Tin-containing organolithium compounds and preparation thereof

A tin-containing organolithium compound used as anionic polymerization initiators, characterized in that said compound is represented by the following formula (1):

• R4−xSn(Ya—Zm—Yb—Li)x (1)
• wherein R represents C1-C20-alkyl, C3-C20-cycloalkyl or C6-C20-aryl or substituted aryl;
• Z represents arylene or substituted arylene of formulae (a), (b), (c), (d), (e) or (f):
• Y represents a group derived from conjugated diene homopolymers, monovinyl aromatic hydrocarbon homopolymers or conjugated diene/monovinyl aromatic hydrocarbon colymers;
• x represents a value of 1 or 2;
• m represents a value of 0 or 1;
• a represents a value of 0 to 6, b represents a value of 0 to 6, and a+b is from 0 to 6, provided that m=1 when x=1.

A tin-containing organolithium compound used as anionic polymerization initiators, characterized in that said compound is represented by the following formula (1):

• R4−xSn(Ya—Zm—Yb—Li)x (1)
• wherein R represents C1-C20-alkyl, C3-C20-cycloalkyl or C6-C20-aryl or substituted aryl;
• Z represents straight or branched C1-C20 a divalent hydrocarbon group, C6-C30-arylene or substituted arylene;
• Y represents a group derived from conjugated diene homopolymers monovinyl aromatic hydrocarbon homopolymers or conjugated diene/monovinyl aromatic hydrocarbon copolymers;
• x represents a value of 1 or 2;
• m represents a value of 0 or 1;
• a represents a value of 0 to 6, b represents a value of 0 to 6, and a+b is from 0 to 6, provided that m is 1 and a and b cannot be both 0 when x is 1, with said conjugated diene in the definition of Y being butadiene, isoprene or derivatives thereof and the monovinyl aromatic hydrocarbon being styrene or α-methylstyrene.

A tin-containing organolithium compound used as anionic polymerization initiators, characterized in that said compound is represented by the following formula (1):

• R4−xSn(Ya—Zm—Yb—Li)x (1)
• wherein R represents C1-C20-alkyl, C3-C20-cycloalkyl or C6-C20-aryl or substituted aryl;
• Z represents straight or branched C1-C20 divalent hydrocarbon group, C6-C30-arylene or substituted arylene;
• Y represents a group derived from conjugated diene homopolymers, monovinyl aromatic hydrocarbon homopolymers or conjugated diene/monovinyl aromatic hydrocarbon copolymers;
• x represents a value of 1;
• m represents a value of 1;
• a represents a value of 0, b represents a value of 0 to 6, and a+b is from 0 to 6, provided that b≠0.

A tin-containing organolithium compound used as anionic polymerization initiators, characterized in that said compound is represented by the following formula (1):

• R4−xSn(Ya—Zm—Yb—Li)x (1)
• wherein R represents C1-C20-alkyl, C3-C20-cycloalkyl or C6-C20-aryl or substituted aryl;
• Z represents straight or branched C1-C20 divalent hydrocarbon group, C6-C30-arylene or substituted arylene;
• Y represents a group derived from conjugated diene homopolymers, monovinyl aromatic hydrocarbon homopolymers or conjugated diene/monovinyl aromatic hydrocarbon copolymers;
• x represents a value of 1;
• m represents a value of 1;
• a represents a value of 0 to 6, b represents a value of 0 to 6, and a+b is from 0 to 6, provided that that a≠0 and b≠0.

A tin-containing organolithium compound used as anionic polymerization initiators, characterized in that said compound is represented by the following formula (1):

• R4−xSn(Ya—Zm—Yb—Li)x (1)
• wherein R represents C1-C20-alkyl, C3-C20-cycloalkyl or C6-C20-aryl or substituted aryl;
• Z represents straight or branched C1-C20 divalent hydrocarbon group, C6-C30-arylene or substituted arylene;
• Y represents a group derived from conjugated diene homopolymers, monovinyl aromatic hydrocarbon homopolymers or conjugated diene/monovinyl aromatic hydrocarbon copolymers;
• x represents a value of 2;
• m represents a value of 0 or 1;
• and a+b=0.

A tin-containing organolithium compound used as anionic polymerization initiators, characterized in that said compound is represented by the following formula (1):

• R4−xSn(Ya—Zm—Yb—Li)x (1)
• wherein R represents C1-C20-alkyl, C3-C20-cycloalkyl or C6-C20-aryl or substituted aryl;
• Z represents straight or branched C1-C20 divalent hydrocarbon group, C6-C30-arylene or substituted arylene;
• Y represents a group derived from conjugated diene homopolymers, monovinyl aromatic hydrocarbon homopolymers or conjugated diene/monovinyl aromatic hydrocarbon copolymers;
• x represents a value of 2;
• m represents a value of 0;
• and a represents a value of 0 to 6, b represents a value of 0 to 6, and a+b is from 0 to 6, provided that a+b≠0.

A tin-containing organolithium compound used as anionic polymerization initiators, characterized in that said compound is represented by the following formula (1):

• R4−xSn(Ya—Zm—Yb—Li)x (1)
• wherein R represents C1-C20-alkyl, C3-C20-cycloalkyl or C6-C20-aryl or substituted aryl;
• Z represents straight or branched C1-C20 divalent hydrocarbon group, C6-C30-arylene or substituted arylene;
• Y represents a group derived from conjugated diene homopolymers, monovinyl aromatic hydrocarbon homopolymers or conjugated diene/monovinyl aromatic hydrocarbon copolymers;
• x represents a value of 2;
• m represents a value of 1;
• a represents a value of 0, b represents a value of 0 to 6, and a+b is from 0 to 6, provided that b≠0.

A tin-containing organolithium compound used as anionic polymerization initiators, characterized in that said compound is represented by the following formula (1):

• R4−xSn(Ya—Zm—Yb—Li)x (1)
• wherein R represents C1-C20-alkyl, C3-C20-cycloalkyl or C6-C20-aryl or substituted aryl;
• Z represents straight or branched C1-C20 divalent hydrocarbon group, C6-C30-arylene or substituted arylene;
• Y represents a group derived from conjugated diene homopolymers, monovinyl aromatic hydrocarbon homopolymers or conjugated diene/monovinyl aromatic hydrocarbon copolymers;
• x represents a value of 2;
• m represents a value of;
• a represents a value of 0 to 6, b represents a value of 0 to 6, and a+b is from 0 to 6, provided that a≠0 and b≠0.

A method for preparing a tin-containing organolithium compound used as anionic polymerization initiators, said compound being represented by the following formula (1):

• R4−xSn(Ya—Zm—Yb—Li)x (1)
• wherein R represents C1-C20-alkyl, C3-C20-cycloalkyl or C6-C20-aryl or substituted aryl;
• Z represents straight or branched C1-C20 divalent hydrocarbon group, C6-C30-arylene or substituted arylene;
• Y represents a group derived from conjugated diene homopolymers, monovinyl aromatic hydrocarbon homopolymers or conjugated diene/monovinyl aromatic hydrocarbon copolymers;
• x represents a value of 1;
• m represents a value of 1;
• a represents a value of 0 to 6, b represents a value of 0 to 6, and a+b is from 0 to 6, comprising the steps of:
• i) preparing a bislithium compound of formula (2):
• LiZLi (2)
• wherein Z represents straight or branched C1-C20 divalent hydrocarbon group, C6-C30-arylene or substituted arylene;
• ii) adding a halide of formula (3):
• R3SnX (3)
• wherein R represents C1-C20-alkyl, C3-C20-cycloalkyl or C6-C20-aryl or substituted aryl;
• X is halogen selected from fluorine, chlorine, bromine and iodine;
• and optionally
• iii) adding and polymerizing conjugated diene monomers, monovinyl aromatic hydrocarbon monomers or mixtures thereof, prior to or after step ii), to form a low molecular weight oligomer having an active site.

A method for preparing a tin-containing organolithium compound as defined in claim 54, comprising the steps of:

• i) preparing the bislithium compound of formula (2)
• LiZLi (2)
• wherein Z represents straight or branched C1-C20 divalent hydrocarbon group, C6-C30-arylene or substituted arylene;
• and
• ii) adding the halide of formula (3)
• R3SnX (3)
• wherein R represents C1-C20-alkyl, C3-C20-cycloalkyl or C6-C20-aryl or substituted aryl;
• and X is halogen selected from fluorine, chlorine, bromine and iodine;
• and
• iii) reacting the halide of formula (3) with the bislithium compound resulting from step i), to obtain a compound of formula (1a):
• R3SnZLi (1a)
• wherein Z represents straight or branched C1-C20 divalent hydrocarbon group, C6-C30-arylene or substituted arylene and R represents C1-C20-alkyl, C3-C20-cycloalkyl or C6-C20-aryl or substituted aryl.