Redox polymerizable composition with photolabile reducing agents

Patent metadata

Field	Value
Publication number	US-10836844-B2
Application number	US-201615772173-A
Country	US
Kind code	B2
Filing date	Nov 23, 2016
Priority date	Dec 3, 2015
Publication date	Nov 17, 2020
Grant date	Nov 17, 2020

Abstract

Polymerizable compositions comprising a redox initiator system is disclosed. The redox initiators comprises a photolabile reducing agent, that photolyzes and initiates the redox cycle. Dental compositions comprising dental resins and the photolabile redox initiator system are also described.

First claim

What is claimed is:

1. A polymerizable composition comprising a polymerizable component, and a redox initiation system comprising:
a) a transition metal complex that participates in a redox cycle;
b) an oxidizing agent
c) a photolabile reducing agent of the formula:

where
each of R 1 and R 2 are H, an alkyl, an aryl, or R Photo , with the proviso that at least one of R 1 and R 2 is R Photo ;
R Photo is a photolabile group;
each of R 3 and R 4 are independently H, an alkyl, an aryl comprising an ester, an ether, a urethane or a carbonate functional group.

2. The polymerizable composition of claim 1 , wherein the photolabile group R Photo is selected from phenacyl groups, 2-alkylphenacyl groups, ethylene-bridged phenacyl groups, p-hydroxyphenacyl groups, benzoin groups, o- or p-nitrobenzyl groups, o-nitro-2-phenethyloxycarbonyl groups, coumarin-4-yl methyl groups, benzyl groups, o- or p-hydroxylbenzyl groups, o- or p-hydroxynaphthyl groups, 2,5-dihydroxyl benzyl groups, 9-phenylthioxanthyl, 9-phenylxanthyl groups, anthraquinon-2-yl groups, 8-halo-7-hydroxyquinoline-2-yl methyl groups, and pivaloylglycol groups.

3. The polymerizable composition of claim 1 wherein the transition metal complex is of the formula:
[ML p ] n+ A − , wherein M is a transition metal that participates in a redox cycle,
L is a ligand, A− is an anion, n is the formal charge on the transition metal having a whole number value of 1 to 7, and p is the number of ligands on the transition metal having a number value of 1 to 9.

4. The polymerizable composition of claim 1 wherein the redox initiator system is present in the composition in amounts, from 0.1 to about 10 parts by weight, based on 100 parts by weight of the polymerizable component of the polymerizable composition.

5. The polymerizable composition of claim 1 wherein further comprising a secondary reducing agent selected from tertiary amines; aromatic sulfinic salts; thioureas; and mixtures thereof.

6. The polymerizable composition of claim 1 wherein the oxidizing agent of the redox initiator system is selected from persulfuric acid and salts thereof; peroxides, salts of transition metals, perboric acid and salts thereof, permanganic acid and salts thereof, perphosphoric acid and salts thereof, and mixtures thereof.

7. The polymerizable composition of claim 1 comprising one or more polymerizable vinyl monomers and the redox initiator system, wherein the vinyl monomer is selected from vinyl ethers, vinyl esters, styrenes, substituted styrene, vinyl halides, divinylbenzene, alkenes, isoprene, butadiene and mixtures thereof.

8. The polymerizable composition of claim 1 wherein the molar ratio of the transition metal complex relative to oxidizing agent is from 1:1000 to 1:5.

9. The polymerizable composition of claim 1 wherein the mole ratio of the oxidizing agent to the photolabile reducing agent is from 1:1.5 to 1.5:1.

10. The polymerizable composition of claim 1 further comprising 1-35 parts by weight of a toughening agent, relative to 100 parts by weight of the polymerizable component of the polymerizable composition.

11. The polymerizable composition of claim 1 wherein at least one of R 3 and R 4 comprises a C 12 -C 20 alkyl group.

12. The polymerizable composition of claim 1 wherein the transition metal complex is Cu(II) naphthenate.

13. A method of polymerization of the polymerizable composition of claim 1 comprising combining a first mixture comprising the transition metal complex and a second mixture comprising the oxidizing agent and the photolabile reducing agent, a polymerizable component in the first and/or the second mixture, and irradiating the resulting combined mixture to photolyze the photolabile transition metal complex and initiate the redox polymerization cycle.

14. A multilayer article comprising a coating of the polymerizable composition of claim 1 on a substrate.

Assignees

• 3M Innovative Properties Co

Inventors

• Townsend Erik M
• Moser William H
• Ranade Shantanu R
• Shafer Kathleen S
• Kropp Michael A
• Behling Ross E
• Clapper Jason D

Classifications

• C07D407/14 Primary

  containing three or more hetero rings · CPC title

• C08F222/1025

  of aromatic dialcohols · CPC title

• C08F220/1808

  C8-(meth)acrylate, e.g. isooctyl (meth)acrylate or 2-ethylhexyl (meth)acrylate · CPC title

• C08F220/1804

  C4-(meth)acrylate, e.g. butyl (meth)acrylate, isobutyl (meth)acrylate or tert-butyl (meth)acrylate · CPC title

• C07D307/33

  in position 2, the oxygen atom being in its keto or unsubstituted enol form · CPC title