Hydrocarbon-based polymers comprising two end groups with 2-oxo-1,3-dioxolan-4-yl endings, preparation thereof and use thereof

Patent metadata

Field	Value
Publication number	US-9359459-B2
Application number	US-201314651798-A
Country	US
Kind code	B2
Filing date	Dec 13, 2013
Priority date	Dec 14, 2012
Publication date	Jun 7, 2016
Grant date	Jun 7, 2016

Abstract

Process for the preparation of a hydrocarbon polymer comprising two end groups having 2-oxo-1,3-dioxolan-4-yl final parts by ring opening metathesis in the presence of a metathesis catalyst, of a chain transfer agent comprising a carbonate ring and of a compound of formula comprising at least one C 6 -C 16 ring having a carbon-carbon double bond.
Hydrocarbon polymer capable of being obtained by this process.
Process for the preparation of polyurethanes by reaction of this polymer and of a compound comprising at least one amine group, and polyurethanes thus obtained.

First claim

The invention claimed is:

1. A process for the preparation of at least one hydrocarbon polymer comprising two end groups having 2-oxo-1,3-dioxolan-4-yl final parts, said process comprising at least one stage of ring opening metathesis polymerization in the presence:
of at least one metathesis catalyst;
of at least one chain transfer agent (CTA) compound of formula (15):

the Z group being composed of at least one alkylene group optionally connected to a divalent carboxyl or oxy group, the Z group comprising from 1 to 19 carbon atoms and q being an integer equal to 0 or 1; and
of at least one compound comprising at least one hydrocarbon ring, carbon atoms per ring, said ring comprising at least one carbon-carbon double bond, or substituted derivatives of this compound, said compound being of formula (7):

in which:
each carbon-carbon bond of the chain denoted is a double bond or a single bond, in accordance with the valency rules of organic chemistry;
the R 1 and R 6 groups are either both hydrogen or each different from hydrogen and bonded to one another as members of one and the same ring or heterocycle which is saturated or unsaturated, said unsaturated rings comprising at least one carbon-carbon double bond, and said unsaturated rings including aromatics;
the R 2 , R 3 , R 4 and R 5 groups are each, independently or not of the other groups, a hydrogen, a halo group, an alkoxycarbonyl group or an alkyl group, it being possible for the R 2 to R 5 groups to be bonded to one another as members of one and the same saturated or unsaturated ring or heterocycle;
m and p are integers each within a range extending from 0 to 5, the sum m+p being itself within a range from 0 to 6;
said stage being carried out for a period of time strictly of greater than 3 h when the compound of formula (15) is 4-vinyl-1,3-dioxolan-2-one and for a period of time of greater than or equal to 2 h in all the other cases.

2. The preparation process as claimed in claim 1 , said process being such that the compound of formula (15) is 4-vinyl-1,3-dioxolan-2-one, 4-(vinyloxymethyl)-1,3-dioxolan-2-one, 4-(acryloyloxymethyl)-1,3-dioxolan-2-one, a 4-(alkenyloxymethyl)-1,3-dioxolan-2-one or a 4-(alkenoyloxymethyl)-1,3-dioxolan-2-one.

3. The preparation process as claimed in claim 1 , said process additionally comprising at least one additional hydrogenation of carbon-carbon double bonds.

4. A hydrocarbon polymer comprising two end groups having 2-oxo-1,3-dioxolan-4-yl final parts which is obtained by the process as claimed in claim 1 .

5. The hydrocarbon polymer comprising two end groups having 2-oxo-1,3-dioxolan-4-yl final parts as claimed in claim 4 , said hydrocarbon polymer being of formula (1):

in which:
each carbon-carbon bond of the chain denoted is a double bond or a single bond, in accordance with the valency rules of organic chemistry;
the R 1 and R 6 groups are either both hydrogen or each different from hydrogen and bonded to one another as members of one and the same ring or heterocycle which is saturated or unsaturated, said unsaturated rings comprising at least one carbon-carbon double bond, and said unsaturated rings including aromatics;
the R 2 , R 3 , R 4 and R 5 groups are each, independently or not of the other groups, a hydrogen, a halo group, an alkoxycarbonyl group or an alkyl group, it being possible for the R 2 to R 5 groups to be bonded to one another as members of one and the same saturated or unsaturated ring or heterocycle;
the Z group is composed of at least one alkylene group optionally connected to a divalent carboxyl or oxy group, the Z group comprising from 1 to 19 carbon atoms;
q is a number equal to 0 or 1;
m and p are integers each within a range extending from 0 to 5, the sum m+p being itself within a range from 0 to 6; and
x and y are each an integer, independently of one another, the sum x+y being such that the number-average molar mass Mn of the hydrocarbon polymer of formula (1) is within a range from 600 to 20 000 g/mol, and the polydispersity (PDI) of the hydrocarbon polymer of formula (1) is within a range from 1.1 to 3.0.

6. The hydrocarbon polymer comprising two end groups having 2-oxo-1,3-dioxolan-4-yl final parts as claimed in claim 5 , said hydrocarbon polymer being of formula (2) or of formula (3):

in which , m, p, q, Z, x, y, R 1 , R 2 , R 3 , R 4 , R 5 and R 6 have the meanings given in claim 5 and the bond means that the bond is oriented geometrically on one side or the other with respect to the double bond (cis or trans).

7. The hydrocarbon polymer comprising two end groups having 2-oxo-1,3-dioxolan-4-yl final parts as claimed in claim 5 , said hydrocarbon polymer being of formula (4):

in which , m, p, q, Z, x and y have the meanings given in claim 5 .

8. The hydrocarbon polymer comprising two end groups having 2-oxo-1,3-dioxolan-4-yl final parts as claimed in claim 7 , said hydrocarbon polymer being of formula (5) or of formula (6):

in which the bond means that the bond is oriented geometrically on one side or the other with respect to the double bond (cis or trans).

9. A process for the preparation of polyurethanes comprising the reaction of at least one hydrocarbon polymer as claimed in claim 4 with at least one compound comprising at least one amine group.

10. A polyurethane obtained by the preparation process as claimed in claim 9 .

11. The process according to claim 1 , wherein the metathesis catalyst is a ruthenium-containing catalyst.

12. The process according to claim 1 , wherein the catalyst is a Grubbs catalyst.

13. The process according to claim 1 , wherein the compound comprising at least one hydrocarbon ring has 6 to 16 carbon atoms per ring.

14. The process according to claim 1 , wherein the compound comprising at least one hydrocarbon ring has 6 to 12 carbon atoms per ring.

15. The hydrocarbon polymer according to claim 5 , wherein the PDI is 1.4 to 2.5.

16. The process according to claim 9 , wherein the hydrocarbon polymer is reacted with at least one compound comprising at least two amine groups.

17. The process according to claim 16 , wherein the compound comprising at least two amine groups is a diamine, triamine or polyamine.

Assignees

• Bostik Sa

Inventors

• Michaud Guillaume
• Simon Frederic
• Fouquay Stephane
• Annunziata Liana
• Guillaume Sophie
• Carpentier Jean Francois

Classifications

• C08G61/08

  of carbocyclic compounds containing one or more carbon-to-carbon double bonds in the ring · CPC title

• C08G71/04 Primary

  Polyurethanes · CPC title

• C08G2261/3322

  derived from cyclooctene · CPC title

• C08G2261/1644

  comprising other functional groups, e.g. OH groups, NH groups, COOH groups or boronic acid · CPC title

• C08F132/04 Primary

  having one carbon-to-carbon double bond · CPC title