IP Library Granted Patent US 9,434,823
Granted Patent B2
US 9,434,823 · App. 14/352,158 · Granted Sep 6, 2016

Diene copolymer including at least two blocks, method for synthesizing same and rubber composition containing same

Inventors: Rachid Matmour (Clermont-Ferrand, FR); Nicolas Seeboth (Clermont-Ferrand, FR)
Assignees: COMPAGNIE GENERALE DES ETABLISSEMENTS MICHELIN; MICHELIN RECHERCHE ET TECHNIQUE S.A.
C08G81/021B60C1/00C08G81/022C08L53/00C08L53/02C08F2438/01
View Patent ↗
Loading inventors, assignments & file history…
Monitor This Case
Get email alerts when status or documents change.
Order Certified Copies
Most orders are placed with the USPTO same day — all within 24 business hours.
Order via The Patent Place →
Pre-filled with this patent's details
Quick Facts
Patent No.
US 9,434,823
App. No.
14/352,158
Granted
Sep 6, 2016
Kind
B2
Abstract

A process for the synthesis of a diene copolymer comprising at least two blocks, at least one of the blocks being composed of a diene elastomer, characterized in that it comprises a stage of 1,3-dipolar reaction of two polymers defined as being: a) a diene elastomer bearing an alkyne functional group at one or each of its chain ends, and b) a polymer bearing at least one azide functional group. This process of synthesis can be adjusted, whatever the nature of the monomers necessary to form each of the blocks of the copolymer. Each block can be synthesized with an appropriate chemistry, independently of the other block.

Claims (21)

1. A process for the synthesis of a diene copolymer comprising at least two blocks, at least one of the blocks being composed of a diene elastomer, comprising a 1,3-dipolar reaction of two polymers defined as being:

a diene elastomer bearing an alkyne functional group at one or each of its chain ends, and

a polymer bearing at least one azide functional group.

2. The process for the synthesis of a diene block copolymer according to claim 1 , wherein the diene elastomer bears an alkyne functional group at one or each of its chain ends corresponds to the following formula 2:

(A-E) n -X  Formula 2

in which wherein:

X denotes a hydrocarbon group of valency n or a group resulting from a functionalization, coupling and star-branching agent comprising at least one atom chosen from O, N, Si or Sn;

A is a monovalent hydrocarbon radical comprising an alkyne functional group;

E denotes the diene elastomer, and

n is an integer ranging from 1 to 12.

3. The process for the synthesis of a diene block copolymer according to claim 2 , wherein X comprises at least one group selected from the group consisting of amine, silanol, alkoxysilane, alkoxysilane bearing an amine group, epoxide, ether, ester, hydroxyl, and carboxylic acid groups.

4. The process for the synthesis of a diene block copolymer according to claim 2 , wherein A represents a substituted or unsubstituted aliphatic alkynyl radical having from 2 to 15 carbon atoms.

5. The process for the synthesis of a diene block copolymer according to claim 4 , wherein A represents a 5-trialkylsilyl-4-pentynyl group.

6. The process for the synthesis of a diene block copolymer according to claim 2 , wherein A represents a monovalent radical corresponding to the following formula 3:

in which wherein:

* denotes a point of bonding with the elastomer chain E which is located in the ortho, meta or para position of A with respect to the group comprising the carbon-carbon triple bond,

R 1 and R 2 , and also R 3 and R 4 , which can be borne by the ortho, meta or para position, denote, independently of one another, denote a hydrogen atom, a C 1 -C 15 alkyl group, a C 5 -C 15 cycloalkyl group, a C 6 -C 15 aryl group or a C 7 -C 15 arylalkyl group which can be separated from the aromatic nucleus by a heteroatom, such as O or S, and

R 5 denotes a hydrogen atom, a C 1 -C 5 alkyl group, a cycloalkyl group, a C 6 -C 15 aryl group, a C 7 -C 15 arylalkyl group, or a protective group for the alkyne functional group.

7. The process for the synthesis of a diene block copolymer according to claim 1 , further comprising, prior to the reaction of the two polymers a) and b), synthesis of the diene elastomer comprising the anionic polymerization of at least one conjugated diene monomer initiated by an organolithium compound comprising an alkyne bond, thereby preparing a living diene elastomer bearing, at a chain end, a protected or unprotected alkyne bond.

8. The process for the synthesis of a diene block copolymer according to claim 7 , further comprising, on conclusion of the anionic polymerization stage, subjecting the living elastomer to a functionalization by reaction with a functionalization, coupling, or star-branching agent thereby forming a diene elastomer bearing a protected or unprotected alkyne functional group at one or each of its chain ends.

9. The process for the synthesis of a diene block copolymer according to claim 1 , further comprising deprotecting of the alkyne functional group.

Assignments (2)
ASSIGNMENT OF ASSIGNOR'S INTEREST Recorded Jun 8, 2020
From: MICHELIN RECHERCHE ET TECHNIQUE S.A.
To: COMPAGNIE GENERALE DES ETABLISSEMENTS MICHELIN
Reel/Frame 052863/0624 →
ASSIGNMENT OF ASSIGNOR'S INTEREST Recorded Sep 25, 2014
From: MATMOUR, RACHID; SEEBOTH, NICOLAS
To: COMPAGNIE GENERALE DES ETABLISSEMENTS MICHELIN; MICHELIN RECHERCHE ET TECHNIQUE S.A.
Reel/Frame 033817/0255 →
Priority Claims (1)
FR 11 59399 · Oct 18, 2011 · national
Continuity (1)
Related Publication 20140228510A1 · Aug 14, 2014