Titanium-based catalyst for vitrimer resins of epoxy/anhydride type

Patent metadata

Field	Value
Publication number	US-10155842-B2
Application number	US-201515306000-A
Country	US
Kind code	B2
Filing date	Apr 23, 2015
Priority date	Apr 24, 2014
Publication date	Dec 18, 2018
Grant date	Dec 18, 2018

Abstract

The present invention relates to a composition containing, besides a thermosetting resin of epoxy type and a hardener of anhydride type, at least one catalyst comprising an organometallic titanium complex. This composition enables the manufacture of vitrimer resins, that is to say resins that can be deformed in the thermoset state. It also relates to a kit for manufacturing this composition, an object obtained from this composition and a kit for manufacturing this object. Another subject of the invention relates to an organometallic titanium complex corresponding to the structure titanium bis(3-phenoxy-1,2-propane dioxide) (Ti(PPD)2), and the use thereof as vitrimer effect catalyst in systems based on epoxy resin and on hardener of anhydride type.

First claim

The invention claimed is:

1. A composition comprising at least:
a catalyst comprising titanium bis(3-phenoxy-1,2-propane dioxide) (Ti(PPD) 2 ),
a thermosetting resin comprising at least one epoxide function and optionally at least one free hydroxyl and/or ester function, and
a thermosetting-resin curing agent selected from carboxylic acid anhydrides,
wherein the thermosetting resin is selected from the group consisting of glycidyl esters, glycidyl ethers, glycidyl amines and glycidyl isocyanurates, comprising at least two glycidyl groups per molecule, and epoxidized olefin compounds which are linear, branched or cyclic comprising more than six members.

2. The composition as claimed in claim 1 , wherein the catalyst further comprises titanium isopropoxide.

3. The composition as claimed in claim 1 , wherein the thermosetting resin is selected from the group consisting of glycidyl esters, glycidyl ethers, glycidyl amines and glycidyl isocyanurates, comprising at least two glycidyl groups per molecule, and mixtures thereof.

4. The composition as claimed in claim 1 , wherein the thermosetting resin is selected from the group consisting of epoxidized olefin compounds which are linear, branched or cyclic comprising more than six members, and mixtures thereof.

5. The composition as claimed in claim 1 , wherein the thermosetting resin is selected from the group consisting of: bisphenol A diglycidyl ether (DGEBA), tetraglycidyl methylene dianiline (TGMDA), bisphenol F diglycidyl ether, Novolac resins, trimethylol triglycidyl ether (TMPTGE), the diglycidyl ester of phthalic, isophthalic or terephthalic acid, tetrabromo bisphenol A diglycidyl ether, 1,4-butanediol diglycidyl ether, the epoxidized cycloaliphatic resin represented by formula (II), triglycidyl isocyanurate (TGIC), poly(glycidyl methacrylate), and mixtures thereof

6. The composition as claimed in claim 1 , wherein the thermosetting resin is selected from the group consisting of bisphenol A diglycidyl ether (DGEBA), tetraglycidyl methylene dianiline (TGMDA), Novolac resins and glycidyl methacrylate.

7. The composition as claimed in claim 1 , wherein the amount of curing agent is such that the number of moles of epoxide functions of the thermosetting resin ranges from 50% to 300%, relative to the number of moles of anhydride functions of the curing agent.

8. The composition as claimed in claim 1 , wherein the content of thermosetting resin and of curing agent ranges from 10% to 90% by weight, relative to the total weight of the composition, the remainder to 100% being provided by the catalyst and optionally by one or more additional compounds selected from the group consisting of:
polymers, pigments, dyes, fillers, plasticizers, long or short fibers, woven or nonwoven fibers, flame retardants, antioxidants, lubricants, wood, glass, metals, and mixtures thereof.

9. The composition as claimed in claim 1 , further comprising at least one epoxide-opening additional catalyst.

10. The composition as claimed in claim 1 , further comprising at least one polyol.

11. The composition as claimed in claim 10 , wherein the polyol is glycerol, trimethylolpropane or pentaerythritol.

12. The composition as claimed in claim 1 , comprising at least one thermosetting resin selected from the group consisting of bisphenol A diglycidyl ether (DGEBA), tetraglycidyl methylene dianiline (TGMDA), Novolac resins, and glycidyl methacrylate, and at least one carboxylic acid anhydride.

13. A kit for producing a composition as claimed in claim 1 , comprising at least:
a first composition comprising the catalyst;
a second composition comprising the curing agent; and
a third composition comprising the thermosetting resin.

14. A method for producing an object made of thermoset resin that is hot-deformable, comprising using the composition as claimed in claim 1 .

15. An object comprising a thermoset resin obtained from a composition as defined in claim 1 .

16. A process for deforming an object, comprising applying to an object in accordance with claim 15 a mechanical stress at a temperature (T) above the glass transition temperature Tg of the thermoset resin.

17. The composition as claimed in claim 1 , wherein the thermosetting resin is a glycidyl ether.

18. A kit for producing a composition as claimed in claim 1 , comprising:
a first composition comprising the catalyst and the curing agent; and
a second composition comprising the thermosetting resin.

19. A kit for producing a composition as claimed in claim 1 , comprising:
a first composition comprising the catalyst and the thermosetting resin; and
a second composition comprising the curing agent.

20. A method of producing a composition as claimed in claim 1 , comprising combining the catalyst, the thermosetting resin, and the curing agent.

21. An organometallic titanium complex corresponding to the structure titanium bis(3-phenoxy-1,2-propane dioxide) (Ti(PPD) 2 ).

22. A method comprising using the organometallic titanium complex as claimed in claim 21 as a vitrimer effect catalyst in a system based on an epoxy resin and on a curing agent of anhydride type.

Assignees

• Arkema France
• Centre Nat Rech Scient
• Ecole Superieure Physique & Chimie Ind Ville De Paris

Inventors

• Duquenne Christophe
• Mougnier Sebastien-Jun
• Tournilhac Francois-Genes
• Leibler Ludwik

Classifications

• C07F7/28

  Titanium compounds · CPC title

• C08G59/685

  Carboxylates · CPC title

• C08G59/682

  Alcoholates · CPC title

• C08G59/42 Primary

  Polycarboxylic acids; Anhydrides, halides or low molecular weight esters thereof · CPC title

• C08G59/683 Primary

  Phenolates · CPC title