Method for producing functionalised telechelic oligomers

Patent metadata

Field	Value
Publication number	US-9845382-B2
Application number	US-201415101064-A
Country	US
Kind code	B2
Filing date	Dec 3, 2014
Priority date	Dec 3, 2013
Publication date	Dec 19, 2017
Grant date	Dec 19, 2017

Abstract

This invention relates to a method for producing functionalized telechelic oligomers, comprising two steps. The first step relates to bringing a raw material comprising at least one high-molecular-weight polymer comprising at least two unsaturations, into contact with a solution comprising at least one metathesis catalyst and at least one functionalizing agent. The second step relates to the separation of the functionalized telechelic oligomers produced by the metathesis reaction in ionic liquid medium of the first step.

First claim

The invention claimed is:

1. Method for producing functionalized telechelic oligomers, comprising:
a) bringing a raw material consisting of at least one high-molecular-weight polymer comprising at least two unsaturations, into contact with a solution comprising at least one ionic liquid, at least one metathesis catalyst and at least one functionalising agent chosen from hydrogenocarbonated molecules having a symmetrical disubstituted carbon-carbon double bond and two functions having a general formula:

wherein, R can be a group:
—COR, R being chosen from a group comprising hydrogen, substituted or unsubstituted alkyl, substituted or unsubstituted aryl;
—COOR, R being chosen from a group comprising hydrogen, substituted or unsubstituted alkyl, substituted or unsubstituted aryl, methyl-1,3-dioxolanone, methyl-oxirane;
—OR, R being chosen from a group comprising hydrogen, substituted or unsubstituted alkyl, substituted or unsubstituted aryl, methyl-1,3-dioxolanone, methyl-oxirane;
—NR′R″, R′ and R″ being identical or different, each one chosen from a group comprising hydrogen, substituted or unsubstituted alkyl, substituted or unsubstituted aryl, acetyl, tert-butyl-acetyl;
—[N + R′R″R′″,X − ], R′, R″, R′″ being identical or different and each one chosen from a group comprising substituted or unsubstituted alkyl, substituted or unsubstituted aryl and X − being an anion chosen from the group comprising fluoride, chloride, iodide, bromide, tosylate, triflate;
—SR, R being chosen from a group comprising hydrogen, substituted or unsubstituted alkyl, substituted or unsubstituted aryl;
—C≡N;
—C(═N)R, R being chosen from a group comprising hydrogen, substituted or unsubstituted alkyl, substituted or unsubstituted aryl;
—SO 2 R, R being chosen from a group comprising hydrogen, substituted or unsubstituted alkyl, substituted or unsubstituted aryl;
—SO 3 R, R being chosen from a group comprising hydrogen, substituted or unsubstituted alkyl, substituted or unsubstituted aryl;
—NO 2 ; and

b) the separation of the functionalized telechelic oligomers produced by the metathesis reaction in an ionic liquid medium of the step a).

2. Method according to claim 1 , wherein said raw material is put into solution with an ionic liquid before it is brought into contact with the solution comprising a metathesis catalyst and a functionalising agent.

3. Method according to claim 1 , wherein the raw material is chosen from the group comprising ethylene-propylene-diene monomer (EPDM), styrene-ethylene-butadiene-styrene (SEBS), styrene butadiene rubber (SBR), acrylonitrile-butadiene (Nitrile Butadiene Rubber NBR), partially hydrogenated acrylonitrile-butadiene (Hydrogenated Nitrile-Butadiene Rubber HNBR), Styrene-Butadiene-Styrene (SBS), thermoplastic elastomer (Thermo-Plastic Elastomer Styrenic TPE), styrenic block copolymer (Thermo-Plastic Elastomer Styrenic TPS), a styrenic block copolymer selected from the group comprising Styrene-Isoprene-Styrene (SIS), Styrene-Ethylene-Butylene-Styrene (SEBS), Styrene-Ethylene-Propylene-Styrene (SEPS), and Styrene-Ethylene-Ethylene/Propylene-Styrene (SEEPS).

4. Method according to claim 1 , wherein the metathesis catalyst is chosen from a group comprising a Grubbs I catalyst, a Grubbs II catalyst, a Hoveyda-Grubbs I catalyst and a Hoveyda Grubbs II catalyst.

5. Method according to claim 1 , wherein the functionalising agent is chosen from the group comprising cis-but-2-ene-diacetate, cis-but-2-ene-diketone, cis-but-2-ene-diol, and cis-but-2-ene-diamine.

6. Method according to claim 1 , wherein the ionic liquid is trihexyl(tetradecyl)phosphonium chloride or N,N-dioctylimidazolium bromide ([DOIM][Br]).

7. Method according to claim 1 , wherein the functionalising agent is cis-but-2-ene-diacetate, the metathesis catalyst is Grubbs II and the ionic liquid is trihexyl(tetradecyl)phosphonium chloride.

8. Method according to claim 1 , wherein the functionalising agent is cis-but-2-ene-diacetate, the metathesis catalyst is Hoveyda-Grubbs II and the ionic liquid is N,N-dioctylimidazolium bromide.

9. Method according to claim 1 , comprising a step wherein the metathesis catalyst contained in the liquid medium resulting from the separation of the step b) is recycled.

10. Composition of functionalized telechelic oligomers able to be produced by the method according to claim 1 , characterized in that the oligomers have a net functionality of 2.

11. Method according to claim 1 , wherein the raw material is a waste material containing rubber, with said method being simultaneously a method for degrading and for recycling said waste material and a method for producing telechelic oligomers.

12. Method according to claim 1 , wherein the raw material is a tire waste.

Assignees

• Centre National De La Recherche Scient (Cnrs)
• Univ De Caen Basse-Normandie
• Univ Maine
• Centre Nat Rech Scient

Inventors

• Pilard Jean-Francois
• Nourry Arnaud
• Dez Isabelle
• Gaumont Annie-Claude
• Mouawia Ali

Classifications

• C08C19/00

  Chemical modification of rubber · CPC title

• C08C19/08

  Depolymerisation · CPC title

• C08J11/16

  by treatment with inorganic material (C08J11/14 takes precedence) · CPC title

• C08J2321/00

  Characterised by the use of unspecified rubbers · CPC title

• C08J11/22 Primary

  by treatment with organic oxygen-containing compounds · CPC title