Method for the synthesis of alpha/alpha-prime-alcoxylated glycerol linear carbonic esters

Patent metadata

Field	Value
Publication number	US-9950988-B2
Application number	US-201314655690-A
Country	US
Kind code	B2
Filing date	Dec 20, 2013
Priority date	Dec 26, 2012
Publication date	Apr 24, 2018
Grant date	Apr 24, 2018

Abstract

A method for the synthesis of α/α′-alcoxylated glycerol linear carbonic esters, wherein the following are brought into contact at a reaction temperature lower than 220° C.: a quantity of at least one precursor selected from the group consisting of α/α′-alcoxylated glycerol cyclo-carbonates; a quantity of at least one catalyst selected from the group consisting of metal oxides, Lewis acids, organometallic catalysts and mineral bases; and a quantity of at least one organic primer. A composition containing at least one novel α/α′-alkoxylated glycerol linear carbonic ester.

First claim

The invention claimed is:

1. A method for synthesizing a group of α/α′-alkoxylated glycerol linear carbonic esters wherein the following are placed in contact at a reaction temperature lower than about 220° C.:
i. a quantity of at least one precursor selected from the group consisting of α/α′-alkoxylated glycerol cyclic carbonates of a formula (XXII):

wherein R 4 , R 5 and R 6 are hydrogen (H), or
R 4 and R 5 are hydrogens (H) and R 6 is an alkyl group or an amino-alkyl group having 1 to 5 carbon atoms, or
R 4 , R 5 and R 6 are selected from the group formed by hydrogen (H) and organic groups of following general formula (VII):

wherein:
R 7 is selected from the group formed of an H and a hydrocarbon group having 1 to 6 carbon atoms;
m is an integer between 0 and 10 inclusive; and
X is selected from among —O— and —NH;

ii. a quantity of at least one catalyst selected from the group consisting of metal oxides, metal alkoxides, Lewis acids, organometallic catalysts and mineral bases; and
iii. a quantity of at least one organic initiator selected from the group consisting of alcohols, polyols and amino-alcohols, wherein:
said alcohols are chosen from pentacyclic glycerol carbonate (GC), ethanol (EtOH), n-butanol (BuOH), and 3-(2-hydroxyethyl)imidazolidin-2-one,
said polyols are chosen from glycerol and glycerol α-methyl ether (GE), and
said amino-alcohols are chosen from amino-alcohols having a main chain comprising 2 to 10 carbon atoms;
wherein at a first step of the method the at least one precursor, the at least one catalyst and the at least one organic initiator are mixed and heated in a gas-tight sealed reactor until they reach the reaction temperature and a pressure called an autogenous pressure inside the sealed reactor which is higher than atmospheric pressure, and
wherein at a second step of the method at the reaction temperature, a gaseous composition is allowed to escape to reduce the autogenous pressure inside the sealed reactor and the reaction temperature is maintained in the sealed reactor for a time of more than about 5 min.

2. The method according to claim 1 , wherein the at least one organic initiator is selected from the group consisting of amino-alcohols having at least one amine selected from the group consisting of primary amines, secondary amines and tertiary amines.

3. The method according to one of claims 1 , wherein the at least one organic initiator is triethanolamine.

4. The method according to claim 1 , wherein the at least one organic initiator is selected from the group consisting of 1-amino-1-cyclopentanemethanol, 4-aminocyclohexanol, amino-1-butanol, 2-amino-1-butanol, 2-amino-1-phenyl-1,3-propanediol, 3-amino-3-phenyl propan-1-ol and 2-amino-3-phenyl-1-propan-1-ol.

5. The method according to claim 1 , wherein the at least one catalyst is selected from the group consisting of zinc sulfate and zinc stearate.

Assignees

• Chryso
• Inst Nat Polytechnique Toulouse
• Inst Nat De La Rech Agronomique Inra

Inventors

• LEISING FRéDéRIC
• MOULOUNGUI ZéPHIRIN

Classifications

• C07C69/96 Primary

  Esters of carbonic or haloformic acids · CPC title

• C07C68/06

  from organic carbonates · CPC title