Process for producing chromenes by catalysis with copper salts intended for the preparation of thermosetting resins

Patent metadata

Field	Value
Publication number	US-11739097-B2
Application number	US-202016937044-A
Country	US
Kind code	B2
Filing date	Jul 23, 2020
Priority date	Jul 23, 2019
Publication date	Aug 29, 2023
Grant date	Aug 29, 2023

Abstract

A process for producing chromenes intended for the preparation of thermosetting resins, includes converting an aromatic propargyl ether of general formula (I) into a chromene by homogeneous catalysis with copper salts in anisole at a temperature between 100 and 170° C. Moreover, a process for preparing a material made of thermoset resin, includes successively a) carrying out the above process; b) polymerizing the reaction product obtained in a) so as to obtain the material made of thermoset resin; c) recovering the material made of thermoset resin obtained in b).

First claim

The invention claimed is:

1. A process for producing chromenes intended for the preparation of thermosetting resins, comprising the step of converting an aromatic propargyl ether of general formula (I) below:

wherein:
R 1 and R 5 represent, independently of one another, a hydrogen atom, or a C 2 -C 6 alkene, C 2 -C 6 alkyne, O—(C 1 -C 6 )alkyl, O—(C 2 -C 6 )alkene or O—(C 2 -C 6 )alkyne group, on condition that at least one of R 1 and R 5 represents a hydrogen atom;
R 2 and R 4 represent, independently of one another, a hydrogen atom, a C 2 -C 6 alkene group, a C 2 -C 6 alkyne group, an O—(C 1 -C 6 )alkyl group, an O—(C 2 -C 6 )alkene group or an O—(C 2 -C 6 )alkyne group;
and R 3 represents a hydrogen atom, an O-(C 1 -C 6 )alkyl group or a C 2 -C 6 alkene group, the alkene group being optionally substituted with a group of general formula (II) below:

wherein:
R 6 and R 9 represent, independently of one another, a hydrogen atom, or a C 2 -C 6 alkene, C 2 -C 6 alkyne, O—(C 1 -C 6 )alkyl, O—(C 2 -C 6 )alkene or O—(C 2 -C 6 )alkyne group, on condition that at least one of R 6 and R 9 represents a hydrogen atom;
and R 7 and R 8 represent, independently of one another, a hydrogen atom, a C 2 -C 6 alkene group, a C 2 -C 6 alkyne group, an O—(C 1 -C 6 )alkyl group, an O—(C 2 -C 6 )alkene group or an O—(C 2 -C 6 )alkyne group;
on condition that at least one of R 1 , R 2 , R 3 , R 4 and R 5 does not represent a hydrogen atom or an O—(C 1 -C 6 )alkyl group;
and the cis/trans isomers thereof and the optical isomers thereof, and racemic mixtures thereof
into a chromene by homogeneous catalysis with copper salts in anisole at a temperature of between 100 and 170° C.

2. The process as claimed in claim 1 , wherein the aromatic propargyl ether of general formula (I) is chosen from the group consisting of propargylated resorcinol, propargylated eugenol, propargylated coupled eugenol, propargylated coupled isoeugenol, propargylated isoeugenol and mixtures thereof and the cis/trans isomers thereof and the optical isomers thereof and racemic mixtures thereof.

3. The process as claimed in claim 2 , wherein the molar percentage of residual propargyl functions of the chromene is less than 11% when the aromatic propargyl ether of general formula (I) is propargylated resorcinol, the molar percentage of residual propargyl functions of the chromene is less than 39% when the aromatic propargyl ether of general formula (I) is propargylated coupled eugenol and the molar percentage of residual propargyl functions of the chromene is less than 35% when the aromatic propargyl ether of general formula (I) is propargylated coupled isoeugenol.

4. The process as claimed in claim 2 , wherein the aromatic propargyl ether of general formula (I) is propargylated resorcinol and wherein the chromene obtained has the formula C and/or D below

5. The process as claimed in claim 4 , wherein the chromene obtained is a mixture of the formulae C and D.

6. The process as claimed in claim 2 , wherein the aromatic propargyl ether of general formula (I) is propargylated resorcinol.

7. The process as claimed in claim 1 , which lasts between 1 and 1000 hours.

8. The process as claimed in claim 7 , which lasts between 2 and 50 hours.

9. The process as claimed in claim 1 , wherein the catalyst is chosen from CuCl and CuCl 2 .

10. The process as claimed in claim 9 , wherein the catalyst is CuCl.

11. The process as claimed in claim 1 , wherein the catalyst content in the reaction medium is between 10 and 10 000 ppm.

12. The process as claimed in claim 11 , wherein the catalyst content in the reaction medium is between 500 and 1500 ppm.

13. A process for preparing a material made of thermoset resin, comprising the following successive steps:
a) carrying out the process as claimed in claim 1 ;
b) polymerizing the reaction product obtained in step a) so as to obtain the material made of thermoset resin;
c) recovering the material made of thermoset resin obtained in step b).

14. The process as claimed in claim 13 , wherein the enthalpy of polymerization of step b) is less than 500 J/g.

15. The process as claimed in claim 13 , wherein the coke content of the thermoset resin obtained in step c) is greater than 50%.

16. The process as claimed in claim 1 , wherein the temperature is of between 120 and 160° C.

Assignees

• Arianegroup Sas
• Centre Nat Rech Scient
• Univ Reims Champagne Ardenne

Inventors

• Pouyet Robin
• Coqueret Xavier
• Defoort Brigitte
• Rivieres Bastien

Classifications

• C07D493/04 Primary

  Ortho-condensed systems · CPC title

• B01J27/122

  of copper · CPC title

• C08G61/122

  derived from five- or six-membered heterocyclic compounds, other than imides · CPC title

• C08G2261/11

  Homopolymers · CPC title

• C08G2261/3242

  containing one or more oxygen atoms as the only heteroatom, e.g. benzofuran · CPC title