Dual cure monomers

Patent metadata

Field	Value
Publication number	US-11021574-B2
Application number	US-201716348346-A
Country	US
Kind code	B2
Filing date	Nov 21, 2017
Priority date	Dec 2, 2016
Publication date	Jun 1, 2021
Grant date	Jun 1, 2021

Abstract

Provided are dual cure monomer are of the formula: (I) wherein R* is a (hetero)hydrocarbyl group; X 1 is —O—, —S—, —NR 3 —, —NR 3 —CO—NR 3 , —CO—NR 3 — or NR 3 —CO—, where R 3 is H, C 1 -C 4 alkyl or R 1 -Epoxy; R 1 is a divalent (hetero)hydrocarbyl group; X 2 is —O—, —S—, —NR 4 —, —NR 4 —CO—NR 4 —, —CO—NR 4 —, —NR 4 —CO— where R 4 is H, C 1 -C 4 alkyl or R 2 —CH═CH 2 ; R 2 is a divalent (hetero)hydrocarbyl group; subscripts a and b are at least one, subscripts c and d are at least one, with the proviso that the monomer has at least two epoxy groups and at least two ene groups.

First claim

What is claimed is:

1. A curable composition comprising:
a) a dual cure monomer of the formula:

wherein
R* is a cyclic or acyclic aliphatic group or a cyclic heteroaromatic group;
X 1 is —O—, —S—, —NR 3 —, —NR 3 —CO—NR 3 , —CO—NR 3 —or NR 3 —CO—, where R 3 is H, C 1 -C 4 alkyl or R 1 -Epoxy;
R 1 is a (hetero)hydrocarbyl group;
X 2 is —O—, —S—, —NR 4 —, —NR 4 —CO—NR 4 —, —CO—NR 4 —, —NR 4 —CO — where R 4 is H, C 1 -C 4 alkyl or R 2 —CH═CH2;
R 2 is a (hetero)hydrocarbyl group;
each of subscripts a,b, and c and d are at least one,
with the proviso that the monomer has at least two epoxy groups and at least two ene groups; and
b) a polythiol.

2. The composition of claim 1 wherein R* is the residue of a polyol.

3. The composition of claim 1 wherein R 1 and R 2 is an alkylene.

4. The composition of claim 1 wherein R* is the residue of an isocyanurate.

5. The composition of claim 1 wherein the polythiol is of the formula:
R 30 (SH) y

where R 30 is (hetero)hydrocarbyl group having a valence of y, and y is ≥2.

6. The composition of claim 5 where R 30 is an aliphatic or aromatic group, optionally containing one or more functional groups consisting of esters, amides, ethers, urethane, thioethers, and urea functional groups, and y is ≥2.

7. The composition of claim 5 where R 30 is an aliphatic, cycloaliphatic, aromatic or alkyl-substituted aromatic moiety having from 1 to 30 carbon atoms and optionally 1 to 4 catenary heteroatoms of oxygen, nitrogen or sulfur.

8. The composition of claim 5 wherein said polythiol is obtained by esterification of a polyol with a terminally thiol-substituted carboxylic acid.

9. The composition of claim 1 , wherein the dual-cure monomer is of the formula:

wherein
R 21 is a (hetero)hydrocarbyl group;
R 22 is a (hetero)hydrocarbyl group;
R 23 is a (hetero)hydrocarbyl group;
X 21 , X 22 and X 23 are each independently S—, —O — or NR 13 —, where R 13 is H, C 1 -C 4 subscripts b and c and e are at least one.

10. The composition of claim 1 , further comprising an epoxy resin.

11. The composition of claim 1 , further comprising a polyene.

12. The composition of claim 1 , wherein the stoichiometric molar ratio of thiol groups of the polythiol to ene groups plus the epoxy groups is from 0.75:1 to 1:0.75.

13. A dual-cure monomer of the formula:

wherein
R 10 is a cyclic or acyclic aliphatic group or a cyclic heteroaromatic group;
R 11 is a divalent (hetero)hydrocarbyl group;
R 12 is a divalent (hetero)hydrocarbyl group;
X 1 and X 2 are each independently is —O—, —S—, —NR 3 —, —NR 3 —CO—NR 3 , —CO—NR 3 — or NR 3 —CO—, where R 3 is H, C 1 -C 4 alkyl
subscripts a, b, c and d are at least one, with the proviso that the monomer has at least two epoxy groups and at least two ene groups.

14. The dual-cure monomer of claim 13 wherein R 10 is an alkylene having 2-10 carbon atoms.

15. The dual-cure monomer of claim 13 wherein R 11 and R 12 are divalent hydrocarbyl groups.

16. A dual-cure monomer of the formula:

wherein
R 21 is a (hetero)hydrocarbyl group;
R 22 is a (hetero)hydrocarbyl group;
R 23 is a (hetero)hydrocarbyl group;
X 21 , X 22 and X 23 are each independently OH or —NR 13 H, where R 13 is H, C 1 -C 4 subscripts b and c and e are at least one,
with the proviso that the monomer has at least two epoxy groups and at least two ene groups.

17. The composition of claim 1 , further comprising a photoinitiator and a base catalyst.

Assignees

• 3M Innovative Properties Co

Inventors

• Moser William H
• Townsend Erik M
• Dailey Ian

Classifications

• C08G75/04 Primary

  from mercapto compounds or metallic derivatives thereof (C08G75/0204 takes precedence) · CPC title

• C08G59/22

  Di-epoxy compounds · CPC title

• C08G75/12

  Polythioether-ethers (C08G75/0245 takes precedence) · CPC title

• C08G75/045 Primary

  from mercapto compounds and unsaturated compounds · CPC title