Addition-fragmentation oligomers

Patent metadata

Field	Value
Publication number	US-9463146-B2
Application number	US-201314652134-A
Country	US
Kind code	B2
Filing date	Nov 27, 2013
Priority date	Dec 17, 2012
Publication date	Oct 11, 2016
Grant date	Oct 11, 2016

Abstract

Addition-fragmentation oligomers of the general formula Z—B y -A-(B-A) x -B-A-B y —Z, where the A monomers units are derived from a diester or diacid, the B monomer units are derived from a difunctional monomer having functional groups co-reactive and at least one of the A or B monomers comprise a 1-methylene-3,3-dimethylpropyl group.

First claim

What is claimed is:

1. An addition-fragmentation oligomer of the formula:

wherein
R A and R B are each a (hetero)hydrocarbyl group, wherein at least one of R A and R B is

X 1 is —O or NR 5 —, where R 5 is H or C 1 -C 4 alkyl;
Z comprises an ethylenically unsaturated polymerizable group;
y is 0 or 1;
x is 0 or 1, and at least one of x or y must be one.

2. The addition-fragmentation oligomer of claim 1 wherein both R A and R B are

3. The addition-fragmentation oligomer of claim 1 wherein Z comprises a (meth)acrylate or vinyl group.

4. The addition-fragmentation oligomer of claim 1 where y is 1.

5. A method of preparing the addition-fragmentation oligomer of claim 1 by combining:
a compound of the formula:
a) R 1 —O—CO—R A —CO—O—R 1 , wherein R A is a (hetero)hydrocarbyl group and R 1 is H or alkyl;
with a compound of the formula:
b) X 2 —R B —X 2 , wherein R B is a (hetero)hydrocarbyl group and X 2 is functional group reactive with the acid or ester functional groups of compound a), and

a compound of the formula:
c) (Z) d -X 3 , where Z comprises an ethylenically unsaturated group, and X 3 is reactive functional group, reactive with the functional groups of compounds a) or b) and d is 1 or 2.

6. The method of claim 5 wherein compound a) is in stoichiometric excess to compound b).

7. The method of claim 6 wherein R 1 is H, X 2 comprises an epoxy group and X 3 comprises an isocyanate group.

8. The method of claim 6 wherein the molar equivalents of amount of compound c) is ≧twice the amount of compound a) minus the amount of compound b).

9. The method of claim 5 wherein compound b) is in stoichiometric excess to compound a).

10. A polymerizable composition comprising the addition-fragmentation oligomer of claim 1 , at least one free-radically polymerizable monomer, and an initiator.

11. The polymerizable composition of claim 10 comprising:
a) 85 to 100 parts by weight of an (meth)acrylic acid ester;
b) 0 to 15 parts by weight of an acid functional ethylenically unsaturated monomer;
c) 0 to 10 parts by weight of a non-acid functional, ethylenically unsaturated polar monomer;
d) 0 to 5 parts vinyl monomer; and
e) 0 to 100 parts of a multifunctional (meth)acrylate;
based on 100 parts by weight total monomer a) to d), and
f) 0.1 to 12 parts by weight of the addition-fragmentation oligomer, based on 100 parts by weight of a) to e), and
g) an initiator.

12. The polymerizable composition of claim 11 further comprising 0.01 to 100 parts of a multifunctional (meth)acrylate.

13. An article comprising a layer of the polymerizable composition of claim 11 on a substrate.

14. A method of bonding two substrates together comprising the steps of coating the polymerizable composition of claim 10 to a surface of one or both substrates, wherein the coating of polymerizable composition is at least partially cured, contacting the coated surfaces optionally with pressure, and further curing the polymerizable compositions if necessary.

15. A hardcoat composition comprising one or more multifunctional (meth)acrylate monomers or (meth)acrylate oligomers, and the addition-fragmentation oligomer of claim 1 .

16. The hardcoat composition of claim 15 comprising:
a) 0.1-10 wt. % of the addition fragmentation oligomer;
b) 20-80 wt. % of multifunctional (meth)acrylate monomers and/or multifunctional (meth)acrylate oligomers,
c) 0 to 25 wt. % range of (meth)acrylate diluent, (0-25 wt. %); and
d) 20 to 75 wt. % of silica.

17. A curable dental composition comprising:
a) at least one dental resin comprising at least two ethylenically unsaturated group;
b) an addition-fragmentation oligomer of claim 1 ; and
c) optionally an inorganic oxide filler.

18. The dental composition of claim 17 wherein the dental resin is an isocyanurate resin, a tricyclodecane resin, cyclic allylic sulfide resins; methylene dithiepane silane resins; and poly(meth)acryloyl-containing resins, or mixtures thereof.

19. The dental composition of claim 17 wherein the dental composition further comprises at least one other (meth)acrylate monomer is selected from ethoxylated bisphenol A dimethacrylate, 2-hydroxyethyl methacrylate, bisphenol A diglycidyl dimethacrylate, urethane dimethacrylate, triethlyene glycol dimethacrylate, glycerol dimethacrylate, ethylenegylcol dimethacrylate, neopentylglycol dimethacrylate (NPGDMA), polyethyleneglycol dimethacrylate, and mixtures thereof.

20. A method of treating a tooth surface, the method comprising
a) providing a curable dental composition of claim 17 ;
b) placing the dental composition on a tooth surface in the mouth of a subject; and
c) hardening the hardenable dental composition.

Assignees

• 3M Innovative Properties Co

Inventors

• Fornof Ann R
• Moser William H
• Krepski Larry R
• Joly Guy D
• Abuelyaman Ahmed S
• Falsafi Afshin
• Gaddam Babu N

Classifications

• A61K6/887

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

• A61K6/889

  Polycarboxylate cements; Glass ionomer cements · CPC title

• C08F2/38 Primary

  Polymerisation using regulators, e.g. chain terminating agents {, e.g. telomerisation} · CPC title

• C07C269/02

  from isocyanates with formation of carbamate groups · CPC title

• C08F2438/03

  Use of a di- or tri-thiocarbonylthio compound, e.g. di- or tri-thioester, di- or tri-thiocarbamate, or a xanthate as chain transfer agent, e.g . Reversible Addition Fragmentation chain Transfer [RAFT] or Macromolecular Design via Interchange of Xanthates [MADIX] · CPC title