Ultrafast cyclic ether-amine photopolyaddition and uses thereof

Patent metadata

Field	Value
Publication number	US-12227612-B2
Application number	US-201917280354-A
Country	US
Kind code	B2
Filing date	Sep 25, 2019
Priority date	Sep 27, 2018
Publication date	Feb 18, 2025
Grant date	Feb 18, 2025

Abstract

The present invention relates to compositions (self-thermally) curable on demand under the triggering action of UV-visible to near-infrared irradiation of moderate intensity, method of using same for accelerated photopolyaddition of cyclic ether-amine resins or ultrafast dark curing of cyclic ether-amine resins, and articles obtained by such method. The invention also relates to a resin casting, film or coated substrate, and an adhesive layeror bonding agent, comprising acyclic ether-amine resin obtained by an accelerated curing process according to the invention. The invention additionally relates to the use of a composition of the invention for increasing the delamination strength of laminated composite materials.

First claim

The invention claimed is:

1. A composition curable on demand under the triggering action of UV-visible to near-infrared irradiation comprising:
(a) at least one polyfunctional cyclic ether component comprising at least two cyclic ether moieties, wherein the at least one polyfunctional cyclic ether component is selected from:
polyfunctional aromatic epoxy compounds selected from:

polyfunctional heteroaliphatic epoxy compounds selected from:

epoxy prepolymers obtained from reaction of diols with epichlorhydrine, selected from bisphenol A diglycidyl ether, 1,4-butanediol diglycidyl ether;
epoxy prepolymers obtained from reaction of diamines with epichlorhydrine, selected from 4,4′-diaminodiphenyl methane tetraglycidyl ether;
or a mixture of two or more of the above;

(b) at least one polyfunctional amine component comprising at least two primary or secondary amine moieties; and
(c) a photoinitiating system generating catalytic species comprising:
at least one suitable photoinitiator or photosensitizer that absorbs light at a UV-visible to near-infrared irradiation under which the composition is to be cured; and
at least one oxidation agent able to react with the photoinitiator or the photosensitizer, selected from iodonium salts, sulfonium salts, and thianthrenium salts.

2. A process for accelerated photopolyaddition of a cyclic ether-amine resin comprising the step of exposing the composition according to claim 1 to UV-visible to near-infrared irradiation.

3. A process for dark curing a cyclic ether-amine resin comprising the step of exposing the composition according to claim 1 to UV-visible to near-infrared irradiation.

4. A process for accelerated curing of a cyclic ether-amine resin comprising the step of exposing to a UV-visible to near-infrared irradiation the composition according to claim 1 .

5. A process according to claim 4 , wherein the irradiation intensity is greater than or equal to 25 mW/cm 2 and less than or equal to 100 W/cm 2 .

6. The process according to claim 4 , wherein the duration of exposure of the resin to the UV-visible to near-infrared irradiation is 1 to 800 seconds.

7. The process according to claim 4 , further comprising a step of mixing or impregnating composite reinforcements with said composition prior to the UV-visible to near-infrared irradiation.

8. The process according to claim 7 , wherein the composite reinforcements are glass fibers, carbon fibers, aramid fibers, basalt fibers, silica fibers, polymer fibers, natural fibers or a mixture of two or more of those.

9. The process according to claim 4 , wherein crosslinking/curing of the composition occurs throughout the whole thickness of the composition.

10. The process according to claim 4 , wherein the process is carried out under air.

11. A resin casting, film or coated substrate comprising a cyclic ether-amine resin obtained by the process according to claim 4 .

12. The coated substrate of claim 11 , wherein the substrate includes metal, glass, ceramic, plastic, adhesive, polymer, composite or wood.

13. An adhesive layer or bonding agent comprising a cyclic ether-amine resin obtained by the process according to claim 4 .

14. A composite comprising (i) a cyclic ether-amine resin obtained by the process according to claim 4 , and (ii) a reinforcing agent.

15. A process for forming the composite of claim 14 , said process comprising spraying, coating or applying the composition onto a substrate and subsequently curing said composition under the UV-visible to near-infrared irradiation.

16. A process for increasing the delamination strength of a laminated composite material, said process comprising mixing or impregnating composite reinforcements with the composition of claim 1 .

17. The process according to claim 4 , wherein the composition further comprises an alcohol comprising an —OH group on a carbon α or β to an aromatic or heteroaromatic nucleus.

18. The composition according to claim 1 , wherein the at least one polyfunctional amine component is selected from:
linear or branched chain aliphatic polyamines selected from ethylene diamine, diethylenetriamine (DTA), Triethylenetetramine (TTA), Tetraethylenepentamine (TEPA), Diproprenediamine (DPDA), Diethylaminopropylamine (DEAPA), hexamethylenediamine, 1,5-Diamino-2-methylpentane, 1,3-Diaminopentane, 2,2-Dimethyl-1,3-propanediamine, or aminoethylethanolamine;
alicyclic polyamines selected from N-aminoethylpiperazine (N-AEP),
Menthane diamine (MDA), Isophoronediamine (IPDA), and 2,4,6-tris(dimethylaminomethyl)phenol, piperazinoethylethylene-diamine, diaminoethylpiperazine, aminoethyltris-aminoethylamine, aminoethyl-diaminoethylpiperazine, aminoethylpiperazinoethylethylenediamine, aminoethyl-piperazine,

aliphatic aromatic polyamines selected from 1-N-benzylbenzene-1,4-diamine, m-xylenediamine, xylylenediamine trimer, xylylenediamine derivatives;
aromatic polyamines selected from m-phenylene diamine, diaminodiphenylmethane, diaminodiphenylsulfone, melamine, melamine polyphosphate, 6-phenyl-1,3,5-triazine-2,4-diamine, or melamine cyanurate;
polyetheramines selected from

or a mixture of two or more of these.

19. A composition curable on demand under the triggering action of UV-visible to near-infrared irradiation comprising:
(a) at least one polyfunctional cyclic ether component comprising at least two cyclic ether moieties
(b) at least one polyfunctional amine component comprising at least two primary or secondary amine moieties; and
(c) a photoinitiating system generating catalytic species comprising:
at least one suitable photoinitiator or photosensitizer that absorbs light at a UV-visible to near-infrared irradiation under which the composition is to be cured, wherein the at least one suitable photoinitiator or photosensitizer is selected from
photoinitiators or photosensitizers in UV, near-UV and Visible spectra selected from:
2-hydroxy-2-methyl-1-phenylpropan-1-one, 2-hydroxy-1,2-diphenhylethanone, (diphenylphosphoryl)(phenyl)methanone, 2-(dimethylamino)-1-(4-morpholinophenyl)ethanone, and bisacylphosphine oxide (BAPO);
xanthones, thioxanthones selected from ITX, 2-ITX and CPTX;

eosin Y (EY) and Rose Bengal (RB);

pyrene and anthracene; and

photoinitiators or photosensitizers in red to Near infrared spectra selected from:

Assignees

• Centre Nat Rech Scient
• Univ Haute Alsace

Inventors

• Garra Patxi
• Lalevée Jacques
• Morlet-Savary Fabrice
• Dietlin Céline
• Caron Aurore

Classifications

• C08K5/45

  Heterocyclic compounds having sulfur in the ring · CPC title

• C08K5/03

  aromatic {, e.g. C6H5-CH2-Cl} · CPC title

• C08G2170/00

  Compositions for adhesives · CPC title

• C08G2150/00

  Compositions for coatings · CPC title

• C08G59/5033

  aromatic · CPC title