Process for preparing polyols

Patent metadata

Field	Value
Publication number	US-10138200-B2
Application number	US-201615569880-A
Country	US
Kind code	B2
Filing date	Jun 15, 2016
Priority date	Jun 30, 2015
Publication date	Nov 27, 2018
Grant date	Nov 27, 2018

Abstract

The present invention relates to a process for preparing polyols. In particular, the present invention relates to the preparation, in a single step, of polyols by a process involving a hydrohydroxymethylation reaction starting from a composition A comprising one or more compounds of formula (I).

First claim

The invention claimed is:

1. A process for preparing polyols from a composition A, said composition A comprising one or more compounds of formula (I)

wherein
R 1 , R 2 , R 3 , R 4 , R 5 , R 6 and R 7 are, independently of one another, and for R 3 and R 7 independently for each of the n units, selected from the group consisting of H, —OR 15 , C 1 -C 10 alkyl which is unsubstituted or substituted with one or more —OR 15 groups, C 6 -C 12 aryl which is unsubstituted or substituted with one or more —OR 15 groups, or C 3 -C 10 cycloalkyl which is unsubstituted or substituted with one or more —OR 15 groups, and a group of formula (Ia)

R 15 represents H or C 1 -C 10 alkyl which is unsubstituted or substituted with one or more —OH groups;
a, b, x and y are independently of one another, independently for each group of formula (Ia), independently for each [(CH 2 ) a —C═C—(CH 2 ) b ] r unit and independently for each [(CH 2 ) x —C═C—(CH 2 ) y ] p unit, an integer between 0 and 20
r is an integer between 1 and 10
p is an integer between 1 and 10
n is an integer between 1 and 7;
said process comprising a step a) of placing together, with stirring and under an atmosphere of hydrogen and of carbon monoxide:
at least one precatalyst which is a complex comprising a transition metal chosen from column 9 of the periodic table,
a tertiary amine, or a non-quaternary ammonium salt thereof, of formula NR 8 R 9 R 10 wherein R 8 , R 9 and R 10 represent, independently of one another, a C 1 -C 10 alkyl, a C 6 -C 12 aryl or a C 3 -C 10 cycloalkyl, or R 8 and R 9 form, together with the nitrogen atom to which they are attached, a heterocycle comprising four, five or six ring members,
said composition A comprising said compound of formula (I).

2. The process as claimed in claim 1 , characterized in that step a) is carried out at a temperature between 70° C. and 180° C.

3. The process as claimed in claim 1 , characterized in that said at least one compound of formula (I) is of formula (II)

wherein
a, b, x and y are, independently of one another, independently for each group of formula (Ia), independently for each [(CH 2 ) a —C═C—(CH 2 ) b ] r unit and independently for each [(CH 2 ) x —C═C—(CH 2 ) y ] p unit, an integer between 0 and 20
p is, independently for each [(CH 2 ) x —C═C—(CH 2 ) y ] p unit, an integer between 1 and 5;
r is, independently for each [(CH 2 ) a —C═C—(CH 2 ) b ] r unit, an integer between 1 and 5;
R 1 , R 2 , R 3 , R 4 and R 5 are, independently of one another, and for R 3 independently for each of the n units, selected from the group consisting of H, —OR 15 , C 1 -C 10 alkyl which is unsubstituted or substituted with one or more —OR 15 groups, and a group of formula (Ia) as described above,
R 15 represents H or C 1 -C 10 alkyl which is unsubstituted or substituted with one or more —OH groups;
n is an integer between 1 and 4.

4. The process as claimed in claim 3 , characterized in that said at least one compound of formula (I) is of formula (II) wherein
a and x can be, independently of one another, independently for each [(CH 2 ) x —C═C—(CH 2 ) y ] p unit and independently for each [(CH 2 ) a —C═C—(CH 2 ) b ] r unit, an integer between 1 and 12;
b and y can be, independently of one another, independently for each [(CH 2 ) x —C═C—(CH 2 ) y ] p unit and independently for each [(CH 2 ) a —C═C—(CH 2 ) b ] r unit, an integer between 0 and 12;
R 1 , R 2 , R 3 , R 4 and R 5 are a hydrogen;
p is 1, 2 or 3 independently for each [(CH 2 ) x —C═C—(CH 2 ) y ] p unit;
r is 1, 2 or 3 independently for each [(CH 2 ) a —C═C—(CH 2 ) b ] r unit;
n is 1.

5. The process as claimed in claim 1 , characterized in that the tertiary amine is of formula NR 8 R 9 R 10 wherein R 8 , R 9 and R 10 represent, independently of one another, a C 1 -C 10 alkyl, or R 8 and R 9 form, together with the nitrogen atom to which they are attached, an azetidine, diazetidine, pyrrolidine, imidazolidine or pyrazolidine heterocycle.

6. The process as claimed in claim 1 , characterized in that the precatalyst is a complex comprising rhodium as transition metal and one or more ligands.

7. The process as claimed in claim 1 , characterized in that it is carried out under pressure of a hydrogen and carbon monoxide atmosphere, said pressure being between 50 bar and 200 bar.

8. The process as claimed in claim 1 , characterized in that the molar ratio between the carbon monoxide and the hydrogen is between 2:1 and 1:10.

9. The process as claimed in claim 1 , characterized in that the molar ratio between the amine and the transition metal is greater than 20.

10. The process as claimed in claim 1 , characterized in that said composition A comprising one or more compounds of formula (I) is a vegetable oil having an average unsaturation number of less than 3.5.

11. The process as claimed in claim 1 , characterized in that a, b, x and y are independently of one another, independently for each group of formula (Ia), independently for each [(CH 2 ) a —C═C—(CH 2 ) b ] r unit and independently for each [(CH 2 ) x —C═C—(CH 2 ) y ] p unit, are between 0 and 15.

12. The process as claimed in claim 1 , characterized in that r is between 1 and 5 inclusive.

13. The process as claimed in claim 1 , characterized in that p is between 1 and 5 inclusive.

14. The process as claimed in claim 1 , characterized in that x and y are each independently between 1 and 10 inclusive.

15. The process as claimed in claim 5 , characterized in that R 8 , R 9 and R 10 represent, independently of one another, C 1 -C 10 alkyl, or R 8 and R 9 form, together with the nitrogen atom to which they are attached, a pyrrolidine.

16. The process as claimed in claim 6 , characterized in that the at least one of said one or more ligands is at least one of CO, acetylacetonate, cyclooctadiene, norbornene or acetate.

17. The process as claimed in claim 8 , characterized in that the molar ratio between the carbon monoxide and the hydrogen is between 1:1 and 1:5.

18. The process as claimed in claim 9 , characterized in that the molar ratio between the amine and the transition metal is greater than 50.

19. The process as claimed in claim 10 , characterized in that the average unsaturation number of less than 3.4.

Assignees

• Pivert S A S
• Centre Nat Rech Scient
• Univ Dartois

Inventors

• Hapiot Frederic
• Monflier Eric
• Vanbesien Theodore

Classifications

• C07C67/347 Primary

  by addition to unsaturated carbon-to-carbon bonds · CPC title

• C07C31/225

  Glycerol · CPC title

• C11C3/02

  by esterification of fatty acids with glycerol · CPC title

• C07C69/675

  of saturated hydroxy-carboxylic acids · CPC title