CA2124731C - Metallocenes and processes therefor and therewith - Google Patents

Metallocenes and processes therefor and therewith

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Publication number
CA2124731C
CA2124731C CA002124731A CA2124731A CA2124731C CA 2124731 C CA2124731 C CA 2124731C CA 002124731 A CA002124731 A CA 002124731A CA 2124731 A CA2124731 A CA 2124731A CA 2124731 C CA2124731 C CA 2124731C
Authority
CA
Canada
Prior art keywords
cyclopentadienyl
fluorenyl
group
compound
process according
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Fee Related
Application number
CA002124731A
Other languages
French (fr)
Other versions
CA2124731A1 (en
Inventor
Helmut G. Alt
Konstantinos Patsidis
M. Bruce Welch
Rolf L. Geerts
Bernd Peifer
Syriac J. Palackal
Darryl R. Fahey
Harold R. Deck
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Phillips Petroleum Co
Original Assignee
Phillips Petroleum Co
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from US08/075,712 external-priority patent/US5399636A/en
Application filed by Phillips Petroleum Co filed Critical Phillips Petroleum Co
Publication of CA2124731A1 publication Critical patent/CA2124731A1/en
Application granted granted Critical
Publication of CA2124731C publication Critical patent/CA2124731C/en
Anticipated expiration legal-status Critical
Expired - Fee Related legal-status Critical Current

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • B01J31/12—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides
    • B01J31/14—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides of aluminium or boron
    • B01J31/143—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides of aluminium or boron of aluminium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/1616—Coordination complexes, e.g. organometallic complexes, immobilised on an inorganic support, e.g. ship-in-a-bottle type catalysts
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/1616—Coordination complexes, e.g. organometallic complexes, immobilised on an inorganic support, e.g. ship-in-a-bottle type catalysts
    • B01J31/1625—Coordination complexes, e.g. organometallic complexes, immobilised on an inorganic support, e.g. ship-in-a-bottle type catalysts immobilised by covalent linkages, i.e. pendant complexes with optional linking groups
    • B01J31/1633—Coordination complexes, e.g. organometallic complexes, immobilised on an inorganic support, e.g. ship-in-a-bottle type catalysts immobilised by covalent linkages, i.e. pendant complexes with optional linking groups covalent linkages via silicon containing groups
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/22—Organic complexes
    • B01J31/2282—Unsaturated compounds used as ligands
    • B01J31/2295—Cyclic compounds, e.g. cyclopentadienyls
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C13/00—Cyclic hydrocarbons containing rings other than, or in addition to, six-membered aromatic rings
    • C07C13/28—Polycyclic hydrocarbons or acyclic hydrocarbon derivatives thereof
    • C07C13/32—Polycyclic hydrocarbons or acyclic hydrocarbon derivatives thereof with condensed rings
    • C07C13/54—Polycyclic hydrocarbons or acyclic hydrocarbon derivatives thereof with condensed rings with three condensed rings
    • C07C13/547—Polycyclic hydrocarbons or acyclic hydrocarbon derivatives thereof with condensed rings with three condensed rings at least one ring not being six-membered, the other rings being at the most six-membered
    • C07C13/567—Polycyclic hydrocarbons or acyclic hydrocarbon derivatives thereof with condensed rings with three condensed rings at least one ring not being six-membered, the other rings being at the most six-membered with a fluorene or hydrogenated fluorene ring system
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    • C07C22/00—Cyclic compounds containing halogen atoms bound to an acyclic carbon atom
    • C07C22/02—Cyclic compounds containing halogen atoms bound to an acyclic carbon atom having unsaturation in the rings
    • C07C22/04—Cyclic compounds containing halogen atoms bound to an acyclic carbon atom having unsaturation in the rings containing six-membered aromatic rings
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    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C49/00—Ketones; Ketenes; Dimeric ketenes; Ketonic chelates
    • C07C49/587—Unsaturated compounds containing a keto groups being part of a ring
    • C07C49/703—Unsaturated compounds containing a keto groups being part of a ring containing hydroxy groups
    • C07C49/747—Unsaturated compounds containing a keto groups being part of a ring containing hydroxy groups containing six-membered aromatic rings
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    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
    • C07C51/16—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation
    • C07C51/31—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation of cyclic compounds with ring-splitting
    • C—CHEMISTRY; METALLURGY
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    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
    • C07C51/347—Preparation of carboxylic acids or their salts, halides or anhydrides by reactions not involving formation of carboxyl groups
    • C07C51/373—Preparation of carboxylic acids or their salts, halides or anhydrides by reactions not involving formation of carboxyl groups by introduction of functional groups containing oxygen only in doubly bound form
    • C—CHEMISTRY; METALLURGY
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    • C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
    • C07C51/347—Preparation of carboxylic acids or their salts, halides or anhydrides by reactions not involving formation of carboxyl groups
    • C07C51/377—Preparation of carboxylic acids or their salts, halides or anhydrides by reactions not involving formation of carboxyl groups by splitting-off hydrogen or functional groups; by hydrogenolysis of functional groups
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    • C07C63/33—Polycyclic acids
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    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C65/00—Compounds having carboxyl groups bound to carbon atoms of six—membered aromatic rings and containing any of the groups OH, O—metal, —CHO, keto, ether, groups, groups, or groups
    • C07C65/32—Compounds having carboxyl groups bound to carbon atoms of six—membered aromatic rings and containing any of the groups OH, O—metal, —CHO, keto, ether, groups, groups, or groups containing keto groups
    • C07C65/34—Compounds having carboxyl groups bound to carbon atoms of six—membered aromatic rings and containing any of the groups OH, O—metal, —CHO, keto, ether, groups, groups, or groups containing keto groups polycyclic
    • C07C65/36—Compounds having carboxyl groups bound to carbon atoms of six—membered aromatic rings and containing any of the groups OH, O—metal, —CHO, keto, ether, groups, groups, or groups containing keto groups polycyclic containing rings other than six-membered aromatic rings
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    • C07F17/00—Metallocenes
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    • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic System
    • C07F7/02—Silicon compounds
    • C07F7/08—Compounds having one or more C—Si linkages
    • C07F7/0803—Compounds with Si-C or Si-Si linkages
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    • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic System
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    • C07F7/0803—Compounds with Si-C or Si-Si linkages
    • C07F7/081—Compounds with Si-C or Si-Si linkages comprising at least one atom selected from the elements N, O, halogen, S, Se or Te
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    • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic System
    • C07F7/02—Silicon compounds
    • C07F7/08—Compounds having one or more C—Si linkages
    • C07F7/0803—Compounds with Si-C or Si-Si linkages
    • C07F7/0825—Preparations of compounds not comprising Si-Si or Si-cyano linkages
    • C07F7/0827—Syntheses with formation of a Si-C bond
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    • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic System
    • C07F7/02—Silicon compounds
    • C07F7/08—Compounds having one or more C—Si linkages
    • C07F7/12—Organo silicon halides
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    • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic System
    • C07F7/22—Tin compounds
    • C07F7/2208—Compounds having tin linked only to carbon, hydrogen and/or halogen
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    • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic System
    • C07F7/30—Germanium compounds
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    • C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
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    • C08F4/00—Polymerisation catalysts
    • C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
    • C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
    • C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
    • C08F4/619—Component covered by group C08F4/60 containing a transition metal-carbon bond
    • C08F4/6192—Component covered by group C08F4/60 containing a transition metal-carbon bond containing at least one cyclopentadienyl ring, condensed or not, e.g. an indenyl or a fluorenyl ring
    • C08F4/61922—Component covered by group C08F4/60 containing a transition metal-carbon bond containing at least one cyclopentadienyl ring, condensed or not, e.g. an indenyl or a fluorenyl ring containing at least two cyclopentadienyl rings, fused or not
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    • C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
    • C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
    • C08F4/62—Refractory metals or compounds thereof
    • C08F4/64—Titanium, zirconium, hafnium or compounds thereof
    • C08F4/659—Component covered by group C08F4/64 containing a transition metal-carbon bond
    • C08F4/65916—Component covered by group C08F4/64 containing a transition metal-carbon bond supported on a carrier, e.g. silica, MgCl2, polymer
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
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    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
    • B01J2231/10—Polymerisation reactions involving at least dual use catalysts, e.g. for both oligomerisation and polymerisation
    • B01J2231/12—Olefin polymerisation or copolymerisation
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B01J2231/50—Redistribution or isomerisation reactions of C-C, C=C or C-C triple bonds
    • B01J2231/52—Isomerisation reactions
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    • B01J2231/641—Hydrogenation of organic substrates, i.e. H2 or H-transfer hydrogenations, e.g. Fischer-Tropsch processes
    • B01J2231/643—Hydrogenation of organic substrates, i.e. H2 or H-transfer hydrogenations, e.g. Fischer-Tropsch processes of R2C=O or R2C=NR (R= C, H)
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    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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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.

Description

, 2~47~1 ~

.
,.
, , . .
.~
, ........................................................................... .

NETALLO~EN~S AND ~RO~;S~hS ~ uk AND THEREWIT~

.~ :
,i~ This application 1s a continuAtion~in-psrt of copending U.S.
~, ~
'~ Patent Application S.N. 75,712 filed Jnne 11, 1993; copending U.S.
Patcnt Application S.N. 75,931 filed June 11, 1993; copending U.S.
Patent Application S.N. 984,054 filed November 30, 1992; and copendlng U.S. Patent Application S.N. 734,853 filed July 23, 1991 as a CIP of S.N. 697,363 filed Msy 9, 1991, now U.S. Patent 5,191.132. The disclosures of all the sbove-ment1Oned applications are incorporated ~ herein by refarence.

-~ Field 3f the Invention The present invention relates to a metallocene composition~ 8 process for preparing the composition, and a process for using the composition. The present invention also r~lates to organic c ~uullds suitable for making metallocenes.

~ Back~round of tha Invention '! Since the discovery of ferrocene in 1951, a number of b ~etallocenes have been prepared by the combinfltion of anions having the , ~ ~

212 ~ CA
~ 2 ; cyclopentadienyl structure with varloufi transitlon met~ls. The term "cyclopentadlenyl structure" as used herein ~efers to the following structurs.

, j ~ C C ~
.''' I I
~j'', C~c~C/

Such "cyclopentadlenyl structure" can be formed by addition of various metal alkyls to cyclopentadiene and "cycl~pentadiene-type" ccm~unds~
The term "cyclopentadiene-type compound" as used herein refers to compounds containing the cyclopentadiene strllcture. Examples of cyclopantadiene-type compounds include unsubstituted cyclopentadiene, unsubstituted indene, unsubstituted te~rahydroindene~ unsubstituted fluorene, and substituted varieties of such compounds.
Many of the cyclopentadiene-type metallocenes have been found useful in catalyst systems for the polymerization of olefins. It has been noted in the art that variatlons in the chemical structure of such cyclopentadienyl-type metallocenes cfln have significflnt effects upon the suitability of the metallocene as a polymerization catalyst. For example, the size and substitutions on cyclopentadienyl-type ligands has been found to affect the activity o~ the catalyst, the stereoselectivity of the catalyst, the stability of the catalyst, and other properties oE
the resultlng polymer; however, the effects of various substituents is .
~ still largely an empirical matter, that is, experiments must be <~ conducted in order to determine ~ust what effect a particulax variation will have upon a particu]ar type of cyclopentadienyl-type metallocene.

Some examples of some cyclopentadienyl-type metallocenes are disclosed '-~ in U.S. patent Nos. 4,530,g1~; 4,808,561; ~nd 4,892,851, the disclosures , '' of which are incorporated hereLn by reference.

In the past most polymer-~zfltlon work has been done using ~ ., homogeneous, i.e. soluble, metallocenes rflther than heterogenous systems ~' in which the metallocene is Insoluble during the polymeri~ation.

However, for many industrial applications it wou1d be desirflble to have insoluble supported forms of metallocenes thflt are still active as - polymerization catalysts.
I
It is also envisioned that such heterogeneous catalysts would have other uses. For example, the compositions could posslbly be used as catalysts for hydrogenation, alkene epo~idation, a]kene isomerization, ketone reduction, stereoselective fllkene polymerizfltion, and as reagent for stereoselective cobalt-mediated reactions, alkyltitanium addition reactions with aldehydes, and formation of allylic amines.
Accordingly, an object of the present invention is to provide methods for producing such heterogeneons catalysts. Still anoth~r obJect is to provide novel organic compounds suitable for use in preparing metallocenes.
An object of the present invention is thus to provide certain new organic compounds, including brldged ligands and metallocenes.

,., Another object of the present invention is to provide a method for preparing new organic compounds including bridged ligands and metallocenes. A further object of the present invention is to provide supported, bridged ligands and metallocenes. Yet a further object of the present invention is to provide A process for preparing the supported, bridged ligands and metallocenes. Still another obJect of . .

i 212 ~ 7 31 ~ 4 S" the present invention is to provide polymeriY,ation catalysts employing tha supported metallocenes. Yet flnother oh~ect of the present lnvention is to provide processes for the polym~ri7.ation of olefins using tho ,; supported metallocene catfllyst systems. ~tLll yet another object of the present invention is to provide polymer~q produced using such supportsd, metallocena catalysts.
. ~

' Summary of thc Inv~ntion :, In accordance wlth the present invention there ls provided a method for forMing a supported cyclopentadiene-type compound comprising contacting a cyclopentadiene-type compound containing ~n activa halogen with sn inorganic support having surface hydroxyl group. Also in accordance with the present invention there is provided a method of prsparing a supported metallocene comprtsing reacting the supported cyclopentadiene-type compound with a transition metal compound under suitable conditions to form said supported metallocene.
Still further in accordance with the present lnvention th~re is provided a process for producing bridged cyclopentadiene-type ligands having a bridge having at least one branch having olefinic unsaturation.
Metsllocenes of such ligands are also provided. In accordance with yet another embodiment of the present invention there is provided a process ~, for producing bridged cyclopentadiene-type ligands hsving a bridge having st least one branch that has an active halogen. The resulting new ligands and supported metallocenes produced therefrom are also ~;
provided.
In accordance with another aspect of the present invention there is provided supported metallocenes wherein at least two ..

., ;

,,,1 .,, 2 1 2 ~1 7 3 1 33213CA
~' : s i metallocenes of differing flCtiVity are both ~onded tc an inorganic .~
support having surface hydroxy groll~s.
According to snother embodtment of the in~ention, a process for olefin polymeri2ation is provlded which comprises contacting 8n olefin under olefin polymerization condttions with a compositlon comprising the inventive bridged supported metallocene prepared as described above, optionally, in cnmbination with a suitable actlvator.
According to yet another embodiment of the invention there is provided a polymer product resulting from such a polymerl~ation process.

,,, Det~lled Description of the Inv~ntion A wide variety of cyclopentadiene-type compounds ha~ing active halogens are suitable for the present invention. Included are bridged cyclopentadiene compounds in which two cyclopentadiene-type compounds flre bound together by a bridge having an active halogen as well as unbridged cyclopentadiene compounds in which a cyclopentadiene-type c~ ulld has Q radical having an active halogen. Ex~mples of the latt~r include such compounds of the formula Z-l~-X
n wherein Z is a cyclopentadiene type radical; A is Si, Ge, Sn; and X is , selected from hydrogen, hydrocarbyl radicals, and halogens; wherein at - ~ least one X i~ a halogen, and n is a number filling the remaining i :~
~ valence of A. The hydrocarbyl radicals are other than cyclopentadiene ;~ ~ type radicals and generally contain 1 to 8 carbon atoms. Some specific examples of such compounds include cyclopentadienyl dimethyl silyl chloride, fluorenyl dimethyl silyl chloride, indenyl dimethyl silyl chloride, fluorenyl ethyl chloride, fluorenyl dimethyl methyl chloride, i j ~, 212 ~ 7 31 , ~ fluorenyl methylene chlorlde, fluore~yl diphenyl 8ermflne chloride, ~',!
fluorenyl diphenyl tin chloride, fluorenyl silyl trichlorlde, fluorenyl germane trichlorlde, fluorenyl methyl germflne dichloride and the llke, including such compounds in whlch the cyclopentadiene-type group ,,~ contains one or more substitutents. The currently preferred active halogens are silyl halides.
The unbridged cyclopentfldiene-type compounds can be prepared using the general procedures disclosed in the flforementioned U.S. Patent ~-~ applications S.N. 75,931; S.N. 734,853; and S.N. 697,363, the disclosures of which are incorporated herein by referencs.
Examples of bridged ligands include compounds of the formula 'i, Z-R'-Z whorein each Z can be the same or different substituted or unsubstituted cyclopentadiene-type radical and R' is a structural bridge linking the two Z's, wherein R' contains at least one active halogen.
Some such bridged ligands can be msde using the general techniques ~ taught in U.S. Patent No. 5,191,132 and pending U.S. application S.N.
; 734,853. For example, an alkali metal salt of a cyclopent~diene-type compound can be reacted with a bridge precursor compound X-R'-X whersin each X ls a halide and wherein R' contains at least one actlve halide, to produce either a bis (cyclopentadienyl-type) bridged compound or a ~ mono (cyclopentadienyl-type) compound of the formul~ Z-R'-X which is ; then reacted with an alkali metal salt of A different % compound to produce a bridged compound of the Formul~ %-R'-Z wherein the two %'s are different. Examples of X-R'-X include trih~logenated compounds of Si, Ge, and Sn.
Some specific examples of silyl brldged ligands having active alogsn include for example l-cyclopentadienyl-9-fluorenyl ,' (~

i::

~ ~' 7 2~2~731 . ~ , '' methylchloros.Llflne~ bts(9-flnoreny1)phenylchlorosllane, cyclopentadienyl-9-fluorenylmethylchlorosllane, bis(9-fluorenyl)-phenylchlorosilane, l-cyclopentadieny1-9-fluorenylmethylchlorosilane, , bis(9-fluorsnyl)phenylchlorosilsne, l-cyclopentsdienyl-9-fluorenyl-methylchlorosilane, bis(9-fluorenyl)phenylchlorosilsne, and bis(2,8-difluoro-9-fluorenyl)methylchlorosilane.
In a pMrticulsrly preferred embodiment the bridge R' of tha ligsnd Z-R'-Z has a branch extending ontwflrdly Erom the divfllent R' radlcal, which branch contalns a hslosllyl grollp. Typicslly, the branch would be an alkyl branch contalning 2 to 12 carbon atoms, more commonly, 2 to 5 carbon atoms. Some examples of sllch halogenated branched bridged compounds include 2-(bls-9-fluorenyl-methylsilyl)-1-trichlorosllylethane; l-chlorodimethyl sllyl-5-cyclopentadienyl-5-~9-fluorenyl) hexane; and 5-cyclopentadienyl-5-(9-fluorenyl)-1-trlchlorosilylhexsne.
Halogenated branched bridged ligands can be prepared by the halogenation, i.e. chlorinstion, or hydrosilylstion of a suitable bridged ligand whlch has a brsnch hAving olefinic unsaturation.
Examples of such bridged compounds lnclude those in wh~ch the R' bridge has a branch of the formula R"2C=CH-(R " ')n~ wherein R " ' is a hydrocarbyl radical having 1 to 10 csrbon fltoms, n is 1 or 0, and each R" is the same or dlfferent and selected from the group conslsting of hydrocsrbyl rsdicals hsving 1 to 10 carbon atoms and hydrogen. One of the embodiments of the present invention provides such olafinic branched bridged cyclopentadienyl compounds.
Such olefinic branched ligands csn be prepsred by reacting a dihalo olefinic sildne with an alkali metal salt of a suitsble . 212 ~731 33213CA
.,, ~
cyclopentadlene-type compound to pro-lu~ n compollnd of the formula Z-R'-Z wher~in ~ach Z is th~ Sflme or altern~tively to first produc~ a compound of ths formula ZrR'-X wh~r~{n X is a hAIogsn ~Dd th~n reacting ~;i that compound with an a]k~li metfll ~sAlt of anothsr diffsrsnt ~'.' cyclopsntadlsns-type compound to producs a compound of ths formulfl Z-R'-Z wherein the two Z's differ. Such rsActions can be carrled out P~ uslng conditions of the typs disclossd in U.S. Pfltent 5,191,132. Ths ~ resulting olefinic branchsd ligflnds cfln then bs reflcted with ~"
chlorosilflnss or chloroalkyl silanes to produce branchsd bridgsd ligands in which the brsnch has an activs termtnfll halog~n. Ths hydrosilyfltion r~action can bs carrisd out using conditions snch as disclosed by J.L.
Sp~ier in Adv. Or~anomet. Chem., 49, 1844 (1984).
An alternats tschniqus for iorming ~ olefinic branched b~idg~d ligand involves reacting a carbonyl compound having olsfinlc unsaturation with cyclopentadisns in the prsssncs of pyrrolidins flnd methanol to yisld ~n slksnyl fulvsne which is thsn reactsd with an alksli metal salt of a cyclopsntadisne compound, such ~s, for example, fluorenyl to yield the unsaturatsd-brflnchsd-bridgsd ligand containing two cyclopentadienyl-type groups, i.e. fluorenyl and cyclopentadienyl.
For exampls, one could re~ct 5-hexene-2-one with cyclopentadiene using procedure like that disclosed by Stone ~t al in J. Org. Chem., 49, 1849 (1984) to yield 6-(3-butenyl)-6-methylfnlvene which could then be reacted with fluorenyllithium And sllhsequent hydrolysis to yield 5-cyclopentadienyl-5-(9-fluorenyl)-1-hexens. The terminal fllkenyl group can then be sub~ected to hydrosilyation as described ln the preceding psragraph.

.
. ' .

: The present invention thus envi~iorls vinyl termlnatsd branched bridged ligands of the formula " Z

1) H2C=~-(CH2)n R - R
Z
~ wherein n is a number typicQlly in the r~nge o~ about O to 10: R is Si, ; Ge, C, or Sn; R " is selected from hydrogen, or alkyl groups typically ha~ing 1 to 10 carbon atoms, or aryl groups typically having 6 to 10 carbon atoms. The present invention thus also envisions the halogenation and hydrosilyation reflction products of such vinyl terminated ccr~ounds as well ss the metallocenes of such vinyl terminated compounds.
The metallocenes of such olefinic uns~turated branched-bridged : ligands can be prepared by re~cting the branched-bridged i~ bistcyclopentadlenyl type) ligand with an alkali metal alkyl to produce the divalent ligand salt that is then reacted with the transition metal compound to yield the metallocene, usln~ the techniqucs generally known in the art for formin~ such metallocene~. See for example~ European ~ ~ Published Applicatlon 524,6rj4 whlch corresponds to pending ~.S.
p ~ application S.N. 734,853.
The inorganic support materiflls having surface hydroxyl groups include inorganic oxides, c~rbonates such flS chalk, silicates such as ;~ talc, clay, and the like. Some particularly preferred supports include silicaj alumina, clay, phosphated alumtna, and mixtures thereof.
Phosphated aluminss can be prepared by the steps comprising:
(1~ mixing aluminum nltrate with a phosphate compound, in the presence i ~

i~

:
~ 33213CA
~o 2~ ~7~
of water, to Eorm a solution; (2) flddin~ a haqlc compound, preferably in aqueous form, to the solutlon to produce a solid product; (3) recovering the solid product; ~4) optionfllly, wRshlng the solid product wlth a solvent to prepare a washed-producti (5) drying the solid product or washed product, resulting in fl dried product; and (6) calcining ths dried product to produce the phosphated alumina. Sultable phosphate compounds lnclude, but are not limited to ammonium phosphate (dibasic), ammonium phosphate (monobasic), sodlum phosphate (monobasic), sodium phosphate (dlbflsic), magnesium phosphate, potassium phosphate (dlbasic), potassium phosphate (~onobasic3, mangflnese phosphate, and mixtures thereof. The presently preferred phosphste compound is ammonlum phosphate (monobasic) becsuse of its refldy availflbility and easy of use.
Sultable basic compound employed in step (2) should be able to produce a precipitate from the solution. Examples of suitable basic compound include, but are not limited to, ammonium hydroxide, lithium hydroxide, sodium hydroxide, sodium carbonate, sodium bicarbonate, potassium hydroxide, magnesium hydroxide, barrium phenoxide, calcium hydroxide, calcium phenoxide, RONa, RSNa, and mixtures thereof wherein R is a C~-C6 alkyl radlal. The presently preferred hasic compound is ammonium hydroxide. The solvent used in step (4) to wash the solid product can be an alcohol, elther, ketone, acid. flmide, or water, as long as it does not react with or solubilize the solid product. Fxamples of suitable solvents include, but are not limited tO water, methanol, ethanol, propanol, lsopropanol, butanol, isobutanol, pentanol, dlethyl ether, tetrahydrofuran, acetone, methyl ethyl ketone, acetic acid, dimethylforsmide, and mixtures thereof~ The presently preferred ~olvents ar~ water and ethanol because of their ready evailability. The ~ '- 212 ~ 7 31 .~ 1 1 ~ drylng of step (5) can be a conventtona1 irylng or drylng under reduced ~ 1 pressure. Tha drying temperAtUre can vary widcly from about 50~C to about 150~C under about 0.05 mmHg to abollt ~00 mmHg pressure for about l to about 30 hours, preferably from 60~C to 100~C under 0.05 to 760 mmHg pressure for 5 to 2C hours. The, cfllcining step cfln fllso vary wide,ly , from about 250~C to about 30 minutes to ahout 15 hours, preferably 1 to 7 hours.
In the preparation of the phosph~ted alumina, the molar ratio of the phosphate compound to aluminum nitrate ls generally in the range of from flbout 0.05:1 to about 5:1, preferably from about 0.1:1 to about -~ 2:1, and most preferably from 0.2:t to l:l for best physical form and catalytic activity of phosphated alumin~ when used as a component of the invention composition. The molar rfltio of water to aluminum nitrate is in the range of from about 10 1 to about 200:], dependlng on the solubility of both aluminum and the phosphate compound, preferably about 20:1 to about lO0:1, most preferably 25:1 to 50:1. The molar ratio of the basic compound to aluminum nitrate is in the range of from about ~;~ 0.05:1 to about 10:1, preferably about 0.2:1 to about 5:1 and most ', preferably 0.5:1 to 2:1. The recovery of the solid product in step (3) can he carried out by any known means slich as, for example, filtration, i decantation and centrifugation. The molflr ratio of the washing solvent to aluminum nitrate can vary widely from flbout 5:~ to about 1000:1 depending on the type of solvent used. The washing can also be carried out more than once and/or with a different solvent.
Examples of clays include~ bu~ flre not limited to, kaolinite, halloysite, vermiculite, chlorite, attapulgite, smectite, ~i montmorillonite, illltf, saconite, sepiollte, palygorskits, Fuller's '' '1 2 1 2~ 7 3 l 33213CA

earth, and mixtures thereo~. The pres~ntly preferred clay is a montmorillonlte clay. The presently most preferred clay i9 sodium montmorillonite which is generfllly known AS bentonite.
Examples of porous oxides or mtxed oxides o~ silicon and/or aluminum include those having a specific surface area of 50 to 1,000 sq.m./g, more generally 100 to 800, flnd more preferably 150 to 650 sq.m./~, and whose pore volume is in the range of 0.2 to 3, preferably 0.4 to 3, in particular 0.6 to 2.7 cm3/g. ~uch supports would generally have an average particle size in the rflnge of flbout 1 to about 500 millimicron, more typically about l0 to flhout 200, and more preferably , .i, about 20 to 100 millimicron. Depending upon the specific surface area and the temperature pretreatment, the hydroxyl group number of such supports is in the range of about 0.5 to about 50 mmol, more typically about 1 to about 20, and mors preferably flbout 1.5 to about 10, hydroxyl groups per gram of support.
The bridged or unbridged cyclopentadiene-type compound having an active halogen is reacted with the hydroxyl-contalning support under suitable reaction conditions to obtain a sllpported cyclopentadiene-type compound.
Generally before reacting the support with the halogenated cyclopentadiene-type compound, it i5 prefer8ble to remove adsorptively bound water from the support by drying at ~ temperature in the range of from about 120 to about 800 degrees C, more typicfllly about 200 to about 500 degroes C. The drying can be monitored analytically by titratin8 the OH content of the support materlal flgainst n-butylmagnesillm .
~c chloride. After drying, the support can be stored under an inert gas, for 2xample, ni$rogen or argon to exclude flir and water.

.~

; 2~2~73~ 33213C~

:!
The present invention thus prov1des a process whlch comprises :
contflcting a bridged llgflnd having the formula of Z-R'-Z with an inorgflnic materlal Q to form fl br1dged 11gAnd which is chemlcally bonded to the inorganic moiety Q, wherein eflch % cfln be the same or different, substituted or unsubstituted, hydrocflrbyl rfldicfll having an active hydrogen selected from tt~e group consistlng of cyclopentadlenyl, indenyl, tetrflbydroindenyl, fluoreny], And mixt-Jres thereof; R' i9 a bridge having a re~ctive hfllogen atom~ flnd Q is fln inorganic moiety having surfQce hydroxyl groups such as, for exflmple, sil~ca, aluminfl, clay, phosphated alumina, and mixtures thereof~
It ls also within the scope of the present invention to contflCt two or more bridged ligands of thflt type with the inorganic suppoxt. It is also within the scope of the present invention to form supported ligands contflining two or more t1nbridged cyclopentadienyl-type ligands or a mixture of the unbridged and bridged ligands. In an especially preforred embodiment two or more active halogen-containing ligands are used which have differlng effects upon polymerization.
The conditions employed for contacting of the bridged or unbridged active hfllogen-containing ligflnd flnd the inorganic matsrial csn vary over a wide range. Typically, such is done in the presence of a liquid dlluent, preferflbly a solvent for the ligand. Host preferably, tha reaction is carried out in the presence of a basic compound which will neutralize any acid formed during tne reaction. A typical example would be pyridine. The molar ratio of the llgflnd to the inorganic materifll can also vary over a wide range. Generally the molflr ratio of the ligand to the OH on the surface of the inorgflnic mflterial would be in the range from about l:l to about O.OOOOl~

. .

, '~:! 33213CA
~ ' 14 ~ 31 The resulting supported cyclopentfldienyl-type compoond can ,:
then be used to form a supported metflllocene. Preferably the supported cyclopentadienyl-type compound is sub~ected to puriflcfltion to remove ,~, any undesirable by-products thnt might hAve been produced during lts praparation. Techniques such as extr~ction, solvent washing, and evaporation can be used.

., To form the ~upported metflllocene the supported cyclopentadienyl-type compound i~ then reacted with an organo alkali metal compound to form the corresponding supported cyclopentadienyl alkali metal s~lt whlch is then reflcted with fl suitable transition metal compound under suitable conditions. Typic~lly transition matal hfllide compounds Mre employed of the formull MeXn wherein Me is a transition metal selected from metflls of Groups IIIB, IVB, VB, and VIB of the Periodic Table and n is a number reflectin~ the valence of the metal, generally 3 or 4. Each X in ths formula cfln be the same or different and can be selected from the group consisting of halo~ens, and hydrocarbyl or hydrocarbyloxy groups having l to about 20 carbon atoms.

,~
Pref&rably at least one of the X's is fl h~ logen. The preferred transition metal compounds are those of the metals selected from the group consistin~ of Ti, Zr, Hf, Sc, Y, V, flnd Lfl. The presently most preferred metals are Ti, Zr, V, or Hf. Some examples o~ such transition metal compounds include zirconium tetrflchloride, hafnium tetrachloride, cyclopentadienyl titanium trichloride~ cyclopentadicnyl zirconium trichloride, cyclopentadienyl methyl zirconium dichloride, fluorenyl ~irconium dichloride, 3-methylcyclopentfldienyl zirconium trichloride, 4-methylfluorenyl ~irconium trichloride, indenyl methyl zirconium dichloride, and the like.

!, ~

; ''' 15 .
!
When the supported li~flnd ls fl non-bridged lig~nd it is generally necessary to renct it w1th A ryclopentadienyl-type-containing transition metal compound to form the metflllocene, for example cyclopentadienyl zirconium trichloride, cyclopentadienyl dimethyl zirconium chloride, fluorenyl d:Lmethy] ~irconium dlchloride, or cyclopentfldienyl methyl ~irconium dichloride. In ~ny case, the reaction can be carried out using the same general techniques that h~ve been used in the past to form the unsupported form of such met~llocene.
~enerally, this involves forming an alkali metfl1 sa1t of the supported cyclopentadienyl-type compound and reflcting it with a transition metal halide compound in the presenc~ of a suitflble solvent.
If the unbridged ligand contains residual ~ctive halogen groups, it is generally desirable to reflct the supported ligand with enough organoalkali metal compound so that the active halide will be r~placed with the organic radical of the org~noalkali metal compound before the reaction is begun to prepflre the metallocene. The presently preferred organoalkali metal compounds, here flS in forming cyclopentadianyl salts to form metallocenes, are aliphatic or aromatic salts of lithium or sodium.
Some illustrative, but non-li~iting examples oi bridged supported metallocenes withln the scope of the present invention include, for example, silica-O-l-cyc10pentadienyl-l-cyclopentadienyl-methylsilane zirconium dichloride, sil~ca-O-bis(9-fluorenyl)phenylsilane zirconium dichloride, silica-O-l-cyclopentadienyl-9-fluorenylmethyl-silane hafnium dichloride, silica-O-bis(9-f]uorenyl~phenylsllane hafniu~
dichloride, silica-O-l-cyclopentfldienyl-9-fluorenylmethylsilflne vfln~dium dichloride, silica-O-bis~9-fluorenyl)phenylsilane vanadium dlchlorid~, ' ~ 33213CA
~' 16 212~73~
.~:
~ sillca-O-l cyclopentadlenyl-9-flllorenylmethylsLIflne tltanium dichloride, i slllca-O-bis(9-fluoreny1)phenylsllane tltanium dlchlorlde, ;~ sillca-O-bis(2,8-dlfluoro-9-fluorenyl)m~thylsilane zircontum dichloride, ; silica-O-l-cyclopentadlenyl-9-fluorenylmethylsi]ane zirconium ~, ~ dichloride, alumina-O-l-cyclopentfldisnyl-9-fluorenylmethylsilane zlrcoDium dlchlorLde, bentonite-O-I-cyclo~entadienyl-9-fluorenylmethyl-silane 7~irconium dichloride, and mixtures thereof. The presently ; preferred bridged metallocene is silica-O-l-cyclopentadlenyl-9-' fluorenylmethylsilane zirconlum dichlorlde. In the nflmeS given in this !,,, paragraph the phrase silica-O merely refers to the fact that the bridged metallocene is bonded through the bridge to fl surface oxygen of the support.
Some examples of supported unbridged metallocenes include silica-O-dimethyl silyl cyclopentadienyl-fluorenyl zirconium dichloride, ' silica-O~diphenyl silyl cyclopentadienyl-cyclopentadienyl zlrconium dimethyl, and the like.
Some specific examples of the brldged ligands that can be used x in the present inventlon include thosP having the formula of i,. /%
" X E
n '. ~
wherein each Z can be the same or dif~erent, substituted or unsubstituted, hydrocarbyl radical selected from the group consisting of cyclopentadienyl, indenyl, tetrahydroindenyl, fluorenyl, and mixtur~s thereof; E is a bridge connecting the two Z's and is selected from the group cons1~ting of C, Si, Sn, Ge, ~, Al, N, or P; each X can be the <- l7 sama or different and is ~elected from the ~roup consi~ting of hydrogen, fluorine, chlorine, bromine, iodine, R, OR, NR~, PR2, or mix-tures thereof, wherein R is a Cl to t'20 hydrocnrbyl radical, wherein at least one X ls ~ halide, and wherein n is a number sufficient to fill the valences of E, gener~lly 1 or 2.
Under one embodiment of the present Invention, a substituted or unsubstituted cyclopentAdienyl-type h~drocarbon, Z, having an acidic, replacsabls hydro~en atom is contacted with an organolithlum and an organohalosilane. Z is the same as that disclosed above. The presently preferred hydrocarbons having fln acidic, replflceable hydrogen are cyclopentadiene, indene, tetrahydroindenr, fluorene, or mixtures - thereof. The pre-ferred organolithium is an alkyllithium including butyllithium, methyllithium, ethyllithium, propyllithium, or mixtures thereof. The presently most preferred organolithium is butyllithium.
The presently preferred organohalosilane is an alkylhalosilane or ~rylhalorosilane such as methyltrichlorosilane, ethyltrichlorosilane, propyltrichlorosilane, phenyltrichlorosilane, tolyltrichlorosilane, or , ~
mixtures thereof. The presently most preferred organohalosilane are methyltrichlorosilane, phenyltrichlorosilAne, or mixtures thereof.
This first step of this embodiment of the inventlon can be c~rried out in the presence of a suitab]e solvent. Examples of suitable solvents include, but are not limited to diethyl ether, tetrahydrofuran, hydrocarbons such ~s pentane, hexane, heptflne, cyclohexane, and toluene, and the li~e. According IO the present ~nvention, the reaction pressure and temper~ture for this embodiment flre not particularly critical and c~n vary over a wide range. Atmospheric pressure is presently preferred although hi~her or lower pressures can be employed. TypicallyJ the 212 ~ 7 31 IR
reAction temper~ture is in the rnn~e of from flbout -100~C to about 100~C. Generally, it is convenient to cArry OIIt the fir~t st~p at ., i ambient temperatures.
The molar ratio of th¢ hydrocflrbon hflving at least two acidic, replaceable hydrogens to the organollthium cRn vary over a wid~ range depending on the results desired and is ganerally in the range of from about 5:1 to about 1:5, preferably flbout 2:I to about 1:2, and most preferably about 1:1. Similar mo]flr rntios can be employed for the organohalosilane to the lithiated hydrocarhon. The molar ratio of the solvent to the organolithium is genera]Iy in the range of from about 1000:1 to about 0.1:1, preferably flboI~t 500:I to flbout 0.5:1.
The ligand formed during the first step having the formula of r Z-EXn~l wherein the scopes of E and X flre the same as those dlsclosed above except that one X must be a halogen and n is an integer of 1 or 2, can be then contacted with an organo a]kflli metal compound having the formula of ZMa whorein Z is the same as descrthed above and Ma is an alkali metal. The presently preferred organo alkali metsl compounds represented by the formula of ZMa lnclude cyclopentadienylsodium, ; indenylsodium, tetrahydroindenylsodiIlm, fluroenylsodium, cyclopentadienyllithlum, indenyllithium, tetrahydroindenyllithlum, fluroenyllithium, or mlxtures thereof. The reflction condltions can be the sflme as those disclosed for the prepflrfltion of the hfllogenated compound of the formula Z-EX ~1 This StPp c~n also be carried out in thc presence of a solvent. The scope o~ the solvent is the same as described above. The molar ratio of the llgand to the organo alk81i metal ccn~oulld can vary in a wide range flnd is generally in the rflnge of from ~bout 5:1 to about 1:5, preferably from about 2:1 to about 1:2, and .
~ 33213C~
2~2~731 most preferably about 1.2:1 to 1:1.2. TI1P mo1ar r~tio of the solvent to ~! the organo alkali metal compound cln h~ ~enera11y the same a9 that '~ described for the solvent to the orgflnolithlum in the ~irst step of this i embodiment of the inventlon.
bridged ïi8and having the ~ormulfl of Z-EXn-7" wherein Z, E, X, and n are the same as those descrtbed ahove except that one X i9 a halogen, ls formed in the second step of thls embodiment of the process.
In the third step of this embodiment of the process, the bridged ligand thus formed is contacted with fln inorganic material. The inorganic material is generally used as catflly~st support flnd has the sflma scope as described above. This results in a bridged llgand chemically bonded to the inorganic support. The bridged l{g~nd chemicfllly bonded to fl inorganic support can then be further contacted with an organolithium ' and a metal halide having the formula of MXm, in the iourth step of this i ~ embodiment of the process, under conditions to form a bridged metallocene, whereln M is a metal selected from Ti, Zr, Rf, Sc, YJ V~ or La; m is a number sufflcient to fi]l out the remaining valences of the metal H; and each X can be the same or different, and is selected from the group consisting of alkyl groups, hydrogen, fluorine, chlorine, bromine, and iodine. The reaction conditions for this step can also generally be the same as those descrihed for the first step. Similarly, j~ a solvent can also be present in this step of the invention. The scope of the solvent can be the same as thflt in the first step and the molar ratlo of the solvent to the organoli-thium in thls step is the same as that of the solvent to the organolithium in the first step. The mol~r ratio of the bridged ligand to the organolithium can be in the range of from ~bout 5:l to about 1:5, preferably from about 3:1 to about 1:3, and ' ~ 7 ~ ~ 33213CA
2n most preferably about 1-2. The moliqr rqtio of the oi~g~nolithium to the metal hfllide is genera]ly flbout 2:1.
The supported metallocenes res11]ting from this inventlon can be recovered and puri~ied using convent10na1 techniques known in the art such as filtration and extraction. Tt is genera1ly deslrable to recover the metallocene in a form thflt is free of any substantial amount of by-product impuritles. As a general r111e, it hfls been found that the metallocenes based on unbridged fluorenyl compounds are less stable than the metallocene compounds formed from bridged fl11orenyl compounds.
Since the stability of the various metfll]ocenes varles, it is generally desirsble to use the metallocenes soon aft~qr their preparation or at least to storc the metallocene under ~onditLons favoring their stability. For example the metal10cenes c~n generally be stored in the dark, at low temperat1lre, i.e. below 0~C. and in the absence of oxygen or water.
The supported metallocenes cQn be used in combination with a sultable activator for the polymerization of olefinic monomers. In such processes the metflllocene or the activiqtor can be employed on A solid insoluble particulQte support.
Examples of suitable activator include generally~
organoaluminoxane, tris-perfluorophenyl borate, trityl tetra-perfluorophenyl borate, and any of those organometallic co-catalysts ~hich have in the past been employed in conjunction with transition metal containing olefin polymerization catfllysts. Some typical examples include organometallic compounds of metals of Groups IA, IIA, and IIIB of the Periodic Table. Examples of such compounds have included ~lgan~,letallic halide compounds, organometallic hydrides 212 ~ 7 31 and even metal hydride~s. Some speclf;c exflmples include trlethyl aluminum, tri-lsobutyl alumln~lm, ~lethy] ~luminum chloridc, diethyl alumlnum hydrlde, and the llke.
The currently most preferred activator is an organoaluminoxane. Such compoundsi lnclude, those compounds havlng repefltlng units of the formula R~
-~ Al ~ ~-~p+2 whcre R' is an alkyl group generally hflvlng l to 5 cflrbon atoms; and p is a number between 0 to about lO0, prefer~bly about 5 to nbout 50, and most preferably 10 to 40. The presently most preferred organoalumino~ane is methylalumlnoxane. Organoflluminoxanes, also sometimes referred to as poly~hydrocarbyl alumlnum oxldes) are w~ll known in the art and are generally prepared by reacting an organo hydrocarbylalumlnum compound wlth water. Such a preparation technlques are dlsclosed ln 4,808,561, the dlsclosure of which ls incorporated herein by rieference. The currently preferred co-catalysts are prepared either from trlmethylaluminum or triethylfll~lminum, sometimes referred to as poly~methyl aluminum oxide) flnd poly(ethyl aluminum oxide), respectively. It is also within the scope of the, invention to use an aluminoxane in combination with a tri~lkylaluminum, such as disclosed in U.S. Patent No. 4,794,096, the disclosure of which is incorporated herein by reference.
The supported metallocenes in combination with the organoaluminoxane activator can be used to polymerize olefins. Such polymeri~ations would be carrled out ~n a homogeneous system ln whlch the catalyst and activator were soluble; generally, lt is within the .~ ... 212~31332'3C~

,~ scope of the present invention to cflrry out the polymerizatlons ln the ;- presence of supported forms of the catalyst and/or ~ctivator in a slurry or gas phase polymerization. It is within the scope of the invention to use a mixture of two or more metallocenes or fl mixturs of an inventive bridged metallocene wlth one or more other types of metallocenes.
, The supported metallocenes when used with an orgflnoalumlnoxane ~- are partlcularly useful for the polymerizfltion of mono-unsaturated aliphatic alpha-olefins having 2 to ~0 ~arbon atoms. Examples of such olefins include ethylene, propylene, butene-l, pentene-l, 3-methylbutene-1, hexene-l, 4-methylpentene-], 3-ethylbutene-1, .:
heptene-l, octene-l, decene-1, 4,4-dimethyl-1-pentene, 4,4-dlethyl-1-hexene, 3-4-dimethyl-1-hexene, flnd the like and mixtures thereof. The catalysts are particularly useful for preparing copolymers of ethylene or propylene and generally a minor amount, i.e. no more than about 12 mole percsnt, more typlcally less than about 10 mole percent, of the higher molecular weight olefin.
~ he polymerizations can be c~rried out under a wlde range of conditions depending upon the particlllAr metallocene employed, and the results desired. Examples of typical conditions under which the metallocenes can be used in the polymerl~ation of olefins include conditions such as disclosed in U.S. Pfltents 3,242,099; 4,892,851; and 4,530,914; the disclosures of which are incorporated herein by reference. It is considered that generally any of the polymerization procedures used in the prior art with any transition metal based catalyst systems can be employed with the present fluorenyl-contalning metallocenes.

, ~ '' 23 2~2-~731 Generally the molar ratio o~ the aluminum in the organoaluminoxane to the transit~on met~l ln the metallocens would be ln the range of about 0.1:1 to about 105:l flnd more preferably about S:l to about 104:1. As a general rule, the polymerlzations would be carrled out in the presence of liquid di]uents which do not have an sdverse affect upon the catQlyst system. Examples of such liquid diluents include butane, isobutane, pentflne, hexflne, heptane; oCtAne, cyclohexane, methylcyclohexane, toluene, xylene, and the like. Th~
polymerization temperature can vary over a wide range, temperatures typically would be in the range of about -60~C to about 280~C, more preferably in the range of about 20~C to about 160~C. Typically the prsssure would be in the range of from ~bout 1 to about 500 atmospheres or greater.
The polymers produced with this invention have a wlde range of uses that will be apparent to those skllled in the art from the physlcal properties of the respective polymer. Some of the catalysts are useful for preparing syndiotactic polymers. The term syndiotactic polymer as used herein is intended to include those polymers havlng segments of more than 10 monomeric repeatlng units in whlch the alkyl group of each successlve monomeric unit ls on the opposlte side of the plane of the polymer. Generally, the polymer segments having such syndiotactic microstructure are formed of at least flbout 40 monomeric repeatlng units in which the posltlon of the alkyl group relatlve to the plane of the polymer alternates from one monomeric unit to the next monomerlc unlt.

.

~XAMPLES
A further understanding of the present invention, its various aspects, obJects and advantflges will he provided by the following examples. In these exflmples, flll runs were routinely carried out using the Schlenk technique with the e~clnsion of oxygen and molsture. Se~
genar~lly, D. F. Shriver, The Manlpulfltion of Air-sensitive Compounds~
McGraw-Hlll, 1969. Purlfled and dried argon served as protectlve gas.
The solvents used were dried by distillation over a Na/K alloy (pentane, hexane, toluene, methylene chlorLde, ether and tetrahydrofuran) or phosphorus pentoxide under argon. Tetrahydrofur~n Wa8 additionally purifled over llthium alantate and methylene chloride was additionally purified over calclum hydride. Fluorene WflS purifled over sillca gel prior to use. Analogous procedures were followed by fluoranthene and phenanthrene. The propylene used for polymerization trials was purified for 1 hour at 30~C using methylaluminoxane. A Bar autoclave ~1 liter) was used for the polymerization runs.

E~mpla I
This example illustrates the preparation of a silica-bonded, bridged ligand.
; Fluorene (Z0 g; 120 mmol) was dissolved in 200 mL of ether and slowly mixed with 76 mL of butyllithium (l.fi M in hexane). After the evolution of gas had been completed~ the mi~ture was stirred for 1 hour at room temperature and then the solvent was removed. Then solid fluorenyllithium was added in portions to a solution of 36 g (40 mL, 241 mmol) of mothyltrichlorosilane in 700 mL of pentane. After completion of the additlon, the mixture was stirred for a further period of 1 hour 332l3C~
: " 25 2~2~731 at room te~perature and the reaction mixture Wfl9 then Eiltered over sodium sulfate. The solution was concentrated by evaporation to 30% of its volume and crystalliz~d flt -30~C. The product, 9-fluorenylmethyldichlorosilane, was generflted in the ~orm of a white crystalline powder (yield: 95%).
9-Fluorenylmethyldichlorosil~ne (5 g; 17.9 mmol) was then dissolved in 100 ml of ether and -the restllting solution was mixed with 1.6 g (18 mmol) of cyclopentadlenyl sodium. After 4 hours of stirring at room temperature, the reaction mixture was filtered over sodium sulfate and the sol~ent was removed. A br~ght yel]ow crude product (l-cyclopentadienyl-9-fluorenylmethylchloro~ilane) was obtained which contained 10% bisfluorenylmethylchloro~ ne.
The crude product (5 g) obtained above was dissolved in 100 ml of toluene and the resulting solutton w~s mixed with 5 g of silica gel (Merck No. 7713) and 10 ml of pyrldine. The mixture was held for 34 hours at 80~C and then cooled to room temperature. The supernatant solutlon was decanted, the resulting prodllct (silica-0-l-cyclopenta-dienyl-9-fluorenylmethylsilflne) was wflshed several times with ether and then dried.

E~ampl~
This exa~ple illustrates the preparation of a bridged metallocene chemically bonded to an inorganlc support material.
The silica-0-1-cyclopentadienyl-9-fluorenylmethylsilane prepared in Example I was suspended or slurried in 100 ml of ether and mlxed with 2 mole equivalents (20 ml) of butyllithium (1.6 M ln hexane) per silan~. The reaction mixture was shaken for 24 hours at room 33213C~
2~ ~ 1 29731 temp0rature followed by washlng severfl1 times with ~ther (l00 ml).
After the mixture was agaln suspended 1n lOO ml o~ ether, 5 ~ (l mol equivalent) of zirconium tetxachlortde per silane wis added and the mixture was shaken for another 24 hours.
The reaction mixture was washed with ether as above and the suspension was filtered over sodium su1fate. A metfllloce~e chemically bonded to sllica, i.e., sl]ica-O-l-cyclopentadienyl-9-fluorenylmethyl-silflne zirconlum dichloride was obtalned.

Example III
This example illustrates the use of the bridged metallocene prepared in Example II as catalyst for o1efin polymerization.
Ethylene polymerization WRS conducted for one hour at 90~C in a 3.8 liter stirred, stainless steel reactor in the presence of isobutane diluent, hydrogen as a molecular weight control sgent and methylaluminoxane as the co-catalyst. First the metallocene catalyst was weighed in a dry box and slurried in n-hexane to which a solutlon of methylaluminoxane has been added. One milliliter of the toluene methylaluml~oxane solution was used. ~t was purchased from Schering at a concentration of l.l M. The charge order was metallocene/methylaluminoxane slurry an~ then 2 liters of isobutane.
After heatlng these materials to 90~C, 45 psi of hydrogen as determined from pressure drop in a 300 cc cylinder was introduced, and then ethylene was introduced so that the total reactor pressure was ~aintained at 435 psig for the entire hour. Ethylene was supplied on demand from a pressured reservoir as required during each run.
Polymeri~ation was terminated by ventlng et~ylene and dlluent. The 212~731 33213CI~
, 2~

polymer was recovered, drLed and weighe-l to determlne yie]ds. Catalyst S
productivity is calculated by dividlng polymer weight in grams by the weight of metallocene used in ~rams, or by the wei~ht of metallocene plus methylaluminoxane in grams and is conveniently exprassed 8s g polymer per g de~ired catalyst component per hour (g/g-hr).
,;' The polymerization results Are shown in Table I below.

. ~
T~bl~ I
Prod~ctlvlty ~g/g-hJ b~s~d on Run Catalyst Yield No. ~ g M~talloc~n~H~talloc~ne ~nd HAO
1 0.5 ~ 8 3.5 2 0.5 1.~ 30 13.2 bMAO, rnthylalu~inoxane.
Tha catalys~ used ~n this run was s~lica-~ cycl~ 9-fluor~nYlmoth sllans zlrconiu~ dichlorld~.
Th~ catalyst used ~n this run ~as sllica-O-l-~yclop~ntadl~nyl-9-~luor~nyl~ethyl s~lan~ zlrconlu~ d~chlGride. This catalyst ~1ffer~d fro~ run 1 in th2t tho s~llca in run 2 was ~ndr~ed.

' The results demonstrate that the, supported, bridged metallocenes are useful as olefin polymeri7,~tion catalyst.
., .

E~ample IV
25 grams of fluorene was dtssolved in 150 mL of diethyl ether and slowly r~acted with 94 mL of ~ 1.6 molar solution of butyllithium in hexane. The reaction vessel WflS cooled ln ice. The dark red solution ' from the reaction was stirred overnight at room temperature. Then 9.8 mL of dichloromethylvlnylsilane WflS added. The reactor vessel was still cooled ln lce. The reaction mtxture was stirred 4 hours at room temperature snd then mixed with 50 mL of water. The organlc phase was ~ 33213CA
28 2~473~
drled over a sodlum sulfate and the solvent was evApor~ted ln a vacuum.
The residue was dissolved ln pentsne flnd crystaltlzed at 18~C. A whlte crystalline solid was obtained wh1ch WflS determined to be bis-9-fluorenylmethylvlnylst]ane. t.80 g of the bls-9-fluorenylmethyl-vinylsilane was dlssolved in 30 mT, of trichlorosilane at room temperature. Approximately I milligram of hexachloroplatinic acid was sdded and a reaction mixture stlrred overnlght at room temperature. The solvent was evaporated in a vflcuum. A whLte solid precipitated and was character~zed as 2-(bis-9-fluorenyl-methylsilyl)-1-trichlorosilylethane.
Then 0.6 g of the 2-(bis-9-fluorenylmethylsilyl)-1-i trlchlosllylethane was suspended in 20 mL of toluene along with 2.91 g of sllica gel (Merck No. 7734) the stlica gel had been dehydrated at 400~C.
The suspenslon also included 1 ml, of pyridine. The reactionmixture was heated for 48 hours under reflux, the supernatant was then decanted and the silica gel was washed two times with 50 mL of methanol and five times wlth 50 mL of diethyl ether. The amount of supported bridged fluorenyl compound recovered was 3.16 g.
The recovered supported ligand was then suspended in 50 mL of diethyl ether and mixed with 20 mL of a 1.6 molar solution of n-butyl lithium in hexane. The reaction mixture was stirred for 48 hours at room temperature. The supernatant was then decanted and the residue washed five times with 50 mL of dlethyl ether. Then the solid was combined with 50 mL of diethyl ether and 0.42 g of zirconium dichloride.
That reaction mixture was stirred for 48 hours at room temperature and then a supernatant was decanted and the residue washed five times with 50 mL of diethyl ether. The resulting supported metallocene was then ', 33213C~
29 212~731 dried overnight in a drying cflblnet. This will be referred to as supported catalyst 33.

Exa~ple V
In this synthesis 20.6 mL of cyc1Opentadlene and 11.7 mL of 5-hexene-2~one were dissolved in 100 mI, of methanol. Whils cooling in ice 12.4 mL of pyrrolidine was ac1ded flnd the reaction mixture was stirred overnight at room temperature. Then 9.6 mL of glacial acldic acid was added. The reaction mixture was stirred for one half hour and then the solvent was evaporated in a vacul1m. The residue was dissolved in 200 mL of dlethyl ether and washed five times with lO0 mL of watar.
The organic phase was filtered using fl si]ica gel and drled over sodium sulfata. The solvent WflS evaporated in a vacuum. A yellow oil was recovered which was concluded to be 6-(3-butenyl)-6-methylfulvene.
A solution was prepared by dissolving 10 g of fluorane in lO0 mL of THF and then this was slowly reacted with 37.6 mL of a 1.6 molar solution of n-butyllithium in hexane. This dark red solution was stirred overnight at room temperature. Then a solution was prepared by combining 8.8 g of 6-(butenyl)-6-methy]fu1Yene with 50 mL of THF. This solution was then added dropwise over a period of one half hour to the solution of the fluorenyl lithium salt. That reaction mixture was stirred overnight at room temperature and then lO0 mL of water was added. The organic phase was dried overnight over sodium sulfate and tha solvent was evaporated in a vacuum. The yellow residue was dissolved in pentane and filtered using silica gel. The solvent was concentrated by means of evaporation. Crystalli~ation took place at 2 ~ 2 ~ 7 3 1 about -18~C to give 5-cyclopentdlenyl-5-(9-flllorenyl)-l-hexene ln Q form of a whlte solld.
Then 1.61 g of the brldged llgflnd having ~ vinyl termin~ted brAnch, i.e. S-cyclopantadlenyl-5-(9-flll~renyl)-l-hexene, was dissolved in 10 mL of chlorodlmethylsilane at room temperature. Then npproxlmately 1 mL of hexachloroplfltlnic acid was added and a reaction mlxture stlrred overnight ~t room temperflture. The solvent was then evflporated in a vflcUUm. A white solid W~.9 recovered whlch was concluded to be l-chlorodlmethyl-silyl-5-cyclopentadlenyl-5-(9-fluorenyl)-hexflne.
A portion of this materlal was then contflcted wlth sllica gel (Merck No.
7734) the process lnvolved contactlng 2 g of the silicfl gel drled 8S
explained ln Example IV and 1.56 g of the l-chlorodlmethyl-slly]-5-cyclopentadienyl-5-(9-flllorenyl)-hexane in a manner analogous to that used in the analogous step in Example IV. Then a supported zirconoceDe was prepared by reactlng 1.74 g of that solid with 0.8 g of zirconlum tetrachloride using a technique of the general type disclosed ln Ex~mple IV. The reslllting supported metallocene will be referred to herein ~s catalyst 34A.

ple YI
Another supported ligand WflS prepflred by combining 4.11 g of silica gel (Merck No. 15111) flnd 2.96 g of l-chlorodimethyl-silyl-5-cyclopentadienyl-5-(9-fluorenyl) hexane in a mflnner analogous to that described in Example V. About 4.4 g of this supported fluorenyl compound WflS recovered. Then 3.81 g of that supported fluorenyl compound WflS reacted with 1.76 g of zirconium tetrachloridc in n manner analogous to thflt used performing the .

~l2473~32l3c~

metallocene tn Example IV. The recovere~ sllpported m~tallocene will be referred to hereln as catalyst 34~.

~a~a~nple VII
The supportod zirconocene catalyst of Examp]es IV nnd V were evaluated for the polymerization of ethylene. The polymerizatlons were carrled out in a 1 liter laboratory autoclAve. The technique involved charging the autoclave with 500 mL of hexane snd 10 mL of methylaluminoxane. The supported zirconocene was then suspended in toluena and mixed with methylaluminox~ne and the added to the autoclave.
The autoclave was thermostatically contro]led at 60~C and a constant ethylene pressure of 9 Bar was applied, the reaction WAS stopped after 1 hour. The results of these polym~rlzations are summarized in Table II
below.

Table II
Catalyst Yield g PE/g MetAllocene-hr-bar 34a 19 10 34b 28 16 The results reveal that the supported metallocenes can be employed in the polymerization of ethylene.
Catalyst 34B was also evaluated for the polymerization of propylene. In this case 10 mL of methylaluminoxane was added to the autoclave and 500 mL of propylene was condensed into it. The contents were stirred for 30 minutes at 20 degrees C to dry ths propylene. Ths 32 2~2~7~ 332l3C~
supported zirconocene was agflln suspended ~n to1uene along wlth methylaluminoxflne and added to the Mutoc1flve. Again the reaction was s carried out at 60~C and lnterrupted flfter 1 hour. The reflctlon ylelded 62 grams of polypropylene. The flctiv1ty in terms o~ grams of polyethylene per grflms of metallocene w~s t29.
The results shown ln the above examples clearly demonstrate that the present invention is well fldapted to cflrry out the objects and attain the ends and advantages mentioned flS well flS those inherent therein. While modifications may be made by those skilled ln the art, such modifications are encompflssed withIn the spirit of the present invention as defined by the specification and the c1aims.

Claims (40)

1. A process for preparing 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.
2. A process according to claim 1 wherein said cyclopentadiene-type compound is selected from unbridged cyclopentadiene-type compounds.
3. A process according to claim 2 wherein said cyclopentadiene-type compound is selected from compounds of the formula Z-Si(R)n-X3-n wherein n is a number in the range of 0 to 2, X is a halogen, R is an alkyl or aryl group, and Z is a cyclopentadienyl-type radical selected from the group consisting of substituted or unsubstituted cyclopentadienyl, indenyl, and fluorenyl radicals.
4. A process according to claim 3 carried out in the presence of a basic organic liquid.
5. A process according to claim 4 wherein said basic organic liquid is pyridine.
6. A process according to claim 5 wherein at least two different cyclopentadienyl-type compounds are employed, each of which is selected from those the formula Z-Si(R)n -X3-n wherein n is a number in the range of 0 to 2, X is a halogen, R is an alkyl or aryl group, and Z
is a cyclopentadienyl-type radical selected from the group consisting of substituted or unsubstituted cyclopentadienyl, indenyl, and fluorenyl radicals.
7. A process according to claim 1 employing a bridged cyclopentadienyl-type compound of the formula Z-R'-Z wherein each Z can be the same or different and is selected from the group consisting of substituted or unsubstituted cyclopentadienyl, indenyl, and fluorenyl radicals and R' is a bridge connecting the two Z radicals, said bridge containing an active halogen.
8. A process according to claim 7 wherein R' has the formula wherein R is selected from the group consisting of halides, alkyl radicals, and aryl radicals and X is a halide.
9. A process according to claim 9 carried out in the presence of a basic organic liquid.
10. A process according to claim 10 wherein said basic organic liquid comprises pyridine.
11. A process according to claim 11 wherein said support consists essentially of silica.
12. A process according to claim 7 wherein R' has a branch of the formula wherein X is a halide, each R can be the same or different and is selected from the group consisting of halides, hydrogen, alkyl, and aryl radicals, R" is hydrogen or a hydrocarbyl group having 1 to 10 carbon atoms, and R"' is a hydrocarbyl group having 1 to 10 carbon atoms.
13. A process according to claim 13 wherein each R is Cl.
14. A process according to claim 14 wherein the two Z's are bound to a branched methylene radical.
15. A process according to claim 13 wherein each R is a methyl radical and the two Z's are bound to a branched methylene radical.
16. A process according to claim 13 wherein the two Z's are bound to a branched methyl silyl radical.
17. A process according to claim 13 wherein said cyclopentadienyl-type compound is selected from the group consisting of 2-(bis-9-fluorenyl methylsilyl)-1-trichlorosilyl ethane, 5-cyclopentadienyl-5-(9-fluorenyl)-1-trichlorsilyl hexane, and 1-chlorodimethyl silyl-5-cyclopentadienyl-5-(9-fluorenyl)hexane.
18. The solid product of the process of claim 1.
19. The solid product of the process of claim 17.
20. The solid product of the process of claim 16.
21. A process according to claim 1 wherein at least two different cyclopentadienyl-type compounds having active halogen are reacted with said support.
22. The solid product produced by the process of claim 22.
23. A process for producing a metallocene comprising reacting the supported cyclopentadienyl-type product produced by the process of claim 1 with a suitable transition metal compound under suitable reaction conditions.
24. A supported metallocene produced by the process of claim 24 wherein the cyclopentadienyl-type product is produced by reacting a bridged cyclopentadienyl-type compound in which the bridge contains an active halogen with said inorganic support.
25. a process for polymerizing an olefin comprising contacting said olefin under suitable polymerization conditions with the supported metallocene of claim 25.
26. A polymer produced by the process of claim 26.
27. A process according to claim 26 wherein said supported metallocene contains at least two different metallocenes having different effects upon the olefin polymerization.
28. A process for preparing a bridged metallocene comprising:
(1) contacting a hydrocarbon having at least two acidic, replaceable hydrogens and having the formula of ZH2 with an organolithium and an organohalosilane to prepare a ligand precursor having the formula of HZ-EXn+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-EXn -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 MYm to prepare said bridged metallocene; wherein each Z can be 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, NR2, PR2, or OQ, and mixtures thereof wherein the R is a C1-C20 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 selected from C, Sn, Si, Ge, B, Al, N, P, and mixtures thereof; 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.
29. A process according to claim, 29 producing a metallocene selected from the group consisting of silica-O-1-cyclopentadienyl-1-cyclopentadienylmethylsilane zirconium dichloride, silica-O-bis(9-fluorenyl)phenylsilane zirconium dichloride, silica-O-1-cyclopentadienyl-9-fluorenylmethylsilanne hafnium dichloride, silica-O-bis(9-fluorenyl)phenylsilane hafnium dichloride, silica-O-1-cyclopentadienyl-9-fluorenylmethylsilanne vanadium dichloride, silica-O-bis(9-fluorenyl)phenylsilane vanadium dichloride, silica-O-1-cyclopentadienyl-9-fluorenylmethylsilane titanium dichloride, silica-O-bis(9-fluorenyl)phenylsilane titanium dichloride, silica-O-bis(2,8-difluoro-9-fluorenyl)methylsilane zirconium dichloride, 1-cyclopentadienyl-9-fluorenylmethylchlorosilane zirconium dichloride, bis(9-fluorenyl)phenylchlorosilane zirconium dichloride, 1-cyclopentadienyl-9-fluorenylmethylchlorosilane hafnium dichloride, bis(9-fluorenyl)phenylchlorosilane hafnium dichloride 1-cyclopentadienyl-9-fluorenylmethylchlorosilane vanadium dichloride, bis(9-fluorenyl)phenylchlorosilane vanadium dichloride, 1-cyclopentadienyl-9-fluorenylmethylchlorosilane titanium dichloride, bis(9-fluorenyl)phanylchlorosilane titanium dichloride, bis(2,8-difluoro-9-fluorenyl)methylchlorosilane zirconium dichloride, silica-O-1-cyclopentadienyl-9-fluorenylmethylsilanne zirconium dichloride, alumina-O-1-cyclopentadienyl-9-fluorenylmethylsilane zirconium dichloride, bentonite-O-1-cyclopentadienyl-9-fluorenylmethyl-silane zirconium dichloride, and mixtures thereof.
30. A process according to c1aim 30 producing the metallocene silica-O-1-cyclopentadienyl-9-fluorenylmethylsilane zirconium dichloride.
31. A process for preparing a bridged cyclopentadienyl-type compound having a branch containing a olefinic group comprising reacting a dihalo olefinic silane with a alkali metal salt of a suitable cyclopentadiene-type compound to produce a compound of the formula 2-R'-Z wherein each Z is the same or alternatively to produce a compound of the formula Z-R'-X wherein X is a halogen and then reacting that compound with an alkali metal salt of another different cyclopentadiene-type compound to produce a compound of the formula Z-R'-Z wherein the two Z's differ, said Z's each being individually selected from the group consisting of cyclopentadienyl-type compounds and R' is the organic remnant of the dihalo olefinic silane.
32. A bridged cyclopentadienyl-type compound produced by the process of claim
33. A bridged cyclopentadienyl-type compound of the formula 1) wherein n is a number in the range of about 0 to 10: R is Si, Ge, C, or Sn; R" is selected from hydrogen, or alkyl groups having 1 to 10 carbon atoms, or aryl groups having 6 to 10 carbon atoms.
34. The compound bis-9-fluorenylmethylvinylsilane.
35. A metallocene produced from the compound of claim 34.
36. A process for preparing a bridged cyclopentadienyl-type compound having a branch containing olefinic vinyl group comprising reacting a carbonyl compound having olefinic unsaturation with cyclopentadiene in the presence of pyrrolidine and methanol to yield an alkenyl fulvene which is then reacted with an alkali metal salt of a cyclopentadiene-type compound to yield the unsaturated-branched-bridged ligand containing two cyclopentadienyl-type groups.
37. A process according to claim 37 wherein 5-hexene-2-one is reacted with cyclopentadiene to yield 6-(3-butenyl)-6-methylfulvene which is then reacted with fluorenyllithium and then subjected to hydrolysis to yield 5-cyclopentadienyl-5-(9-fluorenyl)-1-hexene.
38. A bridged cyclopentadienyl-type compound produced by the process of claim 37.
39. The compound 5-cyclopentadienyl-5-(9-fluorenyl)-1-hexene.
40. A metallocene produced from the product of claim 39.
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