Mixtures of aminosilyl-functionalized styrenes, their preparation and their use in the production of elastomeric copolymers

A method for the preparation of an initiator component comprising an alkali metal salt derivative of a mixture of two or more styrene derivatives of Formula (I),

• wherein
• n is 0 or 1;
• R1 and R2 are the same or different and represent an alkyl group containing from 1 to 10 carbon atoms, or an aryl or aralkyl group containing from 6 to 10 carbon atoms;
• and
• i) R3 and R4 are the same or different and each R3 and R4 independently represents i) a hydrocarbyl group containing from 1 to 10 carbon atoms, the hydrocarbyl group optionally being interrupted by at least one heteroatom selected from a silicon atom, an oxygen atom or a nitrogen atom;
• or ii) an aryl or aralkyl group containing from 6 to 10 carbon atoms and optionally at least one heteroatom selected from a silicon atom, an oxygen atom or a nitrogen atom;
• or
• ii) R3 and R4 are bonded to each other to form a heterocyclic ring containing the nitrogen atom and at least one carbon atom and, optionally, at least one heteroatom selected from a silicon atom, an oxygen atom and a nitrogen atom;
• and
• the mixture of the two or more styrene derivatives of Formula (I) comprises (1) para isomer and (2) meta or ortho isomer of one type of the styrene derivative of Formula (I), wherein in the mixture of the two or more styrene derivatives of Formula (I), the weight ratio of the para isomer to the meta or ortho isomer ranges from 1:9 to 9:1,
• the method comprising
• (a) reacting a halogenosilane of Formula (II)
• wherein X1 is selected from chlorine, bromine, and iodine atoms, and R1, R2, R3 and R4 are as defined above,
• with a mixture of two or more magnesium compounds of Formula (III),
• wherein X2 is selected from chlorine, bromine, and iodine atoms to obtain the mixture of two or more styrene derivatives of Formula (I);
• and
• (b) converting the mixture of two or more styrene derivatives of Formula (I) into the alkali metal salt derivative.

A process for the preparation of a copolymer component comprising coupled copolymer and terminally modified copolymer, the process comprising the following steps:

• (1) providing an initiator component comprising an alkali metal salt derivative of a mixture of two or more styrene derivatives of Formula (I),
• wherein
• n is 0 or 1;
• R1 and R2 are the same or different and represent an alkyl group containing from 1 to 10 carbon atoms, or an aryl or aralkyl group containing from 6 to 10 carbon atoms;
• and
• i) R3 and R4 are the same or different and each R3 and R4 independently represents i) a hydrocarbyl group containing from 1 to 10 carbon atoms, the hydrocarbyl group optionally being interrupted by at least one heteroatom selected from a silicon atom, an oxygen atom or a nitrogen atom;
• or ii) an aryl or aralkyl group containing from 6 to 10 carbon atoms and optionally at least one heteroatom selected from a silicon atom, an oxygen atom or a nitrogen atom;
• or
• ii) R3 and R4 are bonded to each other to form a heterocyclic ring containing the nitrogen atom and at least one carbon atom and, optionally, at least one heteroatom selected from a silicon atom, an oxygen atom and a nitrogen atom;
• and
• the two or more styrene derivatives of Formula (I) comprise (x) para isomer and (y) meta or ortho isomer of one type of the styrene derivative of Formula (I), wherein in the mixture of the two or more styrene derivatives of Formula (I), the weight ratio of the para isomer to the meta or ortho isomer ranges from 1:9 to 9:1,
• (2) contacting a monomer component comprising
• i) one or more conjugated diene monomers and
• ii) optionally one or more vinyl aromatic monomers
• with the initiator component, to initiate anionic copolymerization;
• (3) continuing copolymerization, to result in a copolymer;
• (4) optionally continuing copolymerization of the copolymer, in the presence of one or more functionalized monomers, to result in a functionalized copolymer;
• (5) coupling a part of the copolymer of step (3) or the functionalized copolymer of step (4) with one or more coupling agents, to result in coupled copolymer;
• and
• (6) terminally modifying a part of the copolymer of step (3) or the functionalized copolymer of step (4) with one or more terminal modifying agents, to result in terminally modified copolymer,
• wherein the monomer component in step (2) comprises the two or more styrene derivatives of Formula (I).

A process for producing an elastomeric copolymer comprising subjecting

• one or more diene monomers,
• optionally one or more vinyl aromatic monomers and
• a mixture of two or more styrene derivatives of Formula (I)
• wherein
• n is 0 or 1;
• R1 and R2 are the same or different and represent an alkyl group containing from 1 to 10 carbon atoms, or an aryl or aralkyl group containing from 6 to 10 carbon atoms;
• and
• i) R3 and R4 are the same or different and each R3 and R4 independently represents i) a hydrocarbyl group containing from 1 to 10 carbon atoms, the hydrocarbyl group optionally being interrupted by at least one heteroatom selected from a silicon atom, an oxygen atom or a nitrogen atom;
• or ii) an aryl or aralkyl group containing from 6 to 10 carbon atoms and optionally at least one heteroatom selected from a silicon atom, an oxygen atom or a nitrogen atom;
• or
• ii) R3 and R4 are bonded to each other to form a heterocyclic ring containing the nitrogen atom and at least one carbon atom and, optionally, at least one heteroatom selected from a silicon atom, an oxygen atom and a nitrogen atom;
• and
• the mixture of the two or more styrene derivatives of Formula (I) comprises (1) para isomer and (2) meta or ortho isomer of one type of the styrene derivative of Formula (I), wherein in the mixture of the two or more styrene derivatives of Formula (I), the weight ratio of the para isomer to the meta or ortho isomer ranges from 1:9 to 9:1,
• to anionic polymerization conditions,
• wherein an alkali metal salt derivative of the mixture of the two or more styrene derivatives of Formula (I) is used as an initiator for the anionic polymerization.

An elastomeric copolymer comprising repeat units that are derived from

• A) 20 wt. % to 99.95 wt. %, by weight of the copolymer, of one or more diene monomers;
• B) 0 wt. % to 60 wt. %, by weight of the copolymer, of one or more vinyl aromatic monomers;
• and
• C) 0.05 wt. % to 50 wt. %, by weight of the copolymer, of two or more styrene derivatives of Formula (I)
• wherein
• n is 0 or 1;
• R1 and R2 are the same or different and represent an alkyl group containing from 1 to 10 carbon atoms, or an aryl or aralkyl group containing from 6 to 10 carbon atoms;
• and
• i) R3 and R4 are the same or different and each R3 and R4 independently represents i) a hydrocarbyl group containing from 1 to 10 carbon atoms, the hydrocarbyl group optionally being interrupted by at least one heteroatom selected from a silicon atom, an oxygen atom or a nitrogen atom;
• or ii) an aryl or aralkyl group containing from 6 to 10 carbon atoms and optionally at least one heteroatom selected from a silicon atom, an oxygen atom or a nitrogen atom;
• or
• ii) R3 and R4 are bonded to each other to form a heterocyclic ring containing the nitrogen atom and at least one carbon atom and, optionally, at least one heteroatom selected from a silicon atom, an oxygen atom and a nitrogen atom, and
• the one or more vinyl aromatic monomers in B), when present, is different from the two or more styrene derivatives of Formula (I) in C), and
• the two or more styrene derivatives of Formula (I) comprise (1) para isomer and (2) meta or ortho isomer of one type of the styrene derivative of Formula (I), wherein in the mixture of the two or more styrene derivatives of Formula (I), the weight ratio of the para isomer to the meta or ortho isomer ranges from 1:9 to 9:1,
• wherein the elastomeric copolymer is prepared using an alkali metal salt derivative of the two or more styrene derivatives of Formula (I) as an initiator.