Acyl germanium photoinitiators and process for the preparation thereof

Patent metadata

Field	Value
Publication number	US-10533025-B2
Application number	US-201615763959-A
Country	US
Kind code	B2
Filing date	Sep 26, 2016
Priority date	Sep 29, 2015
Publication date	Jan 14, 2020
Grant date	Jan 14, 2020

Abstract

Acyl germanium compound according to general formula [RmAr—(C═O)—]4—Ge and process for the preparation thereof. The compound is suitable as initiator for radical polymerization.

First claim

The invention claimed is:

1. Acyl germanium compound according to general formula (I),
[R m Ar—(C═O)—] 4 -Ge  (I)

in which the variables have the following meanings:
Ar a mono- or polycyclic hydrocarbon radical with 6 to 18 ring-carbon atoms, which can be substituted m times by the R group and which can contain one or more heteroatoms in the ring, wherein
m is an integer from 0 to 6 and cannot be greater than the number of substitutable hydrogen atoms in Ar,
R is halogen, NR 1 2 , OH, OSiR 2 3 , (C═O)R 3 , CN, NO 2 , CF 3 , COOR 4 , or a C 1 - to C 20 -alkyl, -alkenyl, -alkoxy or -alkenoxy radical, which can be linear, branched or cyclic, which can be interrupted by one or more O atoms and which can contain a radically polymerizable group, or ═O, wherein
R 1 -R 3 independently of each other are in each case H or a linear or branched C 1 - to C 12 -alkyl radical and
R 4 is H, a linear or branched C 1 - to C 12 -alkyl radical or SiR 5 3 , wherein
R 5 is a linear or branched C 1 - to C 10 -alkyl radical.

2. Acyl germanium compound according to claim 1 , in which the variables have the following meanings:
Ar an aromatic C 6 -C 10 radical, which can be substituted m times by R, wherein
m is an integer from 1 to 3 and
R is Cl, NR 1 2 , OSiR 2 3 , (C═O) R 3 , CN, NO 2 , CF 3 , COOR 4 , or a C 1 - to C 10 -alkyl, -alkenyl, -alkoxy or -alkenoxy radical, which can be linear, branched or cyclic, which can be interrupted by one or more O atoms, and which can contain a radically polymerizable group, wherein
R 1 -R 3 independently of each other are in each case H or a linear or branched C 1 - to C 8 -alkyl radical and
R 4 is H, a linear or branched C 1 - to C 8 -alkyl radical or SiR 10 3 and
R 5 is a linear or branched C 1 to C 5 alkyl radical.

3. Acyl germanium compound according to claim 1 , in which the variables have the following meanings:
Ar a phenyl radical, pyridyl radical, naphthyl radical, anthryl radical, anthraquinone-yl radical, which can be substituted m times by R, wherein
m is an integer from 1 to 3 and
R is NR 1 2 , CN, NO 2 , CF 3 , a C 1 - to C 3 -alkyl radical or C 1 - to C 3 -alkoxy radical, wherein
R 1 is H or a linear C 1 - to C 3 -alkyl radical.

4. Composition which, relative to its total mass contains 0.001 to 5 wt. % of an acyl germanium compound of Formula (I) according to claim 1 and at least one polymerizable binder.

5. Composition according to claim 4 which contains as polymerizable binder at least one radically polymerizable monomer and/or prepolymer.

6. Composition according to claim 5 , which contains as binder at least one mono- or multifunctional (meth)acrylate or a mixture thereof.

7. Composition according to claim 4 , which contains
0.001-5 wt. % acyl germanium compound of Formula (I),
10 to 99.9 wt.-% polymerizable binder,
0 to 85 wt.-% filler, relative in each case to the total mass of the composition.

8. Process of using an acyl germane according to Formula (I) as initiator for radical polymerization, wherein Formula (I) comprises
[R m Ar—(C═O)—] 4 -Ge  (I)

in which the variables have the following meanings:
Ar a mono- or polycyclic hydrocarbon radical with 6 to 18 ring-carbon atoms, which can be substituted m times by the R group and which can contain one or more heteroatoms in the ring, wherein
m is an integer from 0 to 6 and cannot be greater than the number of substitutable hydrogen atoms in Ar,
R is halogen, NR 1 2 , OH, OSiR 2 3 , (C═O)R 3 , CN, NO, CF 3 , COOR 4 , or a C 1 - to C 20 -alkyl, -alkenyl, -alkoxy or -alkenoxy radical, which can be linear, branched or cyclic, which can be interrupted by one or more O atoms and which can contain a radically polymerizable group, or ═O, wherein
R 1 -R 3 independently of each other are in each case H or a linear or branched C 1 - to C 12 -alkyl radical and
R 4 is H, a linear or branched C 1 - to C 12 -alkyl radical or SiR 5 3 , wherein
R 5 is a linear or branched C 1 - to C 10 -alkyl radical.

9. Acyl germanium compound according to claim 2 , wherein the radically polymerizable group comprises vinyl, methacrylate, (meth)acrylamide or N-alkylacrylamide, and wherein the radically polymerizable group in the case of non-cyclic radicals is terminal.

10. Acyl germanium compound according to claim 3 , wherein R is linear and can bear a terminal radically polymerizable group comprising vinyl, acrylate, methacrylate.

Assignees

• Ivoclar Vivadent Ag

Inventors

• Moszner Norbert
• Lamparth Iris
• Fischer Urs Karl
• Stüger Harald
• Haas Michael
• Demner Georg Gescheidt

Classifications

• C08F4/72

  selected from metals not provided for in group C08F4/44 (C08F4/54 - C08F4/70 take precedence) · CPC title

• A61K6/62

  Photochemical radical initiators · CPC title

• C07F7/30 Primary

  Germanium compounds · CPC title

• C08F2/50

  with sensitising agents · CPC title

• C08F222/1025

  of aromatic dialcohols · CPC title