Anionic polymerization initiator, use thereof for synthesizing a diene elastomer having an alkyne function at the chain end, and functionalized diene elastomer
View Patent ↗An anionic polymerization initiator of formula: in which: Met, which can be borne by the ortho, meta or para position, denotes an alkali metal, R 1 and R 2 , and also R 3 and R 4 , which can be borne by the ortho, meta or para position, denote a hydrogen atom or an alkyl, cycloalkyl, aryl or arylalkyl group, and R 5 denotes an alkyl, cycloalkyl, aryl or arylalkyl group or a protective group for the alkyne functional group. The use of such a polymerization initiator makes possible the synthesis of a diene elastomer bearing, at one or each of its chain ends, a group comprising an alkyne functional group with a high degree of functionalization.
1. A process for the synthesis of a diene elastomer bearing, at one or each of its chain ends, a group comprising an alkyne functional group, comprising the anionic polymerization of at least one conjugated diene monomer initiated by an organometallic compound comprising an alkyne bond of formula 1:
wherein
Met, which can be borne by the ortho, meta or para position with respect to the group comprising the carbon-carbon triple bond, denotes an alkali metal, and
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, 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, and
R 5 denotes a C 1 -C 5 alkyl group, a C 5 -C 15 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.
2. A process for the synthesis of a diene elastomer bearing, at one or each of its chain ends, a group comprising an alkyne functional group according to claim 1 , further comprising functionalizing of the diene elastomer by reaction of the living diene elastomer resulting from the polymerization with a functionalization, coupling or star-branching agent.
3. The process for the synthesis of a diene elastomer bearing, at one or each of its chain ends, a group comprising an alkyne functional group according to claim 1 further comprising deprotecting of the alkyne functional group when R 5 denotes a protective group for the alkyne functional group.
4. A diene elastomer bearing, at one or each of its chain ends, a group comprising an alkyne functional group, corresponding to the following formula 3:
(A-E) n -X Formula 3
wherein:
X denotes a hydrocarbon group of valency n or a group resulting from a functionalization, coupling or star-branching agent comprising at least one atom chosen from O, N, Si or Sn;
A is a monovalent radical corresponding to the following formula 2:
wherein:
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, 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,
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, and
* indicates a point of bonding with the elastomer E,
E, which can be borne by the ortho, meta or para position of A with respect to the group comprising the carbon-carbon triple bond, denotes the diene elastomer, and
n is an integer ranging from 1 to 12.