carbon atoms, in the presence of a dehydrogenation catalyst.

11. The method according to claim 10 , wherein the α-hydroxy ketone of formula (I′) and the organopolysiloxane having at least one SiH group per molecule or the silane HSiR4R5R6 are reacted in respective amounts to provide a molar ratio of hydroxyl groups of the α-hydroxy ketone of formula (I′) to SiH groups of 0.8 to 1.2.

12. A method according to claim 10 , wherein the dehydrogenation catalyst is selected from tris(pentafluorobenzene)borane, zinc dust, and platinum catalysts.

13. A method according to claim 10 , wherein the reaction is carried out at a temperature of from 20 to 100° C.

14. A method of using the compound according to claim 1 as photoinitiator and/or photosensitizer, comprising addition of the compound to a photopolymerizable organopolysiloxane or silicone resin and exposure of the resulting mixture to electromagnetic radiation.

15. The compound according to claim 1 , wherein Si* represents a silane group SiR 4 R 5 R6, wherein R 4 , R 5 and R 6 each independently an aryl group selected from phenyl and benzyl.

16. A compound represented by the following formula (I):

wherein
R 1 and R 2 form together with the carbon atom to which they are attached a cyclohexyl ring;
Si* represents an organopolysiloxane residue bonded via a silicon atom of this residue to the oxygen shown in formula (I), or a silane group SiR 4 R 5 R 6 , wherein R 4 , R 5 and R 6 each independently designates ethyl, n-propyl or isopropyl; and
R 3 designates a hydrogen atom or a group represented by the following formula (II)

wherein
R 7 and R 8 form together with the carbon atom to which they are attached a cyclohexyl ring; and
Si** is identical to Si*.

17. The compound according to claim 16 , wherein R 3 designates a hydrogen atom.

Assignees

• Henkel Ag & Co Kgaa
• Henkel IP & Holding GmbH

Inventors

• Li Zhiming Pasing
• Zhang Yong
• Li Jinyou
• Lu Zhixiang
• Lu Zheng

Classifications

• C07F7/0838

  Compounds with one or more Si-O-Si sequences (compounds with a ring containing only alternating Si and O atoms, i.e. cyclosilanes C07F7/21) · CPC title

• C08G77/14 Primary

  containing silicon bound to oxygen-containing groups · CPC title

• C08G77/80

  Siloxanes having aromatic substituents, e.g. phenyl side groups · CPC title

• C08J3/28

  Treatment by wave energy or particle radiation · CPC title

• C08J2343/04

  Homopolymers or copolymers of monomers containing silicon · CPC title