Metallocene complex and polymerization catalyst composition containing the same
View Patent ↗Disclosed are a metallocene complex represented by the general formula (I), (II) or (III), and a polymerization catalyst composition containing such a metallocene complex. In the formulae (I), (II) and (III), M represents a lanthanoid element, scandium or yttrium; Cp R independently represents an unsubstituted or substituted indenyl; Cp R′ represents an unsubstituted or substituted cyclopentadienyl, indenyl or fluorenyl; R a -R f independently represents a hydrogen or an alkyl group having 1-3 carbon atoms; X and X′ respectively represent a hydrogen atom, a halogen atom, an alkoxide group, a thiolate group, an amide group, a silyl group or a hydrocarbon group having 1-20 carbon atoms; L represents a neutral Lewis base; w represents an integer of 0-3; and [B] − represents a non-coordinating anion.
1. A metallocene complex represented by the following general formula (I),
where: M represents samarium, neodymium, praseodymium, gadolinium, terbium, cerium, holmium, scandium, or yttrium;
Cp R independently represents an unsubstituted or substituted indenyl group, and is represented by the formula C 9 H 7−x R x wherein x represents an integer of 0 to 7 or is represented by the formula C 9 H 11−x R x wherein x represents an integer of 0 to 11, and R independently represents a hydrocarbyl group or a trimethyl silyl group;
R a to R f independently represents hydrogen or an alkyl group having 1 to 3 carbon atoms;
L represents a neutral Lewis base; and
w represents an integer of 0 to 3.
2. A polymerization catalyst composition, comprising (i) the metallocene complex according to claim 1 and (ii) a co-catalyst.
3. The polymerization catalyst composition according to claim 2 , which is used for polymerizing a conjugate diene.
4. The polymerization catalyst composition according to claim 2 , further comprising an aluminoxane.
5. The polymerization catalyst composition according to claim 2 , further comprising one of or both of an organic aluminum compound and an ionic compound.
6. A method of producing an addition polymer, comprising polymerizing addition-polymerizable monomers in the presence of the polymerization catalyst composition according to claim 2 .
7. The method according to claim 6 , wherein:
the addition-polymerizable monomer is a conjugate diene; and the addition polymer is a conjugate diene polymer.
8. The method according to claim 6 , wherein:
the addition-polymerizable monomer is 1,3-butadiene; and the addition polymer is a butadiene polymer.
9. The method according to claim 6 , wherein:
the addition-polymerizable monomer is a disconjugate olefin; and the addition polymer is a disconjugate olefin polymer.
10. The method according to claim 6 , wherein:
the addition-polymerizable monomer is at least one monoolefin selected from C2 to C10 disconjugate olefins and a styrene; and the addition polymer is a monoolefin polymer or copolymer each obtained by reacting at least one selected from C2 to C10 disconjugate olefins with styrene.
11. The method according to claim 10 , wherein:
the addition-polymerizable monomer further comprises a conjugate diene; and
the addition polymer is a copolymer of the conjugate diene and the monoolefin.
12. A method for producing a half metallocene cation complex represented by the following general formula (III), comprising subjecting a compound represented by the following general formula (IV) to a reaction with an ionic compound represented by the general formula [A] + [B] −
where: M represents a lanthanoid element, scandium, or yttrium;
Cp R′ independently represents an unsubstituted or substituted cyclopentadienyl, indenyl, or fluorenyl group;
X represents a hydrogen atom, a halogen atom, an alkoxide group, a thiolate group, an amide group, a silyl group, or a hydrocarbon group having 1 to 20 carbon atoms;
L represents a neutral Lewis base;
w represents an integer of 0 to 3;
[A] + represents a cation; and
[B] − represents a non-coordinating anion.
13. The method according to claim 12 , wherein Cp R′ represents an unsubstituted or substituted indenyl group.
14. The metallocene complex according to claim 1 , wherein R independently represents a methyl group, an ethyl group, a phenyl group, a benzyl group or a trimethyl silyl group.