Polymeric photoinitiators and photoinitiator monomers

Patent metadata

Field	Value
Publication number	US-9296835-B2
Application number	US-201314401125-A
Country	US
Kind code	B2
Filing date	May 14, 2013
Priority date	May 16, 2012
Publication date	Mar 29, 2016
Grant date	Mar 29, 2016

Abstract

The present invention provides polymeric photoinitiators being co-polymers of photoinitiator monomers and at least one further monomer, as well as photoinitiator monomers being intermediates in the preparation of such polymeric photoinitiators. Additionally, there is provided polyacrylate obtained by radical polymerization of at least one acrylate monomer (Ac) in the presence of such polymeric photoinitiators. In the photoinitiator monomers and polymeric photoinitiators, a photoinitiator moiety, a hydrolytic stable linker and two polymerizable functional groups are incorporated into the photoinitiator structure.

First claim

The invention claimed is:

1. A polymeric photoinitiator, being a co-polymer of at least one monomer (A) with at least one monomer (B), wherein:
the at least one monomer (A) comprises formula (II):

wherein Ar 1 and Ar 2 are each independently selected from the same or different aryl, where Z may be present at any position on Ar 2 , where each aromatic ring is independently optionally substituted with one or more substituents;
Z is a linker moiety selected from a single bond, a C 1 -C 12 alkylene, a C 2 -C 12 alkenylene, a C 3 -C 8 cycloalkyl, an aryl, a heterocyclyl, a —(C 1 -C 12 alkylene)-aryl-, an -aryl-(C 1 -C 12 alkylene)-, a —(C 1 -C 12 alkylene)-heterocyclyl-, a -heterocyclyl-(C 1 -C 12 alkylene)-, a —[O—(C 1 -C 12 alkylene)] m -, a —[S—(C 1 -C 12 alkylene)] m -, a —[(C 1 -C 12 alkylene)-O] m —, a —[(C 1 -C 12 alkylene)-S-] m -, a —[O—(C 1 -C 12 alkylene)] m -O—, a —[S—(C 1 -C 12 alkylene)] m -S—, a —[O—(C 1 -C 12 alkylene)] m -S—, a —[S—(C 1 -C 12 alkylene)] m -O—; a —C(═O)—, a —[C(═O)—(C 1 -C 12 alkylene)] m -, a —[C(═O)-aryl] m -, and
a —[C(═O)-heterocyclyl] m -;
R 1 is selected from H, a C 1 -C 12 alkyl, a C 2 -C 12 alkenyl, a C 3 -C 8 cycloalkyl, an aryl, a heterocyclyl,
a —[O—(C 1 -C 12 alkylene)] m -H, a —[S—(C 1 -C 12 alkylene)] m -H, a —C(═O)—H, a —[C(═O)—(C 1 -C 12 alkylene)] m -H, a —[C(═O)-aryl] m -H and a —[C(═O)-heterocyclyl] m -H;
X 1 and X 2 are each independently selected from a single bond, a C 1 -C 12 alkylene, a C 2 -C 12 alkenylene, a C 3 -C 8 cycloalkyl, an aryl, a heterocyclyl, a —[O—(C 1 -C 12 alkylene)] p , and a —[S—(C 1 -C 12 alkylene)] p ;
wherein X 1 , X 2 , R 1 or Z each independently may be linked to one another to form one or more ring structures;
W 1 and W 2 are each independently selected from —OH, —CH 2 OH, —COOH, —COOR 2 , —COO-aryl, —SH, —CH 2 SH, —NH 2 , —NHR 2 , —NCO, —NCS, —C(═O)—Cl, and —O—C(═O)—Cl;
R 2 is selected from an optionally substituted C 1 -C 12 alkyl and aryl;
m is an integer from 1-10;
n is an integer of 1 or 2, with the proviso that when n is 2, R 1 is absent;
p is an integer from 1-10; and
wherein any alkyl, alkenyl, alkylene, alkenylene, cycloalkyl, aryl, or heterocyclyl moiety each independently is an optionally substituted with one or more substituents selected from —F, —Cl, —Br, —I, —CN, —NO 2 , —C 1 -C 6 alkyl, aryl, —O—(C 1 -C 6 alkyl), —S—(C 1 -C 6 alkyl), —S(O)—(C 1 -C 6 alkyl), and —SO 2 —(C 1 -C 6 alkyl);
wherein the at least one monomer (B) has the structure of formula (V):
W 3 -Q-W 4   (V)

Q is selected from the group consisting of optionally substituted C 1 -C 12 alkylene, optionally substituted C 1 -C 12 alkenylene, optionally substituted C 3 -C 8 cycloalkyl, optionally substituted C 3 -C 12 heterocyclyl, optionally substituted aryl and optionally substituted biaryl;
W 3 and W 4 are each independently selected from —F, —Cl, —Br, —I, —OSO 2 R 4 , —OSO 2 —Ar 3 , —OH, —CH 2 OH, —COOH, —COOR 4 , —COO-aryl, —SH, —CH 2 SH, —NH 2 , —NHR 4 , —NCO, —NCS, —C(═O)—Cl, and —O—C(═O)—Cl, wherein R 4 is selected from an optionally substituted C 1 -C 12 alkyl; or W 3 and W 4 are linked to each other forming a cyclic lactone or thiolactone; and
wherein W 1 , W 2 , W 3 and W 4 are selected such that W 1 reacts with W 3 to form a urethane, urea, amide, thiourethane, thiourea, dithiourethane, ester, ether, carbonate, phosphonite, phosphonate, phosphate, allophanate or biuret moiety, and W 2 reacts with W 4 to form a urethane, urea, amide, thiourethane, thiourea, dithiourethane, ester, ether, carbonate, phosphonite, phosphonate, phosphate, allophanate or biuret moiety.

2. The polymeric photoinitiator according to claim 1 , wherein Z is selected from a C 1 -C 12 alkylene, a C 2 -C 12 alkenylene, a C 3 -C 8 cycloalkyl, an aryl, a heterocyclyl, a —[O—(C 1 -C 12 alkylene)] m -, a —[S—(C 1 -C 12 alkylene)] m -, a —[(C 1 -C 12 alkylene)-O] m —, a —[(C 1 -C 12 alkylene)-S-] m -, a —[O—(C 1 -C 12 alkylene)] m -O—, a —[S—(C 1 -C 12 alkylene)] m -S—, a —C(═O)—, a —[C(═O)—(C 1 -C 12 alkylene)] m -, a —[C(═O)-aryl] m -, and a —[C(═O)-heterocyclyl] m -, where any of these moieties independently is optionally substituted with one or more substituents.

3. The polymeric photoinitiator according to claim 1 , wherein n is 1.

4. The polymeric photoinitiator according to claim 1 , wherein n is 2.

5. The polymeric photoinitiator according to claim 1 , wherein R 1 is selected from H, a C 1 -C 12 alkyl, a C 2 -C 12 alkenyl, a —[O—(C 1 -C 12 alkylene)] m -H, a —[S—(C 1 -C 12 alkylene)] m -H, a —C(═O)—H, and a —[C(═O)—(C 1 -C 12 alkylene)] m -H, where any alkyl, alkylene, or alkenyl moiety independently is optionally substituted with one or more substituents.

6. The polymeric photoinitiator according to claim 1 , wherein X 1 and X 2 each independently are selected from a C 1 -C 12 alkylene, a C 2 -C 12 alkenylene, a —[O—(C 1 -C 12 alkylene)] m , and a —[S—(C 1 -C 12 alkylene)] m , where any alkylene or alkenylene moiety independently is optionally substituted with one or more substituents.

7. The polymeric photoinitiator according to claim 1 , wherein m is an integer from 1-5.

8. The polymeric photoinitiator according to claim 1 , wherein W 1 and W 2 each independently are selected from —OH, —CH 2 OH, —COOH, —COOR 2 , —COO-aryl, —SH, —CH 2 SH, —C(═O)—Cl, and —O—C(═O)—Cl.

9. The polymeric photoinitiator according to claim 1 , wherein W 1 and W 2 each independently are selected from —CH 2 OH, —COOH, —COOR 2 and —CH 2 SH.

10. The polymeric photoinitiator according to claim 1 , wherein X 1 and X 2 both are an optionally substituted C 1 -C 12 alkylene, being the same or different, and W 1 and W 2 both are —CH 2 OH.

11. The polymeric photoinitiator according to claim 1 , wherein Ar 1 and Ar 2 each independently are optionally a substituted phenyl; where Z may be attached at any position on Ar 2 .

12. The polymeric photoinitiator according to claim 1 , wherein Z is present at the para-position on Ar 2 .

13. The polymeric photoinitiator according to claim 1 , wherein formula (II) comprises formula (III):

wherein Z may be attached at any position on the phenyl rings and the phenyl rings are each independently optionally substituted.

14. The polymeric photoinitiator according to claim 1 , wherein formula (II) comprises formula (IIIa):

wherein Z may be attached at any position on the phenyl ring and the phenyl rings are each independently optionally substituted.

15. The polymeric photoinitiator according to claim 1 , wherein formula (II) comprises formula (IV):

wherein Z may be attached at any position on the aryl ring and the aryl rings are each independently optionally substituted.

16. The polymeric photoinitiator according to claim 1 , wherein formula (II) comprises formula (IVa):

wherein Z may be attached at any position on the aryl ring and the aryl rings are each independently optionally substit

Assignees

• Coloplast As

Inventors

• Madsen Niels Joergen
• Sehnal Petr
• Anderson David George
• Nielsen Bo Rud

Classifications

• C08F2/50 Primary

  with sensitising agents · CPC title

• C08G18/3215

  containing aromatic groups or benzoquinone groups · CPC title

• C08G18/6674

  with compounds of group C08G18/3203 · CPC title

• C08G63/00

  Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule (polyester-amides C08G69/44; polyester-imides C08G73/16) · CPC title

• C07C49/84

  containing ether groups, [IMAGE cpc-sch-C07C-0958.gif] groups,[IMAGE cpc-sch-C07C-0959.gif] groups, or[IMAGE cpc-sch-C07C-0960.gif] groups · CPC title