Photoinitiators with protected carbonyl group

Patent metadata

Field	Value
Publication number	US-10968197-B2
Application number	US-201716338605-A
Country	US
Kind code	B2
Filing date	Oct 9, 2017
Priority date	Oct 20, 2016
Publication date	Apr 6, 2021
Grant date	Apr 6, 2021

Abstract

Disclosed are of the protected photoinitiators of the formula: wherein Aryl1 is an aromatic or heteroaromatic ring; Aryl2 is an aromatic ring; each R 1 is an alkyl, an aryl, an electron donating group or an electron withdrawing group, and subscript a is 0 to 3; each R 2 is an alkyl, an aryl, an electron donating group or an electron withdrawing group, and subscript b is 0 to 3; Prot is a protected carbonyl group.

First claim

What is claimed is:

1. A protected photoinitiator of the formula:

wherein,
Aryl 1 is an aromatic or heteroaromatic ring;
Aryl 2 is an aromatic ring;
each R 1 is an alkyl, an aryl, an electron donating group or an electron withdrawing group, and subscript a is 0 to 3;
each R 2 is an alkyl, an aryl, an electron donating group or an electron withdrawing group, and subscript b is 0 to 3;
Prot is a protected carbonyl group.

2. The protected photoinitiator of claim 1 wherein Aryl 1 is selected from:

wherein ˜ indicated the ring attachment, R 1 is an alkyl, an aryl, an electron donating group or an electron withdrawing group, and subscript a is 0 to 3.

3. The protected photoinitiator of claim 1 wherein Aryl 2 is selected from phenyl and napthyl.

4. The protected photoinitiator of claim 1 wherein Prot is a cyclic or acyclic ketal.

5. The protected photoinitiator of claim 1 wherein Prot is selected from thioketals, dithioketals, O-substituted cyanohydrins, substituted hydrazones, oxazolidines, imidazolidines or thiazolidines protecting groups.

6. The protected photoinitiator of claim 1 having at least one electron-donating R 1 or R 2 groups.

7. The protected photoinitiator of claim 1 having at least one electron-withdrawing R 1 or R 2 groups.

8. A polymerizable composition comprising at least one free-radically polymerizable monomer, and the protected photoinitiator of claim 1 .

9. The polymerizable composition of claim 8 wherein the monomer is a (meth)acrylate monomer.

10. The polymerizable composition of claim 8 wherein the monomer is a multifunctional (meth)acrylate monomer.

11. The polymerizable composition of claim 8 comprising
i. up to 100 parts by weight of an (meth)acrylic acid ester;
ii. 0 to 15 parts by weight of an acid functional ethylenically unsaturated monomer;
iii. 0 to 15 parts by weight of a non-acid functional, ethylenically unsaturated polar monomer;
iv. 0 to 5 parts by weight vinyl monomer;
v. 0 to 100 parts by weight of a multifunctional (meth)acrylate relative to i-iv, wherein the sum of I. to Vii is 100%.

12. The polymerizable composition of claim 8 comprising a reactive oligomer having pendent polymerizable groups comprising:
a) greater than 50 parts by weight of (meth)acrylate ester monomer units;
b) 1 to 10 parts by weight of monomer units having a pendent, free-radically polymerizable functional group,
c) 0 to 20 parts by weight of other polar monomer units, wherein the sum of the monomer units is 100 parts by weight.

13. The polymerizable composition of claim 12 wherein the reactive oligomer may be represented by the formula:
-[M Unsatd ] o [M ester ] p [M polar ] q -,  II

where
[M Undatd ] represents monomer units having a pendent, free-radically polymerizable functional groups and subscript “o” is the parts be weight thereof;
[M ester ] represents (meth)acrylate ester monomer units and subscript “p” represents the parts by weight thereof; and
[M polar ] represents polar monomer units and subscript “q” represents the parts by weight thereof.

14. The polymerizable composition of claim 8 comprising:
a) 20-80 parts by weight of multifunctional (meth)acrylate monomers and/or multifunctional (meth)acrylate reactive oligomers,
b) 0 to parts by weight range of (meth)acrylate diluent,
c) 20 to 75 wt. % of silica; and
from about 0.1 weight percent to about 5.0 weight percent of the photoinitiator, based on the 100 parts by weight of the polymerizable components of the polymerizable composition.

15. The polymerizable composition of claim 8 further comprising a filler.

16. The polymerizable composition of claim 8 further comprising a chain transfer agent.

17. A curable dental composition comprising a dental resin and the protected photoinitiator of claim 1 .

18. A method of making the protected photoinitiator of claim 1 comprising the steps of coupling of an aromatic acetylide compound with an aromatic methylene halide compound, followed by oxidative ketalization, and oxidation of the alkyne to a diketone.

19. A method of making the protected photoinitiator of claim 1 comprising the steps of coupling of an aryl alkyne with an aryl acyl halide, followed by ketalization, then oxidation of the alkyne to a diketone.

20. The protected photoinitiator of claim 1 comprising at least one electron-withdrawing R 1 group and at least one electron donating R 2 group.

21. The protected photoinitiator of claim 20 wherein the electron donating group is selected from primary amino, secondary amino, tertiary amino, morpholino, hydroxy, alkoxy, aryloxy, alkyl, or combinations thereof, and the electron withdrawing group is selected from halo, cyano, fluoroalkyl, perfluoroalkyl, carboxy, aminocarbonyl, alkoxycarbonyl, aryloxycarbonyl, halocarbonyl, formyl, carbonyl, sulfo, alkoxysulfonyl, aryloxysulfonyl, perfluoroalkylsulfonyl, alkylsulfonyl, azo, alkenyl, alkynyl, dialkylphosphonato, diarylphosphonato, or combinations thereof.

Assignees

• 3M Innovative Properties Co

Inventors

• Volp Kelly A
• Chou Shih-Hung
• Homnick Paul J
• Abuelyaman Ahmed S
• Gong Tao
• Oxman Joel D
• Mahoney Wayne S

Classifications

• A61K6/71

  Fillers · CPC title

• A61K6/30

  Compositions for temporarily or permanently fixing teeth or palates, e.g. primers for dental adhesives · CPC title

• A61K6/62

  Photochemical radical initiators · CPC title

• A61K6/887

  Compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds · CPC title

• C08L33/10

  Homopolymers or copolymers of methacrylic acid esters · CPC title