Transition metal compound, polymerization catalyst using same and process for producing styrenic polymer using said polymerization catalyst

Abstract

There are disclosed a transition metal compound of the general formula RMX a-1 L b (R is a π ligand, a fused polycyclic cyclopentadienyl group in which at least one of many-membered rings to which cyclopentadienyl groups are fusedly bonded is a saturated ring, M is a transition metal, X is a σ ligand, L is a Lewis base, a is the valency of M, and b is 0, 1 or 2); a polymerization catalyst for styrene, etc. comprising the above transition metal, preferably further comprising an oxygen atom containing compound ionic compound or organoboron compound and optionally a Lewis base; and a process for producing a polymer of a compound containing an ethylenically unsaturated double bond or an acetylenic polymer, especially a syndiotactic polystyrene by using the above polymerization catalyst. The catalyst is particularly effective for producing highly syndiotactic polystyrene minimized in residual metals amounts at a low cost in enhanced efficiency.

What is claimed is: 
     
       1. A polymerization catalyst for a compound containing an ethylenically unsaturated double bond or an acetylenic bond, which catalyst comprises: (A) a transition metal compound represented by formula (I)   RMX.sub.a-1 L.sub.b                                        (I)        wherein R is, as a π ligand, a fused bicyclic or tricyclic cyclopentadienyl group in which at least one of many-membered rings to which a cyclopentadienyl group is fusedly bonded is a saturated ring; M is a transition metal, X is a σ ligand, a plurality of moieties X may be the same or different, L is a Lewis base, a is the valency of moiety M, b is 0, 1 or 2 and when L is a plurality, each L may be the same or different; and   (B) an aluminoxane.   
     
     
       2. A polymerization catalyst for a compound containing an ethylenically unsaturated double bond or an acetylenic bond, which catalyst comprises: (A) a transition metal compound represented by formula (I)   RMX.sub.a-1 L.sub.b                                        (I)        wherein R is, as a π ligand, a fused bicyclic or tricyclic cyclopentadienyl group in which at least one of many-membered rings to which a cyclopentadienyl group is fusedly bonded is a saturated ring; M is a transition metal, X is a σ ligand, a plurality of moieties X may be the same or different, L is a Lewis base, a is the valency of moiety M, b is 0, 1 or 2 and when L is a plurality, each L may be the same or different;   component (B) is at least one member selected from the group consisting of an (1) aluminoxane, (2) an ionic compound comprising a noncoordinating anion and a cation, and (3) an organoboron compound; and   (C) a Lewis acid.   
     
     
       3. A polymerization catalyst for a compound containing an ethylenically unsaturated double bond or an acetylenic bond, which catalyst comprises: (A) a transition metal compound represented by formula (I)   RMX.sub.a-1 L.sub.b                                        (I)        wherein R is, as a π ligand, a fused bicyclic or tricyclic cyclopentadienyl group in which at least one of many-membered rings to which a cyclopentadienyl group is fusedly bonded is a saturated ring; M is a transition metal, X is a σ ligand, a plurality of moieties X may be the same or different, L is a Lewis base, a is the valency of moiety M, b is 0, 1 or 2 and when moiety L is a plurality, each L may be the same or different; and   component (B) is an ionic compound comprising a non-coordinating anion and a cation; and   component (C) is a Lewis acid.   
     
     
       4. The .[.transition metal compound.]. .Iadd.polymerization catalyst .Iaddend.according to claim 1, wherein R .Iadd.of said transition metal compound .Iaddend.is selected from the fused polycyclic cyclopentadienyl group represented by any one of formulae (II) to (IV) ##STR9## wherein R 1 , R 2  and R 3  are each hydrogen, halogen, an aliphatic hydrocarbon group having 2 to 20 carbon atoms, an aromatic hydrocarbon group having 6 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an aryloxyl group having 6 to 20 carbon atoms, a thioalkoxyl group having 1 to 20 carbon atoms, a thioaryloxyl group having 6 to 20 carbon atoms, an amino group, an amide group, a carboxyl group or an alkylsilyl group and may be the same as or different from each other; and c, d, e and f are each an integer of one or greater. 
     
     
       5. The .[.transition metal compound.]. .Iadd.polymerization catalyst .Iaddend.according to claim 2, wherein R .Iadd.of said transition metal compound .Iaddend.is selected from the fused polycyclic cyclopentadienyl group represented by any one of formulae (II) to (IV) ##STR10## wherein R 1 , R 2  and R 3  are each hydrogen, halogen, an aliphatic hydrocarbon group having 2 to 20 carbon atoms, an aromatic hydrocarbon group having 6 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an aryloxyl group having 6 to 20 carbon atoms, a thioalkoxyl group having 1 to 20 carbon atoms, a thioaryloxyl group having 6 to 20 carbon atoms, an amino group, an amide group, a carboxyl group or an alkylsilyl group and may be the same as or different from each other; and c, d, e and f are each an integer of one or greater. 
     
     
       6. The .[.transition metal compound.]. .Iadd.polymerization catalyst .Iaddend.according to claim 3, wherein R .Iadd.of said transition metal compound .Iaddend.is selected from the fused polycyclic cyclopentadienyl group represented by any one of formulae (II) to (IV) ##STR11## wherein R 1 , R 2  and R 3  are each hydrogen, halogen, an aliphatic hydrocarbon group having 2 to 20 carbon atoms, an aromatic hydrocarbon group having 6 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an aryloxyl group having 6 to 20 carbon atoms, a thioalkoxyl group having 1 to 20 carbon atoms, a thioaryloxyl group having 6 to 20 carbon atoms, an amino group, an amide group, a carboxyl group or an alkylsilyl group and may be the same as or different from each other; and c, d, e and f are each an integer of one or greater. 
     
     
       7. The polymerization catalyst of claim 4, wherein R is a 4,5,6,7-tetrahydroindenyl group. 
     
     
       8. The polymerization catalyst of claim 5, wherein R is a 4,5,6,7-tetrahydroindenyl group. 
     
     
       9. The polymerization catalyst of claim 6, wherein R is a 4,5,6,7-tetrahydroindenyl group. 
     
     
       10. A process for producing a polymer of a compound containing an ethylenically unsaturated double bond or a polymer of an acetylenic compound, which comprises: polymerizing said ethylenically unsaturated compound or said acetylenic compound in the presence of the polymerization catalyst of claim 1.   
     
     
       11. A process for producing a polymer of a compound containing an ethylenically unsaturated double bond or a polymer of an acetylenic compound, which comprises: polymerizing said ethylenically unsaturated compound or said acetylenic compound in the presence of the polymerization catalyst of claim 2.   
     
     
       12. A process for producing a polymer of a compound containing an ethylenically unsaturated double bond or a polymer of an acetylenic compound, which comprises: polymerizing said ethylenically unsaturated compound or said acetylenic compound in the presence of the polymerization catalyst of claim 3.   
     
     
       13. A process for producing a styrenic polymer, which comprises: copolymerizing a styrenic monomer and another polymerizable unsaturated compound in the presence of the polymerization catalyst of claim 1.   
     
     
       14. A process for producing a styrenic polymer, which comprises: copolymerizing a styrenic monomer and another polymerizable unsaturated compound in the presence of the polymerization catalyst of claim 2.   
     
     
       15. A process for producing a styrenic polymer, which comprises: copolymerizing a styrenic monomer and another polymerizable unsaturated compound in the presence of the polymerization catalyst of claim 3.   
     
     
       16. The process of claim 13, wherein said styrenic polymer exhibits a high degree of syndiotacticity. 
     
     
       17. The process of claim 14, wherein said styrenic polymer exhibits a high degree of syndiotacticity. 
     
     
       18. The process of claim 15, wherein said styrenic polymer exhibits a high degree of syndiotacticity.