Claims
- 1. A method for forming a prepolymerized supported metallocene catalyst system, said method comprising the steps of:
- (a) forming a reaction product of metallocene and alkylalumoxane in a hydrocarbon solvent;
- (b) contacting a volume of the reaction product with a porous support;
- (c) drying the resulting supported catalyst system such that at least 90% of all solvent is removed from the pores of the porous support;
- (d) contacting the dried supported catalyst system of step (c) with a volume of hydrocarbon solution wherein the volume is equal to or less than the total pore volume of the porous support;
- (e) prepolymerizing the supported catalyst system with gaseous monomer; and
- (f) recovering prepolymerized supported catalyst system.
- 2. The method of claim 1 wherein the alkylalumoxane is methylalumoxane.
- 3. The method of claim 1 wherein the metallocene is represented by the general formula: ##STR6## wherein M is a metal of group 4, 5, or 6 of the Periodic Table, R.sup.1 and R.sup.2 are identical or different, are one of a hydrogen atom, a C.sub.1 -C.sub.10 alkyl group, a C.sub.1 -C.sub.10 alkoxy group, a C.sub.6 -C.sub.10 aryl group, a C.sub.6 -C.sub.10 aryloxy group, a C.sub.2 -C.sub.10 alkenyl group, a C.sub.7 -C.sub.40 arylalkyl group, a C.sub.8 -C.sub.40 arylalkenyl group, or a halogen atom;
- R.sup.3 and R.sup.4 are hydrogen atoms;
- R.sup.5 and R.sup.6 are identical or different, preferably identical, are one of a halogen atom, a C.sub.1 -C.sub.10 alkyl group, which may be halogenated, a C.sub.6 -C.sub.10 aryl group, which may be halogenated, a C.sub.2 -C.sub.10 alkenyl group, a C.sub.7 -C.sub.40 arylalkyl group, a C.sub.7 -C.sub.40 alkylaryl group, a C.sub.8 -C.sub.40 arylalkenyl group, a --NR.sub.2.sup.15, --SR.sup.15, --OR.sup.15, --OSiR.sub.3.sup.15 or --PR.sub.2.sup.15 radical, wherein R.sup.15 is one of a halogen atom, a C.sub.1 -C.sub.10 alkyl group, or a C.sub.6 -C.sub.10 aryl group;
- R.sup.7 is ##STR7## .dbd.BR.sup.11,.dbd.AlR.sup.11, --Ge--, --Sn--, --O--, --S--, .dbd.SO, .dbd.SO.sub.2, .dbd.NR.sup.11, .dbd.CO, PR.sup.11, or .dbd.P(O)R.sup.11 ;
- wherein:
- R.sup.11, R.sup.12 and R.sup.13 are identical or different and are a hydrogen atom, a halogen atom, a C.sub.1 -C.sub.20 alkyl group, a C.sub.1 -C.sub.20 fluoroalkyl group, a C.sub.6 -C.sub.30 aryl group, a C.sub.6 -C.sub.30 fluoroaryl group, a C.sub.1 -C.sub.20 alkoxy group, a C.sub.2 -C.sub.20 alkenyl group, a C.sub.7 -C.sub.40 arylalkyl group, a C.sub.8 -C.sub.40 arylalkenyl group, C.sub.7 -C.sub.40 alkylaryl group, or R.sup.11 and R.sup.12, or R.sup.11 and R.sup.13, together with the atoms binding them, can form ring systems;
- M.sup.2 is silicon, germanium or tin;
- R.sup.8 and R.sup.9 are identical or different and have the meanings as stated for R.sup.11 ;
- m and n are identical or different and are zero, 1 or 2, m plus n being zero, 1 or 2; and
- the radicals R.sup.10 are identical or different and have the meanings stated for R.sup.11, R.sup.12 and R.sup.13 wherein further two adjacent R.sup.10 radicals can be joined together to form a ring system.
- 4. The method of claim 1 wherein the metallocene comprises two or more metallocene catalyst components.
- 5. The method of claim 1 wherein the mole ratio of aluminum of the alkylalumoxane to the transition metal of the metallocene is in the range of between 20:1 to less than 500:1.
- 6. The method of claim 1 wherein the olefin monomer is selected from the group consisting of ethylene, propylene, and butene.
- 7. The method of claim 1 wherein the liquid is an aliphatic hydrocarbon selected from the group consisting of pentane, hexane, and heptane.
- 8. The method of claim 3 wherein m=n=0 and M.sup.2 =silicon.
- 9. The method of claim 3 wherein R.sup.5 =R.sup.6 =C.sub.1-10 alkyl.
- 10. The method of claim 3 wherein three of the R.sup.10 radicals=hydrogen and one is a C.sub.6-30 aryl group.
- 11. The method of claim 3 wherein two adjacent R.sup.10 radicals form a fused 4,5-benzo ring and the other two R.sup.10 radicals are hydrogen.
- 12. The method of claim 3 wherein at least one of the R.sup.10 radicals is C.sub.1-10 alkyl.
- 13. The method of claim 1 wherein the metallocene is selected from the group consisting essentially of:
- rac-dimethylsilandiylbis(2-methyl-4,5-benzoindenyl)zirconium dichloride;
- rac-dimethylsilandiylbis(2-methylindenyl)zirconium dichloride;
- rac-dimethylsilandiylbis(2-methyl-4,6-diisopropylindenyl)zirconium dichloride;
- rac-dimethylsilandiylbis(2-methyl-4-phenylindenyl)zirconium dichloride; and
- rac-dimethylsilandiylbis(2-ethyl-4-phenylindenyl)zirconium dichloride;
- Dimethylsilandiylbis(2,4,6-trimethyl-1-indenyl);
- Dimethylsilandiylbis(2-methyl-4-(1-naphthyl)-1-indenyl)zirconium dichloride;
- Dimethylsilandiylbis(2-methyl-4-(2-naphthyl)-1-indenyl)zirconium dichloride.
- 14. The method of claim 1 wherein the volume of reaction product is less than that volume required to form a slurry.
- 15. The method of claim 1 wherein the metallocene is represented by the formula: ##STR8## wherein M.sup.1 is a metal of group 4, 5, or 6 of the Periodic Table, R.sup.1 and R.sup.2 are identical or different, are one of a hydrogen atom, a C.sub.1 -C.sub.10 alkyl group, a C.sub.1 -C.sub.10 alkoxy group, a C.sub.6 -C.sub.10 aryl group, a C.sub.6 -C.sub.10 aryloxy group, a C.sub.2 -C.sub.10 alkenyl group, a C.sub.7 -C.sub.40 arylalkyl group, a C.sub.7 -C.sub.40 alkylaryl group, a C.sub.8 -C.sub.40 arylalkenyl group, or a halogen atom;
- R.sup.3 and R.sup.4 are hydrogen atoms;
- R.sup.5 and R.sup.6 are identical or different, preferably identical, are one of a halogen atom, a C.sub.1 -C.sub.10 alkyl group, which may be halogenated, a C.sub.6 -C.sub.10 aryl group, which may be halogenated, a C.sub.2 -C.sub.10 alkenyl group, a C.sub.7 -C.sub.40 arylalkyl group, a C.sub.7 -C.sub.40 alkylaryl group, a C.sub.8 -C.sub.40 arylalkenyl group, a --NR.sub.2.sup.15, --SR.sup.15, --OR.sup.15, --OSiR.sub.3.sup.15 or --PR.sub.2.sup.15 radical, wherein R.sup.15 is one of a halogen atom, a C.sub.1 -C.sub.10 alkyl group, or a C.sub.6 -C.sub.10 aryl group;
- R.sup.7 is ##STR9## .dbd.BR.sup.11,.dbd.AlR.sup.11, --Ge--, --Sn--, --O--, --S--, .dbd.SO, .dbd.SO.sub.2, .dbd.NR.sup.11, .dbd.CO, PR.sup.11, or .dbd.P(O)R.sup.11 ;
- wherein:
- R.sup.11, R.sup.12 and R.sup.13 are identical or different and are a hydrogen atom, a halogen atom, a C.sub.1 -C.sub.20 alkyl group, a C.sub.1 -C.sub.20 fluoroalkyl group, a C.sub.6 -C.sub.30 aryl group, a C.sub.6 -C.sub.30 fluoroaryl group, a C.sub.1 -C.sub.20 alkoxy group, a C.sub.2 -C.sub.20 alkenyl group, a C.sub.7 -C.sub.40 arylalkyl group, a C.sub.8 -C.sub.40 arylalkenyl group, C.sub.7 -C.sub.40 alkylaryl group, or R.sup.11 and R.sup.12, or R.sup.11 and R.sup.13, together with the atoms binding them, can form ring systems;
- M.sup.2 is silicon, germanium or tin;
- R.sup.8 and R.sup.9 are identical or different and have the meanings as stated for R.sup.11 ;
- m and n are identical or different and are zero, 1 or 2, m plus n being zero, 1 or 2; and
- the radicals R.sup.10 are identical or different and have the meanings stated for R.sup.11, R.sup.12 and R.sup.13 wherein further two adjacent R.sup.10 radicals can be joined together to form a ring system.
- 16. The method of claim 1 wherein the hydrocarbon is selected from the group consisting of pentane, hexane, and heptane.
Parent Case Info
This is a continuation of application Ser. No. 08/499,054, filed Jul. 6, 1995, now abandoned.
US Referenced Citations (5)
Foreign Referenced Citations (4)
Number |
Date |
Country |
0279863B1 |
Oct 1992 |
EPX |
279863 |
Oct 1992 |
EPX |
0629631A2 |
Dec 1994 |
EPX |
WO 94 28034 |
Aug 1994 |
WOX |
Continuations (1)
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Number |
Date |
Country |
Parent |
499054 |
Jul 1995 |
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