Self-blowing isocyanate-free polyurethane foams

Patent metadata

Field	Value
Publication number	US-12503552-B2
Application number	US-202217567420-A
Country	US
Kind code	B2
Filing date	Jan 3, 2022
Priority date	Jul 5, 2019
Publication date	Dec 23, 2025
Grant date	Dec 23, 2025

Abstract

The present invention relates to a curable isocyanate-free formulation for preparing a polyurethane self-blowing foam comprising at least one multifunctional cyclic carbonate having at least two cyclic carbonate groups at the end of the chain (compound A), at least one multifunctional amine (compound B), at least one multifunctional thiol (compound C) and at least one catalyst (compound D), to a process for preparing said foams, to the thus obtained foams and the recycling of said foams.

First claim

The invention claimed is:

1 . A curable isocyanate-free formulation for preparing a polyurethane self-blowing foam comprising at least one multifunctional cyclic carbonate having at least two cyclic carbonate groups at the end of the chain (compound A), at least one multifunctional amine (compound B), at least one multifunctional thiol (compound C) and at least one catalyst (compound D).

2 . The formulation according to claim 1 wherein compound A corresponds to formula I

wherein
i is an integer higher than or equal to 2,
R1 is a carbon bond between the cyclic carbonate rings or is a linear or branched hydrocarbon chain, which may be unsubstituted or substituted and wherein one or several hydrocarbon groups of said hydrocarbon chain may be replaced by an heteroatom, a ketone, a cycloalkyl, an heterocycle, an aryl or an heteroaryl, each of which may be unsubstituted or substituted, said hydrocarbon chain having at least 2 carbon atoms.

3 . The formulation according to claim 1 wherein compound B corresponds to formula II
R2-(NHR′) j   Formula (II)

wherein
j is an integer higher than or equal to 2,
R2 is an aryl or heteroaryl, each of which may be unsubstituted or substituted, or a linear or branched hydrocarbon chain, which may be unsubstituted or substituted, and wherein one or several hydrocarbon groups of said hydrocarbon chain may be replaced by a heteroatom, a cycloalkyl or an heterocycle, each of which may be unsubstituted or substituted, said hydrocarbon chain having at least 2 carbon atoms, and
wherein R′ each independently may be hydrogen, an alkyl or a cycloalkyl.

4 . The formulation according to claim 1 wherein compound C corresponds to formula III
R3-(SH) k   Formula III

wherein
k is an integer higher than or equal to 2,
R3 is a linear or branched hydrocarbon chain, which may be unsubstituted or substituted, and wherein one or several hydrocarbon groups of said hydrocarbon chain may be replaced by an heteroatom, a ketone, a cycloalkyl or an heterocycle, each of which may be unsubstituted or substituted, said hydrocarbon chain having at least 2 carbon atoms, or R3 is a linear or branched polymeric group.

5 . The formulation according to claim 1 wherein compound D is selected from the group consisting of an amine catalyst, an ionic salt or ionic liquid composed of a combination of a cation and an anion, organometallic catalyst and a phosphine-based catalyst.

6 . The formulation according to claim 1 wherein compound A is present in an amount of from 18 to 80 wt %, the percentage being expressed relative to the total weight of the formulation.

7 . The formulation according to claim 1 wherein compound B is present in an amount of from 10 to 80 wt %, the percentage being expressed relative to the total weight of the formulation.

8 . The formulation according to claim 1 wherein compound C is present in an amount of from 1 to 60 wt %, the percentage being expressed relative to the total weight of the formulation.

9 . The formulation according to claim 1 wherein compound D is present in an amount of from 0.1 to 15 wt %, the percentage being expressed relative to the total weight of the formulation.

10 . The formulation according to claim 1 further comprising a monofunctional cyclic carbonate (compound E).

11 . The formulation according to claim 1 further comprising a multifunctional cyclic carbonate having at least two cyclic carbonate groups within the chain (compound F), in an amount of from 1 to 50 wt %, the percentage being expressed relative to the total weight of the formulation.

12 . The formulation according to claim 1 further comprising a monofunctional thiol (compound G).

13 . The formulation according to claim 1 further comprising a polyepoxide (compound H), in an amount of from 0.1 to 50 wt %, the percentage being expressed relative to the total weight of the formulation.

14 . Process for preparing a polyurethane self-blowing foam comprising the steps of providing a formulation as defined in claim 1 and curing said formulation at a temperature between 25° C. and 200° C. so as to promote the formation of CO 2 and form a non-isocyanate polyurethane foam.

15 . Process for preparing a polyurethane foam comprising the steps of
(i) mixing compounds A and B in the presence of compound D so as to form a viscous mixture, (ii) partially curing said mixture so as to form a non-isocyanate polyurethane viscous prepolymer, (iii) adding compound C to said prepolymer,
(iv) curing said mixture obtained in step (iii) so as to form a non-isocyanate polyurethane foam, wherein compounds A, B, C, and D are as defined in any one of claim 1 .

16 . Process for preparing a polyurethane foam comprising the steps of
(i) mixing compounds A and B in the presence of compound C so as to form a viscous mixture, (ii) partially curing said mixture so as to form a non-isocyanate polyurethane viscous prepolymer loaded with unreacted compound C, (iii) adding compound D to said prepolymer, (iv) curing said mixture obtained in step (iii) so as to promote the formation of CO 2 and form a non-isocyanate polyurethane foam,
wherein compounds A, B, C, and D are as defined in claim 1 .

17 . The formulation according to claim 2 wherein i is an integer from 2 to 10.

18 . The formulation according to claim 2 wherein said hydrocarbon chain has from 3 to 60 carbon atoms.

19 . The formulation according to claim 3 wherein j is an integer from 2 to 6.

20 . The formulation according to claim 3 wherein said hydrocarbon chain has from 2 to 60 carbon atoms.

21 . The formulation according to claim 4 wherein k is an integer from 2 to 6.

22 . The formulation according to claim 4 wherein said hydrocarbon chain has from 2 to 60 carbon atoms.

23 . The formulation according to claim 5 wherein compound D is 1,8-diazabicyclo[5.4.0]undec-7-ene or tetrabutylammonium phenolate.

24 . The formulation according to claim 10 wherein a monofunctional cyclic carbonate (compound E) is in an amount from 1 to 50 wt %, the percentage being expressed relative to the total weight of the formulation, and said monofunctional cyclic carbonate is of formula IV

wherein
R4 is hydrogen or a linear or branched hydrocarbon chain, which may be unsubstituted or substituted with a functional group selected from the group consisting of an alcohol, a secondary or tertiary amine, a carboxylic acid, an alkene, and an ester, and wherein one or several hydrocarbon groups of said hydrocarbon chain may be replaced by an heteroatom, a cycloalkyl or an heterocycle, each of which may be unsubstituted or substituted, said hydrocarbon chain having at least 1 carbon atom.

25 . The formulation according to claim 12 wherein the monofunctional thiol (compound G) is present in an amount from 1 to 50 wt %, the percentage being expressed relative to the total weight of the formulation, and said monofunctional thiol corresponding to formula VIII
R17-SH  Formula (VIII)

wherein:
R17 is an aryl group which may be unsubstituted or substituted or a linear of branched polymeric group or a linear or branched hydrocarbon chain which may be unsubstituted or sub

Assignees

• Univ Liege

Inventors

• Detrembleur Christophe
• Thomassin Jean-Michel
• Grignard Bruno
• Monie Florent
• Jerome Christine

Classifications

• C08J9/08

  developing carbon dioxide · CPC title

• C08G2101/00

  Manufacture of cellular products · CPC title

• C08G2110/0025

  rigid · CPC title

• C08G2110/0008

  flexible · CPC title

• C08G2110/005

  < 50kg/m3 · CPC title