AU646537B2 - Metallocene (CO)polymers, process for their preparation and their use as catalysts - Google Patents

Abstract

An immobile (heterogeneous) metallocene catalyst component which can advantageously be employed for the polymerisation of olefins is obtained by the homopolymerisation of suitably substituted (vinyl group-containing) metallocenes from the 4th sub-group of the Periodic Table or by copolymerisation of such metallocenes with (di)vinylaromatic compounds.

Description

Regulation 3,2(2)

AUSTRALIA

Patents Act 1990 6 4* 5

KV;

7 7

ORIGINAL

COMPLETE SPECIFICATION STANDARD PATENT Application Number: Lodged: 0~ 9* 0S*

S

@05555

S

5.55

S

~5S.5 Invention Title: METALLOCENE (CO) POLYMERS, PROCESS FOR THEIR PREPARATION AND THEIR USE AS CATALYSTS *5 5* S. S S S S S*

S

*SSS 55 5555

S

SSSS

.5555 S The following statement is a full description of this invention, including the best method of performing it known to us HOECHST AKTIENGESELLSCHAFT HOE 91/F 007 Dr.LO/je Description Metallocene (co)polymers, process for their preparation and their use as catalysts.

The present invention primarily relates to a process for the preparation of an immobile (heterogeneous) metallocene catalyst component by homopolymerization of metallocenes containing vinyl functional groups or by copolymerization of such metallocenes with (di)vinylaromatic compounds. The polymers prepared in this way have advantageous properties as catalysts in olefin polymerization.

Metallocenes of transition metals are known as catalyst components (cf. US 4 522 982, US 4 542 199 and EP-A 128045). Together with aluminoxanes they form S* *.15 homogeneous transition metal catalysts which are soluble .0 in aromatic and aliphatic hydrocarbons. Thpe- catalysts are highly active. Together with salts of non-coordinat- S.ing anions, metallocenes also form an active system for olefin polymerization (cf. EP-A 277 003/4).

However, soluble catalysts have disadvantages if they are to be used in existing industrial plants, since the latter are as a rule equipped for the use of hetero- S*.i geneous catalyst systems.

S S Metallocene catalysts in which a zirconocene or titano- 25 cene component and an aluminoxane are applied conjointly from a solution to a silicate support have also been disclosed (cf. EP-A 206 794). However, this catalyst system has low activity. Moreover, the catalyst components are not anchored sufficiently firmly to the support and can thus be extracted during the polymerization.

It is also known that metallocene compounds containing silyl ether radicals can be applied to silicate supports with the formation of siloxane bridges (cf. EP-A 293 815).

2 For this purpose it is necessary to remove the water bonded by adsorption to the support material by drying for several hours at a temperature of at most 800 0

C.

It is also known that a heterogeneous metallocene catalyst is obtained if a metallocene compound containing olefin groups is reacted with a poly(methylhydrogenosiloxane) under hydrosilylation catalysis (cf. DE-OS (German Offenlegungsschrift) 38 40 772).

These polymerization catalysts are distinguished by only moderate polymerization activity, especially in comparison with their soluble precursors.

In Pure and Appl. Chem., Vol. 58 '1986) 617-622 the copolymerization of (Cp-vinyl) CpTiCl 2 (Cp cyclopentadienyl) and the like with vinylbenzene is described.

There is no indication of a possible use of the reaction product as a catalyst. Experiments have shown that titanocene-based copolymers of this type have only a low polymerization activity.

**s*e The object was, therefore, to find a catalyst system which is insoluble in conventional solvents including aromatic solvents but nevertheless has a high polymerization activity.

*5 It has been found that the abovementioned disadvantages can be overcome if a zirconocene or hafnocene containing :25 vinyl functional groups is polymerized, optionally together with a (di)vinyl-aromatic compound, and the resulting polymer is used as polymerization catalyst.

The present invention therefore relates to a process for the preparation of an immobile metallocene catalyst component, wherein a metallocene of formula I -3 3 R' M0 [CpR 3 [CpR 6-R,] and/or of formula II Rr1

II)

R1 in which R M41 is zirconitum or hafnium and Cp is a cyclopentadienyl radical,

R

1 and R 2 are identical or different and are a hydrogen *.:atom, a halogen atom, a Cl-C 10 -alky. group, a

C

1 -Cl-alkoxy group, a C 7

-C

2 0 -arylalkyl group, a C.-Cl.-aryl group or a C 6 -Cl-ar.yloxy group, and 5 R 1 and R 2 can also be linked to one another and together with k' can form a metallo ring, the radicals R 3 are identical or different and are a hydrogen atom, a halogen atom, a C 1 -Cl 0 -alkyl group, a Cr,-Cl-aryl group, a C 7

-C

2 0 -arylaiky?, group, a -Cfluoroalkyl group or an organometallic radical, such as Cl-C 1 0 )-trialkylsilyl, C 8

C

1 -aryl-Cl-Cla-dialkyla ilyl, C 1

,-C

1 -alkyl-Cr-C-diaryls ilyl or CG-CIDtriarylsilyl, R 4 and R 5 are identical or different and are a vinyl group,. a C 6

-C

1 -arylvinyl group, a C-C-alkylviny).

5:555:group or a C6-C 1 -vinylaryl group, all of which may be substituted,

R

6 and W 7 are identical or. different and are a cyclopentadienyl, indenyl or fluorenyl radical, it being possible for said rings together with M1 to form a 4 sandwich structure,

R

8 and R e are identical or different, are substituents of R 8 and R 7 and have the meanings given for R 3

R

4 and R 5 with the proviso that R 6 and

R

7 can be monosubstituted or polysubstituted by R 8 or

R

9 but at least one ring R 6 or R 7 must carry at least one radical R 8 or R 9 having the meaning of R 4 and R 5 and

R

10 has the meaning shown in formulae III-VII R R1 1 R"1 R13 R11 R13 R1" R13

M

2

-C-M

2

-M

2 I I I I I14 14 R R 2

R

12

R

1

R

1 2

R

14 R1 R (1I) (IV) (VI) (VII), where

M

2 is silicon, germanium or tin and R. R 1

R

12

R

13 and R4 are identical or different and are a hydrogen atom, a halogen atom, a C 1 =Co-alkyl group, a C 1

-C

1 o-fluoroalkyl group, a C6-Co-aryl group, a C 6 -Co 1 -fluoroaryl group, a Cz-Clo-alkoxy group, a C-Clo-aryloxy group or a C 7

-C

20 -arylalkyl group,

R

11 and R 12 R1 3 and R 1 and R 13 or R 12 and R" together with the atoms linking them can form a ring 20 system and *I m and n are identical or different and are a number from 0 to 5, where m+n must be a 1, is homopolymerized or copolymerized, or a compound of formula I and/or of formula II is copolymerized with a (di)vinyl-aromatic compound.

The immobile metallocene catalyst components prepared by the process according to the invention are novel and are likewise a subject of this invention.

Metallocene catalyst component according to the invention thus signifies: a) homopolymers of compounds I and II, 5 b) copolymers of one or more compounds I and one or more compounds II, c) copolymers of one or more compounds I and one or more (di)vinyl-aromatic compounds, d) copolymers of one or more compounds II and one or more (di)vinyl-aromatic compounds, and e) copolymers of one or more compounds I and II and one or more (di)vinyl-aromatic compounds.

Preferably, in formulae I and II

R

1 and R 2 are identical or different and are a hydrogen atom, a halogen atom, a Cl-C 4 -alkyl group, a

C

1

-C

4 -alkoxy group, a C 7

-C

14 -arylalkyl group, a

C

6 -Clo-aryl group or a C-Co 1 -aryloxy group, and

R

1 and R 2 can also be linked to one another and together with M 1 can form a metallo ring, 0* the radicals R 3 are identical or different and are a hydrogen atom, a halogen atom, a Ci-C 4 -alkyl group, a CG-C 1 -aryl group, a C 7

-C

14 -arylalkyl group, a Ci-C-fluoroalkyl group or an organometallic radical, such as C 1 -Co 1 -trialkylsilyl, C 6 -Co 1 -aryl-Ci-C6-dialkylsilyl, Ci-C 4 -alkyl-C 6 -Co1-diarylsilyl or Cs-Clo-triarylsilyl,

R

4 and R 5 are identical or different, preferably identical, and are a vinyl group, a C-Ci-arylvinyl group, a Ci-C,-alkylvinyl group or a C 6 -Cle-vinylaryl group, which groups may be substituted by a Ci-C 4 -alkoxy group, C 1

-C

4 -alkyl group or OH group,

R

6 and R 7 are identical or different and are a cyclopentadienyl, indenyl or fluorenyl radical, it being possible for said rings together with M 1 to form a sandwich structure,

R

8 and RO are identical or different, are substituents of R 6 and R 7 and have the meanings 6 given for R 3

R

4 and R 5 with the proviso that R 6 and

R

7 can be monosubsttuted or polysubstituted by R 8 or

R

9 but at least one ring R 6 or R 7 must carry at least one radical RO or R 9 having the meaning of R 4 and R 5 and

R

10 has the meaning shown in formulae III-VII, where

M

2 is silicon or germanium and R 1

R

12

R

13 and R 14 are identical or different and are a hydrogen atom, a halogen atom, a Ci-C.-alkyl group, a C-C-fluoroalkyl group, a C.-C, 1 -aryl group, a CL-Clo-fluoroaryl group, a C 1

-C

6 -alkoxy group, a C 6 -Clo-aryloxy group or a Cy-C 1 4 -arylalkyl group,

R

11 and R 12

R

1 3 and R 14

R

1 and R 13 or R 12 and R1 4 together with the atoms linking them can form a ring system, and m and n are identical or different and are a number from 0 to 5, where m+n must be a 1.

In particular, S* R 1 and R 2 are identical or different and are a hydrogen 20 atom, a halogen atom, a Ci-C 4 -alkyl group or a C-C,-aryl group, and

R

1 and R 2 can ,lso be linked to one another and together with A 1 can form a metallo ring, the radicals R 3 are identical or different and are a hydrogen atom, a halogen atom, a C,-C 4 -alkyl group, a C 6 -C10-aryl group or an organometallic radical, such as CI- i~-trialkylsilyl,

R

6 and R 7 are a cyclopentadienyl radical, and Ri 0 has the meaning shown in formulae III-V, where

M

2 is silicon and R 11

R

12

R

13 and R" are identical or different and are a hydrogen atom, a halogen atom, a C,-Cs-alkyl group or a Ce-Co 1 -aryl group, and

R

n and R i RiS and R' 1 and R 13 or R 12 and R 14 together with the atoms linking them can form a ring -7system.

R1 0 is preferably a dialkylsilyl group or a 1,2-alkanediyl group, in particular a dimethylsilyl group or 1,2-ethanediyl group.

R"

1 and R 12 or R3 and R 14 can be linked to one another with the formation of spirocyclic systems such as in the same way as R 11 and R13 or R1 2 and R 14 can form the following ring system

C

S.

R1 2 14 Examples of suitable metallocenes of formula I are:

CI

2 Zr

(I-I)

CIZr (1-2) j (1-3) *C1Zr2 !Z (2 8-

CJ

2 Zr ~~12 Examples for formula II are: ,r0 C1 2 Zr Si .z IlI C170

S

C1.7.

*Sbtiun is a*ehl ru) Th*rprto rcse o te. tloee ecie ar knw.npicpl;c.Junlof.gnmtli he. 28*18)6-7 PA3072adteilsrtv *mets Exmpe if (iviy...i cmond obeue CiyleityZr e (-or11-3).le stree (Sunybitent 4-is ea mthl group).htalnean 1 Thetpreparationoprocesses for the istarefernblydescribed 9 if crosslinking is desired during the polymerization.

These substances are commercially available.

If the metallocane compounds I and/or II are polymerized with vinylbenzene and divinylbenzene, they contain at least one vinyl group. If the compounds I and/or II are copolymerized with vinylbensene but without divinylbenzene, they must then have at least 2 vinyl groups.

The (co)polymerization can take place either by the action of heat (without free radical initiator) or (preferably) by free radical catalysis. In the latter case, free radical forming agents are added in catalytically effective amounts to the reaction mixture. The suitability of a substance as a catalyst (free radical forming agent) for the process according to the invention results in particular from its half life at a given temperature. a, a'-Azo-isobutyronitrile is preferably 0** used. However, numerous compounds from the substance category comprising organic peroxides are also suitable for the said purpose.

:20 Examples of such compounds are: tert-butyl perbenzoate, 2,2-bis-(butylperoxy)butane, di-tert-butyl diperphthalate, tert-butyl perisononanate, tert-butyl peracetate, 2,5-dimethylhexane 2,5-diperbenzoate, 3,5,5trimethylcyclohexanone perketal, mono-tert-butyl per- :4,25 maleate, tert-butyl perisobutyrate, p-chlorobenzoyl peroxide, tert-butyl peroctoate, benzoyl peroxide, diacetyl peroxide, succinyl peroxide, propionyl peroxide, capryloyl peroxide, lauroyl peroxide, decanoyl peroxide, isononanoyl peroxide, tert-butyl perpivalate or 2,4-dichlorobenzoyl peroxide.

For polymerization, the reactants are introduced into a hydrocarbon, preferably into an aromatic hydrocarbon, in particular toluene or xylene, and heated for 1 to 24 h, preferably 4 to 10 h, at 6G-140C, preferably 80-90"C, and 0.1 g portions of a,a'-azo-isobutyronitrile are added 10 1 to 4 times during the reaction. The supernatant is decanted off from the resulting polymer, which is swollen in aromatic solvents, and the product is washed with the solvent used and then dried under vacuum. The residue is washed several times with saturated hydrocarbon, preferably n-hexane or n-pentane, and dried under vacuum.

The vinylmetallocenes of formulae I or II can also readily be homopolymerized by the action of heat (without a free radical initiator). This can be carried out in a high-boiling inert solvent, such as n-octane or xylene, or also, preferably, without a solvent. With this procedure a solid is formed which is insoluble in hydrocarbons.

The homopolymers or copolymers according to the invention can advantageously be used as catalysts for the poly- I merization of 1-olefins of the formula

R

15 CH CH 2 in which R 15 is hydrogen or a straight-chain or branched alkyl group, preferably ethylene, propylene or 4-methylpent(1)-ene.

In addition, the catalyst can also be used for the polymerization of cyclic olefins, such as cyclopentene, cyclohexene or norbornene, diolefins and cyclic diolefins.

It is also possible to copolymerize several olefins of the abovementioned formula or cycloolefins with one another.

For the preparation of polyolefins, a catalyst system is preferably used which, in addition to the metallocene polymer according to the invention, comprises an aluminoxane as cocatalyst. The preparation and the use of such aluminoxanes are known Pasynkiewicz, Polyhedron 9 11 (1990) 429 and EP-A 302 424).

It is also possible to use a salt-like compound of the formula RzNH4-XBR' 4 or of the formula R 3

PHBR'

4 as cocatalyst instead of (or in addition to) an aluminoxane.

In these formulae x is 1, 2 or 3, R is alkyl or aryl, which may be identical or different, and R' is aryl, which may also be fluorinated or partially fluorinated.

In this case, the catalyst consists of the reaction product of the metallocene polymer with one of the said compounds (cf. EP-A 277 004).

Furthermore, the metallocene polymer described above can also be reacted with an alkylating agent, such as a Grignard or lithium compound, in particular Li aluminoalkyl and especially methyllithium. This reaction is of course not required in the case of compounds of formulae 3' I or II which are already appropriately substituted. The product of this reaction is then reacted with the said salt of a non-coordinating anion.

In all cases, an immobile (heterogeneous) catalyst system u: 20 of high polymerization activity is obtained which can advantageously be used for olefin polymerization.

The examples which follow are intended to illustrate the invention in more detail.

.r Example 1: C1 2 ZrCp(Cp-vinyl) 0 25 5.29 g (57.4 mmol) of 6-methylfulvene were dissolved in 100 cm 3 of THF and 38.3 cm 3 of a 1.5 M (57.43 mmol) lithium diisopropylamide/THF complex solution in cyclo- *e4* hexane were added dropwise in the course of 1 h and the mixture was stirred for 2 h at RT. After filtering, the filtrate was evaporated and the Li® (Cp-vinyl)e content was determined by NMR spectroscopy and found to be about the remainder was adhering solvent.

The yield was 6.27 g (about 12 1.13 g (85% pure 11.52 mmol) of Li (Cp-vinyl), dissolved in 30 cm 3 of THF, were added in the course of min at -78 C to a suspension of 3.03 g (11.53 mmol) of Cl 3 CpZr in 30 cm 3 of THF. After warming to RT, the mixture was stirred for a further 3 h and the clear yellow solution was evaporated. The residue was stirred with cm 3 of n-pentane and the mixture evaporated again. After stirring with toluene, the mixture was filtered, the solvent was stripped off and n-pentane was added and, after digestion, stripped off. After taking up in CHCl 3 the mixture was filtered and the filtrate was evaporated and digested with n-pentane, whereupon the oily residue solidified, and the product was filtered off and dried.

Yield: 2.38 g (7.48 mmol 64.8%) of (Cp)(Cp-vinyl)ZrCl2.

The product obtained had the NMR spectrum to be expected (100 MHz, CDC13): 6 5.35 (dd, 1H, Ji 11, JsGM 1Hz), 5.58 (dd, 1H, Jt s 18 Hz), 6.33 6.53 9H, Cp-H), S6.58 (dd, 1H).

SExample 2: Homopolymerization of C1,ZrCp(Cp-vinyl) 20 0.34 g (1.07 mmol) of the complex from Example 1 were dissolved in 10 cm 3 of toluene, 0.1 g of a,a'-azo-isobutyronitrile (AIBN) was added and the mixture was stirred for 2 h at 90"C. A greenish solid formed, which was filtered off and washed with solvent. After drying, 25 0.11 g of product was obtained; the Zr content was 22.5%.

Example 3: Hompolymerization of Cl 2 ZrCp(Cp-vinyl) 0.25 g (0.79 mmol) of the complex from Example 1 was .dissolved in 10 cm 3 of toluene, 0.1 g of AIBN was added and the mixture was stirred for 4 h at 100°C; after adding a further 0.1 g of AIBN, the mixture was stirred on* for a further 6 h at this temperature and the brownish precipitate was filtered off, washed and dried. The 0.18 g of product contained 24% Zr.

Example 4: Cl 2 Zr(Cp-vinyl) 2 1.54 g (85% pure 14 mmol) of Li(Cp-vinyl) in 100 cm 3 of THF were added in portions at -78 0 C to 2.58 g (6.84 mmol) 13 of C1 4 Zr(thf) 2 in 50 cm 3 of THF. After warming to -20 0

C,

the solvent was stripped off in the course of 1 h at RT.

The yellow-orange evaporation residue was extracted with a total of 300 cm 3 of n-hexane/toluene 2:1 (vol) in portions and the extracts were filtered off and evaporated.

n-Pentane and a few cm 3 of toluene were added to the residue and after filtering, the filtrate was evaporated and extracted with a little n-pentane. A whitish residue remains, which was dried under vacuum.

Yield: 0.37 g (1.03 mmol 15%) of (Cp-vinyl) 2 ZrCl 2 The compound had the correct elementary analysis.

Example 5: Me 2 ZrCp(Cp-vinyl) 1.75 cm 3 of a 1.6 N (2.8 mmol) ethereal methyllithium solution were added dropwise at -50 0 C to 0.4 g (1.26 mmol) of the complex from Example 1 in 10 cm 3 of EtO2 and the mixture was stirred for 1 h at 0°C. After replacing the solvent by n-pentane, the mixture was stirred for a further 1 h at RT and evaporated and the residue was extracted with toluene. A white evaporation residue then remains.

Yield: 0.2 g (0.72 mmol 57%) of (Cp)(Cp-vinyl)ZrMe 2 The NMR spectrum shows the integration ratio of 2:1 to be expected for aromatic compounds to saturated hydrocarbon H.

S.o Example 6: Cl 2 Zr(Me2,vinyl-Cp) z SiMe 2 12.7 cm 3 of 1.6 N (20.3 mmol) ethereal methyllithium were added dropwise to 3 g (10.1 mmol) of (2,3-Me 2

CH

2 2 SiMe 2 in 50 cm 3 of Et 2 O and the mixture was then stirred for 2 h at about 35 0 C. The solvent was then stripped off. 2.35 g (10.1 mmol) of ZrCl 4 were suspended in 100 cm 3 of CH 2

CCI

2 at -78°C and the evaporation residue described above was added to the suspension. The mixture was slowly warmed to 0*C and stirred for 1 h at this temperature and, after filtering, the solvent was stripped off. The filtered and evaporated toluene extract was examined by NMR snectroscopy. It shows a complex 14 mixture.

Yield: 0.87 g (2.19 mmol 22%) of rac/meso-{(2,3-Me 2 vinyl-CsH 2 2 SiMe 2 ZrCl 2 Example 7: Copolymerization of Cl 2 ZrCp(Cp-vinyl) A mixture of 0.1 g (0.31 mmol) of the abovementioned complex and 5 cm 3 of vinylbenzene was stirred for 6 h at in 50 cm 3 of toluene/n-hexane (1:4 by volume) with the addition of 0.15 mg of AIBN. After very slight formation of solid, the mixture was evaporated, the residue taken up several times in toluene and the solvent stripped off again. The NMR spectrum of the final residue shows no further vinyl groups.

Yield: 3.4 g of copolymer; Zr content: 0.88%.

Example 8: Terpolymerization of Cl 2 ZrCp(Cp-vinyl) .:15 0.2 g (0.63 mmol) of the abovementioned complex, 0.5 cm 3 of dirir~.benzene and 8.5 cm 3 of vinylbenzene were stirred in 15 cm 3 of toluene with 0.1 g of AIBN for 2 h at After adding a further 20 cm 3 of solvent, the gelatinous oe mass was stirred for a further 3 h at this temperature.

After evaporation, the residue was washed thoroughly with n-pentane and dried.

Yield: 4.57 g; Zr content 0.94%.

Example 9: Terpolymerization of Cl 2 ZrCp(Cp-vinyl) 0.25 g (0.79 mmol) of the complex from Example 1, 1 cm 3 of divinylbenzene and 8.5 cm 3 of vinylbenzene were stirred in 15 cm 3 of toluene with 0.1 g of AIBN at 80 0 C. After 2 h, the gelatinous mass was diluted with 15 cm 3 of toluene and stirred for a further 2 h at the above temperature. The subsequent procedure corresponded to that of Example 8.

Yield: 3.74 g; Zr content: 1.2%.

Example 10: Copolymerization of (Cp-vinyl) 2 ZrC1, 0.2 g (0.56 mmol) of the abovementioned compound and cm 3 of vinylbenzene were stirred in 20 cm 3 of toluene with 0.1 g of AIBN at 75 0 C for 5 h. After evaporation, 15 the resulting mass was washed with n-pentane and dried.

A little vinylbenzene was still discernible in the NMR spectrum, but no vinyl signals from the metallocene compound.

Yield: 3 g; Zr content Example 11: Terpolymerization of Me 2 ZrCp(CP-vinyl) 0.1 g (0.36 mmol) of the abovementioned complex, 0.5 cm 3 of divinylbenzene and 5 cm 3 of vinylbenzene were stirred in 15 cm 3 of toluene with 0.1 g of AIBN at 80°C for 4 h.

The gelatinous product was filtered off, washed and dried.

Yield: 3.7 g; Zr content: 0.7%.

Example 12: Terpolymerization of [(2,3-Me 2 -5-vinyl-C 5

H

2 2 SiMe 2 ]ZrCl 2 0.22 g (0.51 mmol) of the said complex, 1 cm 3 of divinylbenzene and 8 cm 3 of vinylbenzene were stirred ir 30 cm 3 of toluene with 0.1 g of AIBN at 85 0 C for 7 h. After S090. evaporation and thorough washing of the residue .th npentane, the product was dried.

Yield: 4.2 g; 1% Zr content.

Example 13: Hompolymerization of Cl 2 ZrCp(Cp-vinyl) without solvent 0* (by the action of heat) 0.24 g (0.75 mmol) of the said compound was heated at 2 5 115°C for 1 h in a Schlenk vessel. During this period the substance assumes a darker color. The substance was then extracted with toluene and filtered off. 0,19 g of product having a Zr content of 23% was obtained.

Example 14: Reaction of a metallocene polymer with a cocatalyst 2 g of the product from Example 11 were suspended in cm 3 of toluene and 0.13 g (0.15 mmol) of [BuNH][B(CF 5 4 J was added to the suspension at 0°C and the mixture was stirred for 1 h. The supernatant was removed from the dark colored mixture by decanting and 16 the product was washed with solvent and then dried under vacuum.

Yield! 1.87 g; Zr content: 0.6%.

Example 15: Reaction of a metallocene polymer with an alkylating agent and a cocatalyst 2 g of the product from Example 10 were suspended in cm 3 of Et 2 O and 0.4 cm 3 of a 1.5 N (0.64 mmol) ethereal MeLi solution was added at -20 0 C, the mixture was stirred for 1 h at 0°C and filtered, the solvent was replaced by 20 cm 3 of toluene and 0.12 g (0.21 mmol) of [Bu 3 NH][B-(p-tolyl)4 was added. After stirring for 1 h, the product was filtered off, washed and dried.

Yield: 0.19 g; Zr content: 1.3%.

a. Olefin polymerization using a metallocene monomer as catalyst Example 16 900 cm 3 of a diesel oil fraction 100-120"C) were initially introduced into a 1.5 dm 3 reactor and heated to The reactor was charged with 13 mmol of a strength toluene solution of methylaluminoxane and 1 pmol of catalyst (from Example Ethylene was then injected until a final pressure of 7 bar was reached and the 00 mixture was polymerized for 2 h. Aqueous HC1 was then added to the polymer solution. The polymer was isolated, 5 washed with acetone and dried under vacuum. 82.7 g of polyethylene were obtained, corresponding to an activity of 41.4 kg of polymer/mmol Zr.h (see table for further data).

0 Example 17 The procedure was as in Example 16. The polymerization catalyst contained the metallocene monomer from Example 4. 78.9 g of polymer were obtained. This corresponds to a yield of 39.5 kg of polyethylene/mmol Zr.h (see table for further data).

17 Olefin polymerization using metallocene polymers as catalyst Example 18 The procedure was as in Example 16. The catalyst used was the product from Example 7 (0.001 mmol Zr). 72 g of polyethylene were obtained, corresponding to 36 kg of polymer/mmol Zr-h (see table for further data).

Example 19 The polymerization was carried out as in Example 16. The amount of catalyst according to Example 10 which was employed corresponded to 0.0005 mmol Zr. 27.1 g of polyethylene were obtained. This corresponds to 27.1 kg of polymer/mmol Zr.h (see table for further data).

Example *15 The procedure was as in Example 16, except that the catalyst from Example 8 was used (0.5 pmol Zr). The yield after 2 h was 52.6 g of polyethylene having a VI of 620 cm 3 /g (see table).

Example 21 The procedure was as in Example 16, except that the catalyst from Example 9 was used (0.2 pmol Zr). The yield after 2 h was 32.2 g of polyethylene having a VI of 671 cm 3 /g (see table).

Example 22 900 cm 3 of a diesel oil fraction 100-120 0 C) and 0.015 g (corresponding to 0.001 mmol Zr) of catalyst from Example 14 were initially introduced into a 1.5 dm 3 reactor and Yeated to 70"C. After injecting ethylene until a final pressure of 7 bar was reached, polymerization was carried out for 2 h. After decomposition with HC1, the product was washed with acetone and dried.

63.7 g of polyethylene were obtained, corresponding to 31.9 kg of polymer/mmol Zr.h (see table for further data).

18 Example 23 The procedure was as in Example 22, but the catalyst originated from Example 15 and the yield of polyethylene was 68.0 q. This corresponds to an activity of 34 g of polymer/mmol Zr-h (see table for further data).

Example 24 After flushing with nitrogen, a dry 16 dm 3 reactor was filled with 10 dm 3 of liquid propylene. 40 mmol of a toluene solution of methylaluminoxane were then added and the mixture was stirred for 15 min at 30 0

C.

In parallel with this, a mixture of 0.05 mmol of metallocene according to Example 6 and 20 mmol of a toluene solution of methylaluminoxane was prepared and preactivated by leaving to stand for 15 minutes.

S0 *15 This mixture was then added to the reactor, the reaction mixture was heated to 70"C and the polymerization was started. After 1 h the reaction was stopped by cooling and releasing pressure. 2.39 kg of polypropylene were obtained. This corresponds to 47.8 kg/mmol Zr-h (see table for further data).

Example The procedure was as in Example 24. However, the catalyst 0 used was 0.05 mmol of metallocene polymer according to Example 12.

a 1.95 kg of polypropylene were obtained, corresponding to 39 kg of polymer/mmol Zr.h (see table for further data).

*.S

Example 26 cm 3 of cyclopentane, dissolved in 800 ml of diesel oil (boiling point 100-120*C), were initially introduced into a 1.5 dm 3 reactor and the reactor was charged with mmol of a toluene solution of methylaluminoxane and 0.01 mmol of metallocene polymer according to Example 8.

After polymerization for 2 h at 60"C, the reaction was 19 stopped using methanol; the resulting polymer was filtered off and dried. The yield was 6.2 g, corresponding to 0.31 kg of polymer/mmol Zr.h.

Example 27 600 cm 3 of a diesel oil fraction 100-120"C) and 300 cm 3 of cyclopentene were initially introduced into a dm 3 reactor and heated to 60 0 C. The reactor was charged with 60 mmol of a toluene solution of methylaluminoxane and 0.01 mmol of metallocene polymer according to Example 2. After injecting ethylene to a pressure of 7 bar, the batch was polymerized for 2 h, the polymer solution was then added to an acetone/methanol mixture and the cyclopentene/ethylene copolymer was isolated and dried. The yield wa 97.6 g, corresponding 15 to 4.88 kg of copolymer/mmol Zr.h (see table for further data).

*0 Example 28 A 1.5 dm 3 polymerization reactor was flushed with nitrogen and then with ethylene and filled with a solution of 25 g of norbornene in 750 cm 3 of toluene. The reactor was then brought to 25 0 C, with stirring, and 1 bar ethylene was injected.

0 0 20 mmol of a toluene solution of methylaluminoxane were then added to the reactor and the reaction mixture was stirred for 15 min, the ethylene pressure being kept at S"1 bar by metering in further ethylene.

In parallel with this, 0.05 mmol of metallocene polymer according to Example 12 were added to 10 mmol of the S toluene solution of methylaluminoxane and pre-activated by leaving to stand for 15 minutes.

This mixture was then metered into the reactor and the reaction mixture was polymerized for 1 h at 25 0 C, with stirring, the ethylene pressure being kept at 1 bar. The contents were then run off into a vessel containing 20 100 cm 3 Of isopropanol and 2 din 3 of acetone were added to the mixture, V--e resulting mixture was stirred for 10 min and the suspended polymer solid was separated off. The solid was then stirred for 2 h in an alkaline ethanol solution and the polymer was filtered off and dried for h at 80 0 C under vacuum. 19 g of copolymer were obtained, corresponding to 0.3 kg/mmol Zr-h (see table for further data) Abbreviations: Cp cyclopentadienyl THF tetrahydrofuran MO= methylaluminoxane Me methyl Et ethyl RT room temperature VI viscosity index 99 9 9 0 Si 96 9 9 9*9 9 9 9s9*S* 0 9*99 0 9 909**9 0 9. 0 .9 *0 9009 9* 9. 0 0099 9 *.9e 0 *80000 9 9 C. C C

C

C

C

C

C

C

C. C

SC

9. 4*0 C geg C C. C 49 C C C C C* C C S C C C C C C a 4*C C 953 Table: Olefin (co) polymerizationl using metallocene monomers and polymers Example Catalyst from Example MAO [mmol]; No. [inmol Al] Temp. Polymerization 0 C] time [h] Yield [g] Activity [kg/nimol Zr-h]

VI

[Cm 3 lg] 0. 001; 0.001; 0. 001; 0. 0005; 0. 0005; 0. 0002; 0. 001; 0. 001; 0. 05; 0. 05; 0.01; 0. 01; 0. 05; 82.7 78.9 72 27.1 52.6 32.2 63.7 68 2390 1950 6.2 97.6 19 41.4 39.5 36 27.1 52.6 80.5 31.9 34 47.8 39 0.31 4.88 0.3 529 527 707 680 620 671 477 468 43 39 a) 225 a) Sparingly soluble po 1 lymer

Claims (5)

1. A process for the preparation of an immobile metal- locene catalyst component, wherein a metallocene of formula I Ri M1 CpR 3 5 .mR'ml -1(I) R 2 ~',[CpR 3

6.R 5 and/or of formula II Ra R. 2 i n whichR M1 is zirconium or hafnium and 6 1.0 Cp is a cyclopentadienyl radical,, R1 and R2 are identical or different and are a hydrogen atom, a halogen atom, a Cl-C 1 0 -alkyl group, a CI-C 1 -alkoxy group, a C 7 -C 20 -arylalkyl group,,, Cr-Cl-aryl group or a C 8 -C 1 -aryloxy 4 .~5group, and R 1 and R? can also be linked to one another and together with M1 can form a metallo ring, the radicals W 3 are identical or different and are a hydrogen atom, a halogen atom, a C,-C, 0 -alkyl Q 0:Q group, a Cr,-Cl 0 -aryl group, a C 7 -C 2 ,-arylalkyl 4group, a C3-C,-fluoroalkyl group or an organo- metallic radical, such as Cl-C 1 -trialkylsilyl, diaryllzilyl or C 6 -C-triarylsilyl, R 4 and R 5 are identical oxr different and are a vinyl group, a Cr 6 -Cle-arylvinyl group, a Cl-Ce-alkylvinyl 23 group or a C6-C18- vinylaryl group, all of which may be substituted by a Cl-C 4 -alkoxy group, C1-C 4 -alkyl group or OH group, R6 and R7 .re identical or different and are a cyclopentadienyl, indenyl or fluorenyl radical, it being possible for said rings together with MI to form a sandwich structure, R8 and R9 are identical or different, are substituents of R6 and R7 and have the meanings given for R3, R4 and with the proviso that R6 and R7 can be monosubstituted or polysubstituted by R8 or R9, but at least one ring R6 or R7 must carry at least one radical R8 or R9 having the meaning of R4 and RS, and Rio has the meaning shown in formulae III-VII R11 R1i R11 R13 R11 R13 R11 R13 I I I I I I I I -M2- M2- -M2-M2- R12 R12 R12 R14 R12 R14 R12 R14 (iv) (VI) (VII) where M2 is silicon, germanium or tin and R1, R12, R13 and R14 are identical or different and are a hydrogen atom, a halogen atom, a C 6 -Clo-aryl group, a C 6 -Clo-fluoroaryl group, a C 1 -Clo-alkoxy group, a C6-Clo-aryloxy group or a C 7 -C 20 -arylalkyl group, R1 and R12, R13 and R14 and R13 or R12 and R14 together with the atoms linking them can form a ring system and m and n are identical or different and are a number from 0 to 5, where m+n must be a 1, is homopolymerized, or one or more of compounds I is/are copolymerized with one or more of compounds II, or a compound of formula I and/or of formula II is copolymerized with a (di)vinyl-aromatic compound. S 24 2. The process as claimed in claim 1, wherein, in formulae I and II, R 1 and R 2 are identical or different and are a hydrogen atom, a halogen atom, a C 1 -C 4 -alkyl group, a C.I-C 4 -alkoxy group, a C7-C 14 -arylalkyl group, a CO-Clo-aryl group or a C 6 -Cio-aryloxy group, and R 1 and R 2 can also be linked to one another and together with M 1 can form a metallo ring, the radicals R 3 are identical or different and are a hydrogen atom, a halogen atom, a Cz-C 4 -alkyl group, a CO-Cio-aryl group, a C 7 -Cz4-arylalkyl group, a Cz-Ce-fluoroalkyl group or an organo- Smetallic radical, such as C-Clo-trialkylsilyl, "5 C-Co-aryl-C-Cs-dialkylsilyl, C 1 -C 4 -alkyl- C6-Clo-diarylsilyl or Cs-C-triarylsilyl, R 4 and R 5 are identical or different, preferably identical, and are a vinyl group, a C 6 -Cz,-aryl- vinyl group, a Cz-Ca-alkylvinyl group or a C 6 -C 1 -vinylaryl group, which groups may be substituted by a Cz-C 4 -alkoxy group, C 1 -C,-alkyl a, g group or OH group, R and R 7 are identical or different and are a cyclo- pentadienyl, indenyl or fluorenyl radical, it being possible for said rings together with M 1 to form a sandwich structure, a R 8 and R 9 are identical or different, Sare substituents of Re and R 7 and have the mean- ings given for R 3 R 4 and R 5 with the proviso that R 6 and R 7 can be monosubstituted or poly- substituted by R e or R 9 but at least one rinr R 6 or R 7 must carry at least one radical R 8 or R 9 having the meaning of R 4 and R 5 and I a S- 25 SR 10 has the meaning shown in formulae III-VII, where M 2 is silicon or germanium and R 1 R 1 2 R 13 and R 14 are identical or different and are a hydrogen atom, a halogen atom, a Ci-C-alkyl group, a C 1 C-fluoroalkyl group, a Cg-Co 1 -aryl group, a C 6 C 1 -fluoroaryl group, a Ci-C,-alkoxy group, a C,- C 1 0 -aryloxy group or a C 7 -C,-arylalkyl group, R 11 and R 12 R 13 and R 1 R" and R 13 or R 12 and R" together with the atoms linking them can form a ring system, and m and n are identical or different and are a number from 0 to 5, where m+n must be 1. 3. The process as claimed in claim 1 or 2, wherein, in formulae I and II, *'15 R 1 and R 2 are identical or different and are a hydrogen atom, a halogen atom, a Ci-C 4 -alkyl group or a Cg-Co 1 -aryl group, and 1 R 1 and R 2 can also be linked to one another and ~together with M 1 can form a metallo ring, *r* the radicals R 3 are identical or different and are a hydrogen atom, a halogen atom, a Ci-C 4 -alkyl group, a C 6 -C 1 0 -aryl group or an organometallic radical, such as Ci-Co 1 -trialkylsilyl, R 6 and R 7 are a cyclopentadienyl radical, and R 10 has the meaning shown in formulae III-V, where M 2 is silicon and R 1 2 R 13 and R are identical or different and are a hydrogen atom, a halogen atom, a C 1 -C.-alkyl group or a C 6 -Co 1 -aryl group, and R 11 a n d R12, R 1 and R 1 and R 13 or R 12 and R 1 4 together with the atoms linking them can form a ring system. 4. The process as claimed in one or more of claims 1-3, wherein the polymerization is initiated by the action of heat or by means of a free radical forming agent. The process as claimed in claim 4, wherein the free radical forming agent is a,a'-azo-isobutyronitrile. 6. An immobile metallocene catalyst component, which is prepared by the process as claimed in one or more of claims

7. The use of an immobile metallocene catalyst component as claimed in claim 6 as catalyst in olefin polymerization.

8. A polymerized, immobile, metallocene catalyst component comprising a metallocene which has been polymerized or co-polymerized or a metallocene copolymerized with a vinyl-aromatic or divinyl-aromatic compound, said metallocene being one or both of the compounds of formulas I and II S.. S S S S S S S S* S. S S S R1 [C p R 3 R 4 m] [C p R -n Rn n and/c" of formula II R 10 R 6 \R1 whi R2ch R 9 which M1 is zirconium or hefnium and Cp is a cyclopentadienyl radical, Ri and R2 are identical or different and are a hydrogen atom, a halogen atom, a CI-CIO-alkyl group, a CI-CIO-alkoxy group, a C 7 -C 20 -arylalkyl group, a C6-010- aryl group or a C6-Clo-aryloxy group, and Ri and R2 can also be linked to one another and together with M1 can form a metallo ring, the radicals R3 are identical or different and are a hydrogen atom, a halogen atom, a Ci-Clo-alkyl group, a C 6 -Clo-aryl group, a C 7 -C 20 -arylaklyl group, a Ci -Ci o-fluoroalkyl group, Ci -Ci o-trialkylsilyl, C6-Cio-aryl-Cj-Cio- dialkylsilyl, Ci -Ci o-alkyl-C 6 -Ci o-diarylsilyl or C6-Ci o-triarylsilyl, R4 and R5 are identical or different and are a vinyl group, a 06-018- arylvinyl group, a Cl-C8-alkylvinyl group or a C6-CIB-vinylaryl group, all of which may be substituted by a CI-C 4 -alkoxy group, Cl-C4-alkyl group or OH group, .5 R6 and R7 are identical or different and are a cyclopentadienyl, idenyl or .:Soo fluorenyl radical, it being possible for said rings together with Mi to form a sandwich structure, 5R8 and R9 are idertjcaf or different, are substituents of R6 and R7 and have the meanings given for R3, R4 and with the nroviso that R6 and Rl7 can be monosubstituted or polysubstituted by R8 or R9, but at least one ring R6 or R7 Must Ca~rry at lea.5t one radical R8 or R9 having the meaning of R4 and R5, and RIO has the meaning shown in formulae III-ViI R" R11 R13 Ril R13 Ri R13 UC- -M2- C M2 M2- M2 R2R12 R12 R1R2 Ri4 R12 R14 28 where M2 is silicon, germanium or tin and R11, R12, R13 and R14 are identical or different and are a hydrogen atom, a halogen atom, a C-Clo-aryl group, a C6-Clo-fluoroaryl group, a C 1 -Clo-alkoxy group, a C 6 -Clo-aryloxy group or a C7-C 20 -arylalkyl group, R11 and R12, R13 and R14 and R13 or R12 and R14 together with the atoms linking them can form a ring system and m and n are identical or different and are a number from 0 to 5, where m+n must be 1.

9. A process for polymerizing an olefin in the presence of a catalyst, which comprises the step of polymerizing the olefin in the presence of a catalyst comprising the polymerized, immobile, metallocene catalyst component of claim 9. i DATED this 1st day of December, 1993 HOECHST AKTIENGESELLSCHAFT WATERMARK PATENT TRADEMARK ATTORNEYS THE ATRIUM 290 BURWOOD ROAD HAWTHORN VICTORIA 3122 AUSTRALIA [DOC.44] AU1015292.WPC DBM/KJS/SDW HOE 91/F 007 Abstract Metallocene(co)polymers, process for their preparation and their use as catalysts. An immobile (heterogeneous) metallocene catalyst com- ponent which can advantageous2. be used for olefin polymerization is obtained by homopolymerization of appropriately substituted (vinyl group-containing) metal- locenes of group IVb of the periodic table or by copolymerization of such metallocenes with (di)vinyl- aromatic compounds. I V68* pst 4 4 4 6 0 B g SB SB0 *a