Telechelic polyolefin and preparation thereof

Patent metadata

Field	Value
Publication number	US-9598510-B2
Application number	US-201214383404-A
Country	US
Kind code	B2
Filing date	Sep 27, 2012
Priority date	Mar 12, 2012
Publication date	Mar 21, 2017
Grant date	Mar 21, 2017

Abstract

Telechelic polyolefin of formula(I) and its derivatives:

CH 2 ═CH—(CH 2 ) p -A-Z  (I)

wherein:
A represents a (co)polymer comprising at least 95 mol % of (CH 2 —CH 2 ) units; Z is selected from the group comprising halogens, thiols and their derivatives, azides, amines, alcohols, the carboxylic acid function, isocyanates, silanes, phosphorous derivatives, dithioesters, dithiocarbamates, dithiocarbonates, trithiocarbonates, alkoxyamines, the vinyl function, dienes, and the group -A-(CH 2 ) p —CH═CH 2 ; p is a whole number between 1 and 20, most advantageously between 6 and 9.

First claim

The invention claimed is:

1. A process for preparing a telechelic polyolefin of formula (I):
CH 2 ═CH—(CH 2 ) p -A-Z  (I)

wherein:
A represents a (co)polymer comprising at least 95 mol % of (CH 2 —CH 2 ) units;
Z is selected from the group consisting of halogens; thiols and their derivatives; azides; amines; alcohols; the carboxylic acid function; isocyanates; silanes; phosphorous derivatives; dithioesters; dithiocarbamates; dithiocarbonates; trithiocarbonates; alkoxyamines; the vinyl function; dienes; and the group -A-(CH 2 ) p —CH═CH 2 ; and
p is a whole number between 1 and 20,

said process comprising the following steps:
preparing a compound of formula (II):
Y(A-(CH 2 ) p —CH═CH 2 ) m   (II)

wherein m is 2 or 3; and
when m=2, Y is an alkaline earth metal; and
when m=3, Y is an element of group 13; and
cleaving the bond between Y and A-(CH 2 ) p —CH═CH 2 , and functionalizing A-(CH 2 ) p —CH═CH 2 with Z.

2. A process according to claim 1 , wherein the preparing the compound of formula (II) is achieved in the presence of a transition metal or lanthanide complex, and a transfer agent of formula (III):
Y((CH 2 ) p —CH═CH 2 ) m   (III).

3. A process according to claim 2 , wherein the transition metal or lanthanide complex is a metallocene selected from the group consisting of compounds of which the formula contains the base structure: (Cp 1 )(Cp 2 )M or E(Cp 1 )(Cp 2 )M;
M being a group 3 or 4 metal, or a lanthanide; and
Cp 1 , Cp 2 being cyclopentadienyl, fluorenyl or indenyl groups or those groups featuring additional substituents;
E being a bridge between the Cp 1 and Cp 2 ligands, of the formula M′R 1 R 2 , M′ being a group 14 element, and R 1 and R 2 being alkyl or aryl groups having 1 to 20 carbon atoms.

4. A process according to claim 3 , wherein the complex is a metallocene of the formula (C 5 Me 5 ) 2 MX 2 Li(OEt 2 ) 2 , M being a group 3 metal or lanthanide and X being a halogen.

5. A process according to claim 4 , wherein M is a lanthanide.

6. A process according to claim 2 , wherein the telechelic polyolefin is represented by the formula CH 2 ═CH—(CH 2 ) p —(CH 2 —CH 2 ) n —I, I being an iodine atom, p being a whole number between 6 and 9, and n being a whole number between 17 and 360.

7. A process according to claim 1 , wherein the functionalizing step with Z comprises the addition of a compound selected from the group consisting of iodine I 2 , sulfur S 8 and tetraethylthiuram disulfide.

8. A process according to claim 1 , wherein the functionalizing step with Z is an oxidative coupling when Z=-A-(CH 2 ) p —CH═CH 2 .

9. A process according to claim 1 , further comprising, subsequent to the functionalizing with Z, modifying at least one of the chain-ends of the telechelic polyolefin by reaction of the vinyl function and/or of the Z group.

10. A process according to claim 1 , wherein, when m=2, Y is magnesium or zinc, and when m=3, Y is aluminum.

11. A process according to claim 1 , wherein p is a whole number between 6 and 9.

12. A process according to claim 1 , wherein the telechelic polyolefin is represented by the formula CH 2 ═CH—(CH 2 ) p —(CH 2 —CH 2 ) n —I, I being an iodine atom, p being a whole number between 6 and 9, and n being a whole number between 17 and 360.

13. A telechelic polyolefin of formula (I):
CH 2 ═CH—(CH 2 ) p -A-Z  (I)

wherein:
A represents a (co)polymer comprising at least 95 mol % of (CH 2 —CH 2 ) units;
Z is selected from the group consisting of halogens; thiols and their derivatives; azides; amines; alcohols; the carboxylic acid function; isocyanates; silanes; phosphorous derivatives; dithioesters; dithiocarbamates; dithiocarbonates; trithiocarbonates; alkoxyamines; and dienes; and
p is a whole number between 1 and 20.

14. A telechelic polyolefin according to claim 13 , wherein the CH 2 ═CH—(CH 2 ) p — group of formula (I) originates from a transfer agent of formula Y((CH 2 ) p —CH═CH 2 ) m , wherein m is 2 or 3; and when m=2, Y is an alkaline earth metal; and when m=3, Y is an element of group 13.

15. A telechelic polyolefin according to claim 13 , wherein A is a linear polyethylene of formula (CH 2 —CH 2 ) n , n being a whole number between 7 and 3600.

16. A telechelic polyolefin according to claim 13 , wherein the telechelic polyolefin is represented by the formula CH 2 ═CH—(CH 2 ) p —(CH 2 —CH 2 ) n —I, I being an iodine atom, p being a whole number between 6 and 9, and n being a whole number between 17 and 360.

17. A telechelic polyolefin according to claim 13 wherein p is a whole number between 6 and 9.

Assignees

• Univ Claude Bernard Lyon
• Centre Nat Rech Scient
• Cpe Lyon Formation Continue Et Rech

Inventors

• Boisson Christophe
• D'Agosto Franck
• German Ian

Classifications

• C07F3/02 Primary

  Magnesium compounds · CPC title

• C08F8/04

  Reduction, e.g. hydrogenation · CPC title

• C08F8/00

  Chemical modification by after-treatment (graft polymers, block polymers, crosslinking with unsaturated monomers or with polymers C08F251/00 - C08F299/00; of conjugated diene rubbers C08C) · CPC title

• C08F2810/40

  taking place solely at one end or both ends of the polymer backbone, i.e. not in the side or lateral chains · CPC title

• C07F5/063

  Chemistry & Metallurgy · mapped topic