CA2004419A1

CA2004419A1 - Process for the preparation of a heterogeneous metallocene catalyst component

Info

Publication number: CA2004419A1
Application number: CA002004419A
Authority: CA
Inventors: Martin Antberg; Ludwig Bohm; Jurgen Rohrmann
Original assignee: Hoechst AG
Current assignee: Hoechst AG
Priority date: 1988-12-03
Filing date: 1989-12-01
Publication date: 1990-06-03
Also published as: ES2076194T3; DE3840772A1; EP0647650A2; JPH02211253A; ES2147211T3; EP0372414B1; US5071808A; AU618647B2; EP0647650B1; ZA899188B; EP0372414A2; DE58909870D1; DE58909322D1; EP0647650A3; EP0372414A3; AU4573189A

Abstract

Abstract of the disclosure Process for the preparation of a heterogeneous metal-locene catalyst component.

The invention relates to a process for the preparation of a heterogeneous metallocene catalyst component from a suitably substituted metallocene of the sub-group 4 of the Periodic Table of the Elements and from poly(methyl-hydrogensiloxane) under the concomitant action of a catalyst.
The metallocene component and a suitable aluminoxane can be used as catalyst for the polymerization of 1-olefins cyclic olefins, diolefins and cyclic diolefins.

Description

HOECHST ARTIENGESELLSCH~T Dr. DA/fe HOE 88/'F 348 Description Proces~ for the preparation of a heterogeneou~
metallocene catalyst component.

The present inven~ion relates to a process for the preparation of heterogeneous metallocene cataly6t com-ponent~ using poly(methylhydrogensiloxane).

Metallocenes of transition metals are ]cnown as catalyst components (cf. US 4,52~,g82, US 4,542,199 and EP 128,045). Together with aluminoxanes, they form homogeneous transition metal cataly6ts which are soluble in aromatic and aliphatic hydrocarbons. These catalysts are ~ery active. Soluble catalysts are disadvantageou6 if they are to be employed in existing industrial plants ~ince the latter are generally de~igned for the use of heterogeneous cataly~t sy3tems. It was therefore desir-able to find metallocene cataly~t~ which can be u~ed as in~oluble ~olids in the form of a suspension.

Metallocene cataly~ts in which a zirconocene or titano-cene component and ~n aluminoxane are applied together $rom a ~olution onto a silicate ~upport are known (cf.
EP 206,794). However, this catalyst system i8 not very active. In addition, the catalyst component~ are not anchored to the support sufficiently firmly and can thus be extracted during the polymerization.

In addition, it is known that metallocene compounds containing silyl ether radicals can be applied to 5ili cate support~ with formation of siloxane bridges (cf.
DE 3,718,888). For thi~, it i~ nece~sary to remove adsorptively bound water from the ~upport ~aterial by drying for several hour~ at a maximum te~perature of 800C. A certain hydroxyl group content i8 thus estab-li~hed, which i~ determined analytically usin~ n-butyl-magnesium chloride. ~he support conditioned in this way must be stored under an inert gas with exclusion of air and wat~r.

It has now been found that the abovementioned dis-advantages can be avoided if a 6uitably substituted 5 metallocene compound i6 reacted with a poly~methylhydro-gensiloxane) with hydrosilylation cataly~is.

The invention thus rela~es to the process described in the claLms.

To prepare the heterogeneous metallocene catalyst com-ponent according to the invention, compounds of the formula I
Rl , ~ CpR3 5 _ mR4m] 2 - x Mi R2 ~[CpR35 nR5n]X (I) or of the formula II
I

R6 R~
(II) Rl o Ml \ 7' \ 2 R R
R

are used in which Ml i8 titanium, zirconium or hafnium, preferably zirconium, and Cp denotes a cyclopentadienyl radical.

Rl and R2 are identical or different ~nd denote a hydrogen atom, a halogen atom, a Cl-C10-alkyl group, a Cl-C10-alkoxy group, a C7-C20-arylalkyl group, a C~-C10 aryl group, a C6-C~0-aryloxy group, preferably an alkyl group or a halogen atom, in particular a chlorine atom.
Rl and R2 may also be linked to one another and may S form a metallocycle ~ogether with M1.

R3 denotes a hydrogen atom, a halogen atom, a Cl-C10-alkyl group/ a C6-C1O-aryl group, a C7 C20~arylalkyl group, a Cl C10-fluoroalkyl group o:r an organometal-lic radical such as Cl-C1O-trialkylsilyl, C6-C10-aryl-Cl-C1O-dialkyl~ilyl, Cl-C10-alkyl-C&-ClO-di~rylsilyl or C6-C10-tria.rylsilyl.
R3 is preferably a hydrogen atom or a methyl group, in particular a hydrogen atom.

R4 and R5 are identical or different and denote a C2 C10-alkenyl group, a C0-C12-alkenylaryl group, a C2-C10-alkenoxy group r a C2-C~-alkenyl-C1-CH-~ialkyl-silyl group, a C2-C~ alkenyl-C6 C1O-diarylsi}yl group or a C2-C~-alkenyl-Cl-C8-alkyl-C6-C~0-arylsilyl group.
R4 and Rs are preferably a C2-C10-alkenyl group or a C2-C8-alkenyl-C1-C8-dialkylsilyl group.

R~ and R7 are identical or different and denote a cyclopentadienyl, indenyl or fluorenyl radical, it being possible for the five-membered rings mentioned to form a sandwich ~tructure together with Ml.
R6 and R7 are preferably indenyl radicals.

R8 and R3 are identical or different, denote ~ub-~tituents of the five-membered rings R6 and R7 mentioned in the 3-po~ition and are a C2-C10-alkenyl group or an organometallic radical, ~uch as, for example, a C2-C10-alkenyl-Cl-ClO~dialkylsilyl group, a Cl-C1O-alkyl-C2-C10-dialkenyl~ilyl group, a C2-C10-alkenyl-C6-C10-diarylsilyl group or a C~-C10-aryl-C2-C10-dialkenyl6ilyl groupy preferably an alkenyl or alkenyldialkylsilyl group, in particular a hutenyl 2~

or alkyldLmethylsilyl group.

Rl has the meaning shown in the formulae III-VII

Rll R~ Rl3 Rll ~13 ~11 R13 C - - M2 _ - C C - C -- ~ 2~2- - M2 _ M~ -R12 R12 112 R14 112 ~ll4 R12 114 ~III) ~IV) (V) (VI) ~VII~, where M2 is silicon, germanium or tin, preferably silicon, and R11, R~2, R13 and Rl4 are identical or different and denote a hydrogen a~om, a halogen atom, a Cl-C1O-a:Lkyl group, a C,-C10-fluoroalkyl group, a C~-C10-aryl qroup, . a C6-C~O~fluoroaryl ~roup, a Cl-C~-alkoxy group, a C~-! 10 C1O-aryloxy group or a C7-C20-arylalkyl group, prefer-ably a dialkylsilyl group or a 1,2-alkanediyl group, . in particular a dimethylsilyl group or 1,2-ethane-diyl group.

R'l and Rl2 or Rl3 and Rl4 can be linked to one another to form spirocyclic By5temS, such as ~S~ O ~

st dS Rll and Rl3 or Rl2 and Rl4 can form the ring ~ystem below O O
I
C--C

~ o~

x is zero or 1, preferably zero.

m and n are identical or different and denote a number from 7.ero to 5, preferably t to 3, in particular 1.

Examples of ~uitable metallocene compounds of the formula I are ~ ~ ~j [ [ ~ 5i~CH2cH2cH2)(CH3)2 j si~cH2cH~cHz)(cH3)2 Cl2zr~ ~ 5itCH2CH'CH2)~CH3)2 ~ ~1-2) C12Zr[ ~ ~cH2)2cH=cH2 ] ~1~3~

C12Zr[ ~ CH25i(CH=CH2)~CH3)2 ~ ~I 4) .~ 2 C12Zr[ ~ 5,~CH2)4CH-CH2](CH3)2] ~1-5) Cl2zr[ ~ 5~CH'CH2)~CH3)2] ~1-6) C12Zr[ ~ si~CH2CH~CH2)tCH3)2 ]
5i(CH2CH'CH2)(CH3)2 2 Examples of suitable metallocene compounds of the formula II are ~' .
,~
Cl;~Z~ ~

~1 / ~ tll-2) C 12 Z r ~

/~
~1]-3).
,~/
~) ~, The metallocenes contain at least two ole inic functions which react further in a hydrosilylation reaction, catalyzed by a compound of sub-group 8 of the Periodic Table of the Elements, for example osmium, iridium and platinum, preferably by platinum, in particular by hexa-chloroplatinic acid hexahydrate, with a poly(methylhydro-gensiloxane), for example (CH3)3SiO[Si(C~3)H0]35Si~CH3)3~ to form a heterogeneous polymerization catalyst in `:

2~

accordance with the eguation below:

3 ~ / Rl (CH~)3Si ~ O-Si-O~J Si(CH3)3 ~ ~ \ 2 l~3 t CH3 ) 3S i^~ O--5,-C)~5i ~ CH3 )3 ca ~ yst Ml æ2 ~CH3)351~0--5i--0^~5i~CH3)3 For heterogenization, the me~allncene i~ di~solved in a solvent r for example an aliphatic or cycloaliphatic hydrocarbon, for example pentane or cyclohexane, or in an aromatic hydrocarbon, for example toluene or xylene, or in an ether, for e~ample diethyl ether, the poly(methyl-hydrogensiloxane) and the hydrosilylation catalyst are added, and the mixture is warmed for 5 to 120 minutes, preferably 10 to 30 minutes, at ~0 to 90C, preferably 30 to 80C. A gray precipitate then forms and is filtered off, washed and dried.
The course of the reaction can be monitored by IR Bpec-troscopy on the basis of the C=C and Si-H vibration bands.
The heterogenou~ catalyst vbtained according to the invention can be employed for the polymerization of 1-olefins of the formula Rl5-CH=CH

' in which Rl5 denotes hydrogen, a s~raight-chain or bxanched alkyl group, fox example ethylene, propylene or 4-methyl-l-pentene.

In addition, the catalyst can also be employed for the polymerization of the cyclic olefins, ~uch as~ for example, cyclopentene, cyclohexene, norbornene, diolefins and cyclic diolefins.

In this case, an aluminoxane~ whose synthesis i~ known, can be used for the polymerization in addition to the metallocene.

The invention is illustrated by means of the Examples below.

~xa~ple 1 2.89 g (24.04 mmol) of C5H4-(CH2)2CH=CH2, dissolved in 50 cm3 of THF, are added dropwise over the course of 3 hours to 1.3 g ~32.41 mmol) of potassium hydride in 20 cm3 of THF at room temperature, and the batch was ~ubsequently ~tirred overnight. Unreacted potassium hydride i8 filtered off, washed wi~h small portions of ether, dried in vacuo and weighed. 0.78 g (19.45 mmol) were obtained.

12.96 mmol of ~'[C5H4-~CH2)2CH=CH2] were produced.

The cyclopentadienide solution filtered off was added dropwise over the course of 1.5 hours to a ~uspension of 2.46 g (6.52 mmol) of Cl4Zr(THF)2 in 20 ~mJ of TXF at -10C. After the mixture had been ~tirred at room tem-perature for 4 hours, the batch was filter~d, the fil-trate was evaporatedt and the residue was e~tracted u~ing a hydrocarbon. After the combined extracts had been concentratedt the precipitate which formed at -40C was removed and dried in vacuo.

2~

Yield: 1.5 g ~3.75 mmol ~ 57~) of Cl2Zr[C5H4-(CH2~2CH=cH2~ 2 The compound exhibited a lH NMR spectr~m which conformed to expectations and a correct elementary analysis.

~ample ~

The procedure followed was analogous to Example 1, but with the difference that 0.87 g t21.69 mmol) of potassium hydride and 3.56 g (21.67 mmol) of C5H4-Si(CH3)zCH2CH=CH2 were employed. The conversion of pota~sium hydride was complete and the amount of Cl4Zr(THF)2 was 4.08 g (10.82 mm~l).

Yields 2.44 g t4.99 mmol ~ 46%) of Cl2z r [ C5~4~ cH3)2=c~2=cH=cH2] 2 The elementaxv ~lysis and the 'H NMR spectrum conformed to expectations.

~ample 3 10.16 g (22.35 ~mol) of 1,2-[l,l'bis(3-allyldimethylsilylindenyl)ethane were di~solved in 100 cm3 of THF, and 27.95 cm3 of a 1.6 N
butyllithium/hexane solution ~44.72 mmol) were added dropwise at room temperature over the cour~e of 2 hours.
After the batch had been stirred at about 60C for 4 hours, it was evaporated, the residue was ~uspended in a hydrocarbon, the suspension was filtered, and the ~olid was washed, dri~d and weighed. 9.39 g (20.12 mmol ~ 94%) of dilithium salt were produced.
~he dilithium ~alt was ~uspended in 100 cm3 of toluene, and 8.2 g (21.74 mmol) of Cl4ZrtTHF)2 in 100 cm3 of THF
were added at room temperature over the course of 2 hours. After the batch had been stirred overnight, it was evaporated, the residue was extracted with a g hydrocarbon, the extracts were filtered, and the combined filtrates were evaporated.

Yield- S g (8.13 mmol ~ 40~) of ethylenebis[l-(3-allyldimethylsilylindenyl)zirconium]
dichloride.

The compound exhibited a correct elementary analysis.

~xam~l~ 4 O.98 g (~ mmol) of the compound having the formula I-2 were dissolved in 12 cm3 of toluene, and 0.52 tO.23 mmol) of poly(methylhydrogensiloxane) and 0.02 s~of H2PtCl6-6H20 were added. After the mixture had been warmed for a few minute , a dark gray, ~olid phase formed. The supernatant ~olution no longer exhibited Si-H vibration ban~s in the IR ~pectrum. The precipitate was therefore separated off, and washed thoroughly with toluene in order to remove any unreacted, adsorptively bound com-plex. The product was ~uhsequently dried in vacuo. The residue, examined by elementary analysis, contained 10.2%
of Zr.

,, .
~ample 5 The procedure followed was snalogous to Example 4, but with the differ~nce that 0.83 g (1.70 mmol) of the compound having the formula I-2, 0.45 g (O.20 mmol) of poly(methylhydrogensiloxane) and 0.21 g of H2PtC16 6H2O
were employed. The residue, examined by elementary analy-~i~, oontsined 8.4% of Zr.

~mple 6 The procedure followed was analogous to E~ample 4, but with the difference that 1.2 g (3 mmol) of the compound having the formula I-3, 0.74 g (O.33 mmol) of poly-(methylhydro~ensiloxane) and 0.15 g of H2~tC16-6H2O were employed.
The residue, examined by element~ analysis, contained 9.3% of Zr~

E~ample 7 900 cm3 of a diesel oil ~raction (b.p. - 100-120C) were placed in a 1.5 dm3 ateel autoclave ancl heated to 70C.
The reactor was charged with a toluene ~olution of 0.25 g of methylaluminoxane and 0.01 mmol of the heterogeneous catalyst from Example 4. Ethylene was then in~ected to a final pressure of 7 bar, and the mi~ture was polymerized for 2 hours. The catalyst residues in he suspension were decomposed u~ing aqueous HCl. ~he polymPr was isolated, washed with ace~one and dried. 5.1 g of polyethylene were obtained. This corresponds to an activity of ~55 g of pol~mer/mmol of Zr-h (further data in the Table).

~xample 8 600 cm3 of a diesel oil fraction (b.p. ~ lQ0-120C) and 300 cm3 of cyclopentene were placed in a 1. 5 dm3 ~teel autoclave heated to 60C. The reactor was charged with a toluene solution of 0.25 g of methylaluminoxane and O.01 ~mol of the heterogeneou~ catalyst from Example 4.
After ethylene had been in~ected to 7 bar, the batch was polymerized for 2 hours. The polymer ~olution was added to twice the amount of a methanol/acetone mixture. The ethylene-cyclopentene copolymer which precipitated was isolated and dried. ~he yield was 4.2 g, corresponding to an activity of 210 g of polymer/mmol of Zr h (further data in the Table).

~xampl~ 9 900 cm3 of cyclopantene were placed in a 1.5 dm3 ~teel autoclave, which was charged with 0.25 g of meth~lalu-minoxane and 0.01 mmol of the heterogeneous catalyst from Example 4. After the batch had been polymeri~ad for 2~ 9 1~ -2 hours a~ 60C, the polymer ~olution was worked up as in Exa~ple 8. The yield of polymer was 1.6 g, corresponding to an activity of 80 g of polymer/mmol of Zr-h (further data in the Table).

5 Examples 10 and 11 were carried out in corr0spondinq manner to the data in the Table.

.~ ~ , oP

i ~ ~ ~ ~

~:n ~ c: o o o CO ~ ~D N
'~3 U~
.

O O O O O O
t`

~ a ~

9~ ~
O

~ O ~ O ~ C~ I O ~I O ~`d ~ 8 o o ~ o o o o o o o N ~ ' O _ ~
~' ~
_l ll .q . O
~ ~ I` CD O~ O _~ ~

.. . ' .

Claims

1. A process for the preparation of a heterogeneous metal-locene catalyst component from a metallocene of the formula I

(I) or of the formula II
(II) in which M1 titanium, zirccnium or hafnium and Cp denotes a cyclopentadienyl radical, R1 and R2 are identical or different and denote a hydrogen atom, a halogen atom, a C1-C10-alkyl group, a C1-C10-alkoxy group, a C7-C20-arylalkyl group, a C6-C10-aryl group or a C6-C10-aryloxy group, R1 and R2 may also be linked to one another and may form a metallocycle together with M1.
R3 denotes a hydrogen atom, a halogen atom, a C1-C10-alkyl group, a C8-C10-aryl group, a C7-C20-arylalkyl group, a C1-C10-fluoroalkyl group or an organometal-lic radical such as C1-C10-trialkylsilyl, C6-C10-aryl-C1-C10-dialkylsilyl, C1-C10-alkyl-C6-C10-diarylsilyl or C6-C10-triarylsilyl, R4 and R5 are identical or different and denote a C2-C10-alkenyl group, a C2-C12-alkenylaryl group, a C2-C10-alkenoxy group, a C2-C8-alkenyl-C1C8-di-alkylsilyl group, a C2-C8-alkenyl-C8-C10-di-arylsilyl group or a C2-C8-alkenyl-C1-C8-alkyl-C6-C10-arylsilyl group, R6 and R7 are identical or different and denote a cyclopentadienyl, indenyl or fluorenyl radical, it being possible for the five-membered rings mentioned to form a sandwich structure together with M1, R8 and R9 are identical or different, are substituents of the five-membered rings R6 and R7 mentioned in the 3-position and denote a C2-C10-alkenyl group or an organometallic radical, R10 has the meaning shown in the formulae III-VII

(III) (IV) (V) (VI) (VII), where M2 is silicon, germanium or tin and R11, R12, R13 and R14, are identical or different and denote a hydrogen atom, a halogen atom, a C1-C10-alkyl group, a C1-C10-fluoroalkyl group, a C8-C10-aryl group, a C8-C10-fluoroaryl group, a C1-C10-alkoxy group, a C8-C10-aryloxy group or a C7-C20-arylalkyl group, R11 and R12, R13 and R14, R11 and R13 or R12 and R14 can form a ring system together with the atoms linking them, x is zero or 1, m and n are identical or different and denote a number from zero to 5, and a poly(methylhydrogensiloxane), which process is carried out at a temperature of 20-90°C and within 5-120 minutes using a catalyst.

2. The process as olaimed in claim 1, wherein the catalyst is a compound of 8 of the Periodic Table of the elements.

3. The process as claimed in claim 1, wherein the catalyst is H2PtCl6?6H2O.

4. The use of a heterogeneous metallocene catalyst component prepared as claimed in claim 1, together with an alumin-oxane for the polymerization of 1-olefins of the formula R15-CH=CH2, in which Rl5 denotes a hydrogen atom or a straight-chain or branched alkyl group, and for the polymerization of cyclic oleftns, diolefins and of cyclic diolefins.

5. The process as claimed in claim 1, and substantially as described herein.