US 5,466,766 A · Metallocenes and processes therefor and therewith

Abstract

A method is provided for forming a supported cyclopentadiene-type compound comprising contacting a cyclopentadiene-type compound containing an active halogen with an inorganic support having surface hydroxyl group. Also there is provided a method of preparing a supported metallocene comprising reacting the supported cyclopentadiene-type compound with a transition metal compound under suitable conditions. There is also provided a process for producing bridged cyclopentadiene-type ligands having a bridge having branch that has a terminal vinyl group. Also metallocenes of these ligands are provided. Still further there is provided a process for producing bridged cyclopentadiene-type ligands having a bridge having a branch that has a terminal active halogen. The resulting new ligands and supported metallocenes produced therefrom are also provided. There is further provided supported metallocene catalysts wherein at least two metallocenes of differing effectiveness are both bonded to an inorganic support having surface hydroxy groups. Olefin polymerization employing the inventive bridged supported metallocenes is also provided, as well the resulting polymer products.

Claims29

Dependent claims

A process for preparing a supported cyclopentadiene-type compound comprising contacting a cyclopentadiene-type compound having an active halogen with an inorganic support having surface hydroxyl groups under suitable conditions to cause a reaction between the active halogen and a hydroxyl group on the support so that the cyclopentadiene-type group becomes chemically bound to the support.

A process for preparing a bridged metallocene comprising:

(1) contacting a hydrocarbon having at least two acidic, replaceable hydrogens and having the formula of ZH.sub.2 with an organolithium and an organohalosilane to prepare a ligand precursor having the formula of HZ--EX.sub.n+1 wherein at least one X is a halogen;
(2) contacting said ligand precursor with an organo alkali metal compound having the formula of HZMa to form a bridged ligand having the formula of ZH--EX.sub.n --ZH wherein at least one X is a halogen;
(3) contacting said bridged ligand with an inorganic material QH to form a bridged ligand chemically bonded to inorganic moiety Q;
(4) contacting said bridged ligand chemically bonded to inorganic moiety with an organolithium and a metal halide having the formula of MY.sub.m to prepare said bridged metallocene;
wherein each Z is the same or different hydrocarbyl radical selected from the group consisting of cyclopentadienyl, indenyl, tetrahydroindenyl, fluorenyl, and mixtures thereof;
each X can be the same or different and is selected from the group consisting of hydrogen, fluorine, chlorine, bromine, iodine, R, OR, NR.sub.2, PR.sub.2, and OQ, and mixtures thereof wherein the R is a C.sub.1 -C.sub.20 hydrocarbyl radical and Q is an inorganic moiety selected from the group consisting of silica, alumina, clay, phosphated alumina, and mixtures thereof;
each Y can be the same or different and is selected from the group consisting of an alkyl group, hydrogen, fluorine, chlorine, bromine, iodine, and mixtures thereof;
each E is Si;
M is a metal selected from the group consisting of Ti, Zr, Hf, Sc, Y, V, La, and mixtures thereof;
m is a number sufficient to fill out the remaining valences of metal M;
Ma is an alkali metal;
and n is 1 or 2.

9 more elements

Dependencies are inferred from the claim text.

Facts

Application

08/154,224Filed 17 Nov 1993 · continuation in part

Priority

9 May 1991

Granted

14 Nov 1995

Term ends

Not estimatedThe source records don’t support an estimate.

Classification54 codes

C07F 17/00
Metallocenes
B01J 31/143
Of aluminium or boron: of aluminium
B01J 31/1616
Containing coordination complexes: coordination complexes, e.g. organometallic complexes, immobilised on an inorganic support, e.g.…
B01J 31/1633
Immobilised by covalent linkages, i.e. pendant complexes with optional linking groups: covalent linkages via silicon containing groups

Family

Serial697,363Parent of this continuation-in-part · filed 9 May 1991

Serial734,853Parent of this continuation-in-part · filed 23 Jul 1991

Serial984,054Parent of this continuation-in-part · filed 30 Nov 1992

Serial75,712Parent of this continuation-in-part · filed 11 Jun 1993

Serial75,931Parent of this continuation-in-part · filed 11 Jun 1993

US 5,399,636 AParent of this continuation-in-part

US 5,347,026 AParent of this continuation-in-part

US 5,393,911 AParent of this continuation-in-part

US 5,436,305 AParent of this continuation-in-part

US 5,191,132 AParent of this continuation-in-part

US 5,466,766 AThis patent

From the US filing history. Foreign family members aren’t listed.

Metallocenes and processes therefor and therewith

Life of this patent

Metallocenes and processes therefor and therewith

Life of this patent

Abstract

Claims29