Polymerizable polymeric photoinitiators and radiation curable compositions
View Patent ↗A polymerizable polymeric photoinitiator according to Formula (I): wherein: PL represents an n+m+p-functional polymeric core; n and m independently represent an integer from 1 to 30; p represents an integer from 0 to 10; o is 0 or 1; INI represents a group selected from the group consisting of a benzophenone, a thioxanthone, a carbazole, a anthraquinone, a camphor quinone, an α-hydroxyalkylphenone, an α-aminoalkylphenone, an acylphosphine oxide, a bisacyl phosphine oxide, an acylphosphine sulfide, a phenyl glyoxalate, a benzoin ether, a benzyl ketal, an α-dialkoxyacetophenone, a carbazolyl-O-acyl-oxime, an α-haloarylketone and an α-haloaryl sulfone; L 3 and L 4 represent a substituted or unsubstituted divalent linking group comprising 1 to 14 carbon atoms; A represents a radically polymerizable functional group selected from the group consisting of an acrylate, a methacrylate, a styrene, an acryl amide, a methacryl amide, a maleate, a fumarate, an itaconate, an vinyl ether, an allyl ether, an allyl ester, a maleimide, a vinyl nitrile and a vinyl ester; and R4 represents a substituted or unsubstituted alkyl group. Radiation curable compositions containing the polymerizable polymeric photoinitiator and methods for preparing the polymerizable polymeric photoinitiator are also disclosed.
1. A polymerizable polymeric photoinitiator according to Formula (I):
wherein:
PL represents an n+m+p-functional polymeric core;
n and m independently represent an integer from 1 to 30;
p represents an integer from 0 to 10;
o is 0 or 1;
INI represents a group selected from the group consisting of a thioxanthone, a carbazole, a anthraquinone, a camphor quinone, an α-hydroxyalkylphenone, an α-aminoalkylphenone, an acylphosphine oxide, a bisacyl phosphine oxide, an acylphosphine sulfide, a phenyl glyoxalate, a benzoin ether, a benzyl ketal, an α-dialkoxyacetophenone, a carbazolyl-O-acyl-oxime, an α-haloarylketone, and an α-haloaryl sulfone;
L 3 and L 4 represent a substituted or unsubstituted divalent linking group comprising 1 to 14 carbon atoms;
A represents a radically polymerizable functional group selected from the group consisting of an acrylate, a methacrylate, a styrene, an acryl amide, a methacryl amide, a maleate, a fumarate, an itaconate, an vinyl ether, an allyl ether, an allyl ester, a maleimide, a vinyl nitrile, and a vinyl ester; and
R4 represents an alkyl group.
2. The polymerizable polymeric photoinitiator according to claim 1 , wherein PL represents a polyether, a polyester, or a polyamide based polymeric core.
3. The polymerizable polymeric photoinitiator according to claim 2 , wherein n+m+p represents an integer from 2 to 50.
4. The polymerizable polymeric photoinitiator according to claim 1 , wherein PL represents a star shaped, branched, or dendritic polymeric core.
5. The polymerizable polymeric photoinitiator according to claim 1 , wherein L 4 is selected from the group consisting of an alkylene group and an aliphatic ether containing group.
6. The polymerizable polymeric photoinitiator according to claim 1 , wherein R4 represents a methyl group.
7. A radiation curable composition comprising:
the polymerizable polymeric photoinitiator according to claim 1 .
8. A radiation curable inkjet ink comprising:
the polymerizable polymeric photoinitiator according to claim 1 .
9. A radiation curable composition comprising:
the polymerizable polymeric photoinitiator according to claim 1 .
10. A radiation curable inkjet ink comprising:
2-(2-vinyloxyethoxy)ethyl acrylate; and
the polymerizable polymeric photoinitiator according to claim 1 .
11. A radiation curable composition comprising:
the polymerizable polymeric photoinitiator according to claim 1 , which is substantially free of organic solvent.
12. A radiation curable inkjet ink comprising:
the polymerizable polymeric photoinitiator according to claim 1 , which is substantially free of organic solvent.
13. A radiation curable inkjet ink comprising:
2-(2-vinyloxyethoxy)ethyl acrylate; and
the polymerizable polymeric photoinitiator according to claim 1 , which is substantially free of organic solvent.
14. A method of preparing a polymerizable photoinitiator comprising the steps of:
a) providing a polymeric photoinitiator comprising at least one hydroxyl group;
b) providing a monomer according to Formula (II):
wherein
R1, R2, and R3 are independently selected from the group consisting of a hydrogen, an alkyl group, and an aryl group, or R1 and R3 represent the necessary atoms to form a five to eight membered ring;
A represents a radically polymerizable group selected from the group consisting of an acrylate group, a methacrylate group, a styrene group, an acryl amide group, a methacryl amide group, a maleate group, a fumarate group, an itaconate group, a vinyl ether group, an allyl ether group, an allyl ester group, a maleimide, a vinyl nitrile, and a vinyl ester group; and
L represents an optionally substituted divalent linking group comprising 1 to 14 carbon atoms; and
c) catalyzing a reaction between the monomer and the polymeric photoinitiator with a catalyst to a polymerizable polymeric photoinitiator according to Formula (I) defined by claim 1 .
15. The method according to claim 14 , wherein the catalyst is selected from the group consisting of trifluoroacetic acid, trichloroacetic acid, pyridinium tosylate, crosslinked poly(vinylpyridine) hydrochloride, poly(vinylpyridinium) tosylate, and sulfonic acid substituted ion exchangers.
16. The method according to claim 14 , wherein the reaction is performed in the absence of an organic solvent.
17. The method according to claim 15 , wherein the reaction is performed in the absence of an organic solvent.