Polymer-bound bisacylphosphine oxides

1. An oligomer or polymer substituted by one or more bisacylphosphine oxide moieties, wherein the bisacylphosphine oxide moieties are linked via the phosphorous atom, optionally via a spacer group, to the oligomer or polymer backbone, which oligomer or polymer comprises units of formula (Ia),

where

m is an integer equal or greater than 2;

y and z independently of each other are an integer 0-15000;

A is

wherein the asterisk denotes the bond to X;

B 1 and B 2 independently of each other are

wherein A, B 1 and B 2 are incorporated into the same polymer backbone via random or block polymerization;

X is a direct bond, C 1 -C 10 -alkylene, —(CH 2 ) o —NH—CO—O—(CH 2 ) p —*,

—(CH 2 ) o —NH—CO—O—CH 2 —CHOH—CH 2 —*, —(CH 2 ) o —NH—CO—NH—(CH 2 ) p —*,

—(CH 2 ) o —NH—CO—S—(CH 2 ) p —*, —(CH 2 ) o —O—CO—CHR 3 —CH 2 —NH—(CH 2 ) p —*, *—(CH 2 ) o —O—CO—CHR 3 —CH 2 —NH—(CH 2 ) p —, —(CH 2 ) o —CO—O—(CH 2 ) p —*,

—(CH 2 ) o —O—CO—CHR 3 —CH 2 —S—(CH 2 ) p —*,

*—(CH 2 ) o —O—CO—CHR 3 —CH 2 —S—(CH 2 ) p —

—(CH 2 ) o —O—CO—CH(COCH 3 )—CH 2 —C(COOR 3 )CH 2 —*,

—(CH 2 ) o —NH—CH 2 —CH 2 —C(COOR 3 )CH 2 —*,

—(CH 2 ) o —S—(CH 2 ) o —C(COOR 3 )CH 2 —*,

—(CH 2 ) o —O—CO—CH(COCH 3 )—CH 2 —CHR 3 —CO—O—(CH 2 —CH 2 —O) t (CO)CH 2 —*,

—(CH 2 ) o —NH—CH 2 —CHR 3 —CO—O—(CH 2 —CH 2 —O) t (CO)CH 2 —*,

—(CH) o —S—CH 2 —CHR 3 —CO—O—CH 2 —CH 2 —*,

—(CH 2 ) o —S—CH 2 —CHR 3 —CO—O—(CH 2 —CH 2 —O) t (CO)CH 2 —*,

—(CH 2 ) o —NH—CH 2 —CHR 3 —CO—O—CH 2 —CH 2 —*,

—(CH 2 ) o —O—CO—CH(COCH 3 )—CH 2 —CHR 3 —CO—O—CH 2 —CH 2 —*, —(CH 2 ) o —CO—O—CH 2 —CHOH—CH 2 —*,

—(CH 2 ) o —O(CO)—CH 2 —*, —(CH 2 CH 2 O) t —(CO)—CH 2 —*, —(CH 2 ) o —CHOH—CH 2 —O(CO)—CH 2 —* or

wherein the asterisk denotes the bond to the bisacylphosphine oxide moiety;

o, p and q independently of each other are an integer 1-4;

r is an integer 0-2;

s is 0 or 1;

t is an integer 1 or 2;

R 1 is C 1 -C 4 -alkyl, C 1 -C 4 -alkoxy or Cl; and

R 2 is hydrogen, C 1 -C 4 -alkyl, C 1 -C 4 -alkoxy or Cl;

R 3 is hydrogen or methyl;

R 4 is C 1 -C 4 alkyl;

R 5 is methyl, phenyl or ethoxy;

R 6 is C 1 -C 10 alkyl or C 1 -C 9 perfluoroalkyl;

R 7 is C 1 -C 10 alkyl, —CH 2 —O—C 1 -C 10 alkyl, —CH 2 —O—(CH 2 ) o —C 5 -C 8 cycloalkyl,

—CH 2 —O—(CH 2 ) o —C 6 -C 10 aryl, C 1 -C 9 perfluoroalkyl, —CH 2 —O—C 1 -C 10 perfluoroalkyl,

—CH 2 —O—C 6 -C 10 aryl which is unsubstituted or substituted by C 1 -C 4 alkyl, C 1 -C 4 alkoxy or by Cl;

R 8 is hydrogen, C 1 -C 8 alkyl, (CO)O —R 15 or CN;

R 9 is hydrogen, (CO)O—R 15 ;

or R 8 and R 9 are together —(CH 2 ) w —, —CH═CH—CH 2 —, —(CO)—O—(CO)—, —(CO)—N(R 16 )—CO— or

R 10 is hydrogen, C 1 -C 8 -alkyl or —SO 3 − E + ;

R 11 is hydrogen;

or R 10 and R 11 together are —O—CH 2 CH 2 —O—;

R 12 and R 13 independently of each other are C 1 -C 4 -alkyl, vinyl, phenyl or C 1 -C 4 alkoxy;

R 14 is hydrogen, CH 2 Br, CH 2 Cl or I;

R 15 is hydrogen, C 1 -C 4 -alkyl or benzyl;

R 16 is C 1 -C 4 alkyl or phenyl;

w is an integer 3-10;

E is a cation; and

Z is CH 2 or O.

2. An oligomer or polymer of the formula (Ia) according to claim 1 , wherein

z is 0;

y is 0 or is an integer between m and 20 fold m;

R 1 is C 1 -C 4 -alkyl;

R 2 is C 1 -C 4 -alkyl;

X is a direct bond, C 1 -C 10 -alkylene, —(CH 2 ) o —O(CO)—CH 2 —* or

wherein the asterisk denotes the bond to the bisacylphosphine oxide moiety;

o and q are 1;

r is 0;

s is 0;

A is

wherein the asterisk denotes the bond to X;

B 1 is

wherein A and B 1 are incorporated into the same polymer backbone via random or block polymerization;

R 4 is C 1 -C 4 alkyl;

R 5 is methyl, phenyl or ethoxy;

R 8 is hydrogen;

R 9 is hydrogen;

R 12 and R 13 independently of each other are C 1 -C 4 -alkyl, vinyl or C 1 -C 4 alkoxy;

R 14 is hydrogen, CH 2 Br or I; and

Z is CH 2 .

3. An oligomer or polymer according to claim 1 , which is selected from the group consisting of bisacylphosphine oxide-functionalized polystyrenes, bisacylphosphine oxide-functionalized polynorbornes, bisacylphosphine oxide-functionalized polyacrylates, bisacylphosphine oxide-functionalized polythiophenes, bisacylphosphine oxide-functionalized polysiloxanes, bisacylphosphine oxide-functionalized biopolymers, bisacylphosphine oxide-functionalized polyepoxides, bisacylphosphine oxide-functionalized polyvinylesters and bisacylphosphine oxide-functionalized dendritic polymers.

4. A process for the synthesis of an oligomer or polymer according to claim 1 , wherein the oligomer or polymer is obtained by homopolymerization or copolymerization of a functionalized bisacylphosphine oxide compound of formula (II), optionally with one or more monomers containing no bisacylphosphine oxide moiety, and optionally using a suitable catalyst,

wherein

R 1 is C 1 -C 4 -alkyl, C 1 -C 4 -alkoxy or Cl;

R 2 is H, C 1 -C 4 -alkyl, C 1 -C 4 -alkoxy or Cl:

Y is —(CH 2 ) a — or —CH 2 —CHOH—CH 2 —;

a is an integer 1-10;

FG is Cl, Br, OH, SH, NH 2 , N 3 , COOH, COO − E + , COOCH 3 , COONH 2 ,

b is 0, 1 or 2;

c is 1 or 2;

R 3 is hydrogen or methyl;

R 4 is C 1 -C 4 alkyl;

R 5 and R 5a independently of each other are methyl, phenyl or ethoxy;

E is a cation;

provided that, if a is 1, FG is not COOCH 3 or

5. A process for the synthesis of an oligomer or polymer according to claim 1 , wherein the oligomer or polymer is obtained by homopolymerization or copolymerization of a functionalized bisacylphosphine oxide compound of formula (IIa), optionally with one or more monomers containing no bisacylphosphine oxide moiety, and optionally using a suitable catalyst,

wherein

R 1 is C 1 -C 4 -alkyl, C 1 -C 4 -alkoxy or Cl;

R 2 is H, C 1 -C 4 -alkyl, C 1 -C 4 -alkoxy or Cl:

Y is —(CH 2 ) a — or —CH 2 —CHOH—CH 2 —;

a is an integer 1-10;

FG is Cl, Br, OH, SH, NH 2 , N 3 , COOH, COO − E + , COOR 17 , CH═CH 2 ,

b is 0, 1 or 2;

c is 1 or 2;

R 3 is hydrogen or methyl;

R 4 is C 1 -C 4 alkyl;

R 5 and R 5a independently of each other are methyl, phenyl or ethoxy;

E is a cation;

R 17 is C 1 -C 4 alkyl or CH═CH 2 .

6. A process for the synthesis of an oligomer or polymer according to claim 1 , wherein the oligomer or polymer is obtained by reaction of a functional group “FG” in a bisacylphosphine oxide compound of formula (II) with a second functional group on a polymer or copolymer backbone capable of reacting with the functional group on the bisacylphosphine oxide compound, optionally using a suitable catalyst,

wherein

R 1 is C 1 -C 4 -alkyl, C 1 -C 4 -alkoxy or Cl;

R 2 is H, C 1 -C 4 -alkyl, C 1 -C 4 -alkoxy or Cl:

Y is —(CH 2 ) a — or —CH 2 —CHOH—CH 2 —;

a is an integer 1-10;

FG is Cl, Br, OH, SH, NH 2 , N 3 , COOH, COO − E + , COOCH 3 , COONH 2 ,

b is 0, 1 or 2;

c is 1 or 2;

R 3 is hydrogen or methyl;

R 4 is C 1 -C 4 alkyl;

R 5 and R 5a independently of each other are methyl, phenyl or ethoxy;

E is a cation;

provided that, if a is 1, FG is not COOCH 3 or

7. A process for the synthesis of an oligomer or polymer according to claim 1 , wherein the oligomer or polymer is obtained by reaction of a functional group “FG” in a bisacylphosphine oxide compound of formula (IIa) with a second functional group on a polymer or copolymer backbone capable of reacting with the functional group on the bisacylphosphine oxide compound, optionally using a suitable catalyst,

wherein

R 1 is C 1 -C 4 -alkyl, C 1 -C 4 -alkoxy or Cl;

R 2 is H, C 1 -C 4 -alkyl, C 1 -C 4 -alkoxy or Cl:

Y is —(CH 2 ) a — or —CH 2 —CHOH—CH 2 —;

a is an integer 1-10;

FG is Cl, Br, OH, SH, NH 2 , N 3 , COOH, COO + E + , COOR 17 , CH═CH 2 ,

b is 0, 1 or 2;

c is 1 or 2;

R 3 is hydrogen or methyl;

R 4 is C 1 -C 4 alkyl;

R 5 and R 5a independently of each other are methyl, phenyl or ethoxy;

E is a cation;

R 17 is C 1 -C 4 alkyl or CH═CH 2 .

8. A process for the synthesis of an oligomer or polymer according to claim 1 , wherein the oligomer or polymer is obtained by reaction of a symmetric or unsymmetric metal bisacylphosphide oxide with a functional group on a polymer or copolymer backbone capable of reacting with the metal bisacylphosphide, followed by oxidation with a suitable oxidation agent.

9. A photopolymerizable composition comprising

(A) at least one ethylenically unsaturated photopolymerisable compound and

(B) at least one oligomer or polymer according to claim 1 as photoinitiator.

10. A photopolymerizable composition according to claim 9 , comprising (C) further photoinitiators and/or (D) further additives.

11. A coated substrate coated on at least one surface with a composition according to claim 9 .

12. A coated substrate coated on at least one surface with a composition according to claim 10 .