AU630451B2 - Process for the preparation of ethylene polymers - Google Patents

Process for the preparation of ethylene polymers Download PDF

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AU630451B2
AU630451B2 AU55771/90A AU5577190A AU630451B2 AU 630451 B2 AU630451 B2 AU 630451B2 AU 55771/90 A AU55771/90 A AU 55771/90A AU 5577190 A AU5577190 A AU 5577190A AU 630451 B2 AU630451 B2 AU 630451B2
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group
indenyl
cm
rac
zirconium dichloride
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Martin Antberg
Ludwig Bohm
Hartmut Luker
Jurgen Rohrmann
Walter Spaleck
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Hoechst AG
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    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F10/00Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F10/02Ethene
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07FACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F17/00Metallocenes
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F110/00Homopolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F110/02Ethene
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F210/00Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F210/16Copolymers of ethene with alpha-alkenes, e.g. EP rubbers
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F4/00Polymerisation catalysts
    • C08F4/42Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
    • C08F4/44Metals; 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
    • C08F4/60Metals; 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
    • C08F4/62Refractory metals or compounds thereof
    • C08F4/639Component covered by group C08F4/62 containing a transition metal-carbon bond
    • C08F4/63912Component covered by group C08F4/62 containing a transition metal-carbon bond in combination with an organoaluminium compound
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F4/00Polymerisation catalysts
    • C08F4/42Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
    • C08F4/44Metals; 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
    • C08F4/60Metals; 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
    • C08F4/62Refractory metals or compounds thereof
    • C08F4/639Component covered by group C08F4/62 containing a transition metal-carbon bond
    • C08F4/6392Component covered by group C08F4/62 containing a transition metal-carbon bond containing at least one cyclopentadienyl ring, condensed or not, e.g. an indenyl or a fluorenyl ring
    • C08F4/63922Component covered by group C08F4/62 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
    • C08F4/63927Component covered by group C08F4/62 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 two cyclopentadienyl rings being mutually bridged
    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02PCLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00Technologies relating to chemical industry
    • Y02P20/50Improvements relating to the production of products other than chlorine, adipic acid, caprolactam, or chlorodifluoromethane, e.g. bulk or fine chemicals or pharmaceuticals
    • Y02P20/52Improvements relating to the production of products other than chlorine, adipic acid, caprolactam, or chlorodifluoromethane, e.g. bulk or fine chemicals or pharmaceuticals using catalysts, e.g. selective catalysts

Description

COMMONWEALTH OF AUSTRALIA PATENTS ACT 1952-69 COMPLETE SPECIFICATION (OR IGINAL) Class I n Application Number: Lodged: Form t. Class Complete Specification Lodged: Accepted, Published: Priority: .:.Related Art: *0e* ~e5S S S S. S

S.

S *SS S Name of Applicant: Address of Applicant HOECHiST AKTIENGESELLSCH-AFT 50 Bruningstrasse, D-6230 Frankfurt/Main of Germany 80, Federal Republic Actual Inventor :Address for Service WALTER SPALECK, MARTIN ANTBERG, LUDWIG BOHM, HIARTNUT LUKER JURGEN ROHRMA-NN and WATERMARK PATENT TRADEMARK ATTORNEYS.

LOCKED BAG NO. 5, HAWTHORN, VICTORIA 3122, AUSTR'/LIA Complete Specification for the invention entitled: PROCESS FOR THE PREPARATION OF ETHYLENZ POLYMERS The following statement is a full description of this invention, including the best method of performing it known to HOECHST AKTIENGESELLSCHAFT HOE 89/F 155 Dr.DA/St Description Process for the preparation of ethylene polymers The present invention relates to a process for the preparation of polyethylene and ethylene-l-olefin copolymers of various molecular weight ranges with the aid of metallocene/aluminoxane catalysts.

A process for the preparation of polyethylene with the aid of metallocene/aluminoxane catalysts in toluene as suspending agent has already been described [cf.

EP 69,951]. The molecular weights achieved for the polymers are relatively low. No data is given on the morphology of the polymers.

S. Furthermore, a comparable process using a high-boiling hydrocarbon as suspending agent has been disclosed (cf.

EP 170,059). However, the catalyst activities are moderate, and the bulk densities achieved for the polymer are between 0.15 and 0.18 g/cm 3 Furthermore, processes have been described for the preparation of polyethylene and ethylene-l-olefin copolymers with the aid of metallocene/aluminoxane catalysts by polymerization in the gas phase (cf. EP 206,794, 285,443 and 294,942). Here too, only moderately high molecular weights of the polymers and in most cases only poor 25 activities of the catalysts are achieved.

It is common to all the abovementioned processes that, as the metallocene, unbridged biscyclopentadienylzirconium complexes are employed in which the cyclopentadienyl radicals are substituted or unsubstituted, and the metallocene is either employed as such in the polymerization or has been linked to an inert support by appropriate preliminary reaction steps.

2 It has now been found that the preparation of polyethylene and ethylere-l-olefin copolymers by suspension or gas-phase processes with the aid of metallocene/aluminoxane catalysts whose metallocene component is a bridged biscyclopentadienyl complex offers important advantages.

The invention thus relates to a process for the preparation of ethylene polymers by polymerization of ethylene or copolymerization of ethylene with 1-olefins having 3 to 20 carbon atoms at a temperature of from -60 to 200°C and a pressure of from 0.5 to 200 bar in solution, in suspension or in the gas phase, in the presence of a catalyst comprising a metallocene as the transition-metal component and an aluminoxane of the formula II 9 9 for the linear type and/or of the formula III Al 9 for the cyclic type, where, in the formulae II and III,

R

9 is a Ci-C-alkyl group or phenyl or benzyl, and n is an integer from 2 to 50, which comprises carrying out the polymerization in the presence of a catalyst whose transition-metal component is a compound of the formula

I

R

3 1 ^R R M (I) 4 R 2 in which

M

1 is titanium, zirconium, hafnium, vanadium, niobium or tantalum,

R

1 and R 2 are identical or different and are a hydrogen -3atom, a halogen atom, a C,-C, 1 -alkyl group, a CI-Cloalkoxy group, a C 6 ,-Cl-aryl group, a C.-CID-aryloxy group, a C 2 -C-alkenyl group, a C 7

-C

40 -arylalkyl group, a C 7

-C

40 -alkylaryl group or a C 8

-C

4 -arylalkenyl group, R3 and R 4 are identical or different and are a mononuclear or polynuclear hydrocarbon radical which, with the central atom is able to form a sandwich structure, R 5 i s R6R'R 6

'R

8

R

6 C M2/ '7L '7 7 '8

R

6 R8 R 6

R

6

R

6 R R 0 0

-M

2

CR

8 '7 17 2 =AlR 6 =O2, =NR 6 =CO, =PR 6 or R6, where R6, R 7 and R 8 are identical or different and are a hydrogen atom, a halogen a Cl-Cl-alkyl group, a CI-C-f luoroalkyl group, :e :a C 6

-C

10 -fluoroaryl group, a C 6 -Cl.-aryl group, a C 1

C

10 -alkoxy group, a C 2 -Cl-alkenyl group, a C7-C 4 arylalkyl group, a C8-C 4 -arylalkenyl group or a C 7

C

40 -alkylaryl group, or R 6 and R 7 or R 6 and R8, in each case with the atoms connecting them, form a ring, M42 is silicon, germanium or tin, and p is the number 1, 2, 3, 4 or invention comprises an a metallocene of c 3a Throughout this specification, the term "ethylene polymers" is not defined soas to include syndiotactic ethylene polymers.

The catalyst to be used for the process according to the invention comprises an aluminoxane and a metallocene of the formula I S* e.

To *e I I II I i i I I qpU 4

R

3 1 R 1

R

5

M

1

R

2 In the formula I, M is a metal selected from the group comprising titanium, zirconium, hafnium, vanadium, niobium and tantalum, preferably zirconium.

R

1 and R 2 are identical or different and are a hydrogen atom, a Cl-Cio-, preferably C 1

-C

3 -alkyl group, a C 1 -CIo-, preferably C 1

-C

3 -alkoxy group, a C 6 -Clo-, preferably Cs-C.aryl group, a C 6

-C

10 preferably C.-C.-aryloxy group, a

C

2

-C

1 0 preferably C 2

-C

4 -alkenyl group, a C 7

-C

4 0 prefer- 10 ably C 7 -Co-arylalkyl group, a C7-C 40 preferably C 7

-C

12 alkylaryl group, a C 8

-C

40 preferably C.-C 12 -arylalkenyl group or a halogen atom, preferably chlorine.

R

3 and R 4 are identical or different and are a mononuclear or polynuclear hydrocarbon radical which, together with 15 the central atom M 1 is able to form a sandwich structure.

R

3 and R 4 are preferably cyclopentadienyl, indenyl, tetrahydroindenyl or fluorenyl, it also being possible for the basic structures to carry additional substituents.

R

5 is a mono- or polymembered bridge which links the S20 radicals R 3 and R 4 and is S*R RR 6

R

8

R

6 p- p p R6 R 8

R

6

R

6

R

6 M2C -12 O 2 L 7

RR

8 7

R

7

R

7 p

R

6

R

2 '2 CR8.

R R 2 =BR 6, =AlR 6 ,1 =Sol =S0 2

=NR

=CO, =PR 6 or R5, where R 6 R 7 and Ra are identical or different and are a hydrogen atom, a halogen atom, preferably chlorine, a Cl-Cl 0 preferably Cj-

C

3 -alkyl group, in particular a methyl. group, a C,-

C

10 -fluoroalkyl. group, preferably a CF 3 group, a C 6 Cl.-fluoroaryl group, preferably a pentafluorophenyl group, a C 6

-C

1 preferably C, 6 -C.-aryl group, a C 1 Cl 0 preferably Cl-C 4 -alkoxy group, in particular a methoxy group, a C 2

-C

1 0 preferably C 2

-C

4 -alkenyl group, a C 7

-C

4 0 preferably C 7

-C

1 -arylalkyl group, a C 8

-C

4 0 preferably C.-C 2 -arylalkenyl group or a C7- C4 0 -1 preferably C7-C 1 2 -alkylaryl group, or R 6 and R 7 or R 6 and R8 in each case, together with the atoms connecting them, form a ring, m42 is silicon, germanium or tin, preferably silicon or germanium, and p is the number 1, 2, 3, 4 or ***Particularly preferred metallocenes are: 20* *a-iehliybslidey~icn ihoie rac-diehylsilylbis -indenyl) zirconium dichloride, -silacyclobutylbis(l'-indenyl)zirconiur dichloride, rac-dixnethylsilylbis(1-(3-methylindenyl) )zirconium dichloride, rac-1, 1,2,2-tetramethyldisilaethylenebis (1 -indenyl) zirconium dichloride, dimethylsilylbis (3-trimethylsilyl) cyclopentadienyl) zirconium dichloride, and diphenylmethylene (9-f luorenyl )cyclopentadienylzirconium dichloride.

The above-described metallocenes can be prepared by the general reaction scheme below: -6

H

2

R

3 +butylLi -4 HR 3

L.

H

2

R

4 +butylLi HR 4 Li >2i--

HR

3

-R

5

-R

4

H

LiR 3 -R-fL 2 butv1Li.

mic1 4

R

3 i C' I Cl

R

1 Li_ RLi (X Cl, Br, I, 0-tosyl) 0 @0 0* .00 0 0* -7or

H

2

R

3 butylLi 4 HR 3 Li R6 7 R4H C a, HR 3 Li R 6

R

7

C

P4 R b HO 2 butylLi [R6R7c R Li 2 R3 9 M 1 C1 4 M 4 i: 6 r R cl C M R7 Cl q4 RiLi J3 R3

R

R6 Ri R6 R ;1 2 R MRLi 7 Cl F"

R

1 41 4 R

R

The cocatalyst. is an aluminoxane of the formula II R9 R9 R9 9. I A R' ll -0 Al/ for the linear type and/ o of the formula III

R

9 AlOf R 8

R

9 Al 0-

(III)

n+2 for the cyclic type. In these formulae, R 9 is a alkyl group, preferably methyl, ethyl or isobutyl, butyl or neopentyl, or phenyl or benzyl. Methyl is particularly preferred. n is an integer from 2 to 50, preferably 5 to However, the exact structure of the aluminoxane is not known.

The aluminoxane can be prepared in various ways.

One possibility is the careful addition of water to a 10 dilute solution of a trialkylaluminum by introducing the solution of the trialkylaluminum, preferably trimethyl- S aluminum, and the water in each case in small portions into an initially introduced larger amount of an inert solvent and between each portion awaiting the end of the evolution of gas.

In another process, finely powdered copper sulfate pentahydrate is slurried in toluene, and, in a glass flask under an inert gas at about -20°C, sufficient trialkylaluminum is added so that about 1 mole of 0 CuSQ44H 2 0 is available for each 4 Al atoms. After slow hydrolysis with elimination of alkane, the reaction mixture is left at room temperature for 24 to 48 hours, cooling possibly being needed to ensure that the temperature does not exceed 30°C. The aluminoxane dissolved in the toluene is subsequently filtered off from the copper sulfate, and the solution is evaporated in vacuo. It is assumed that the low-molecular-weight aluminoxanes condense in these preparation processes to form higher oligomers with elimination of trialkylaluminum.

Furthermore, aluminoxanes are obtained if trialkylaluminum, preferably trimethylaluminum, dissolved in an inert aliphatic or aromatic solvent, preferably heptane or 9 toluene, is reacted at a temperature of from -20 to 100°C with aluminum salts, preferably aluminum sulfate, containing water of crystallization. In this case, the volume ratio between the solvent and the alkylaluminum used is 1:1 to 50:1 preferably 5:1 and the reaction time, which can be monitored from the elimination of the alkane, is 1 to 200 hours preferably 10 tr Q8 hours.

Of the aluminum salts containing water of crystallization, those are particularly used which have a high content of water of crystallization. Aluminum sulfate hydrate, in particular the compounds A1 2

(SO

4 3 .16H 2 0 and Al 2

(SO

4 3 .18HzO having the particularly high water of crystallization content of 16 and 18 moles of H 2 0/mole of A1 2

(SO)

3 respectively, is particularly preferred.

A further variant for the preparation of aluminoxane is to dissolve trialkylaluminum, preferably trimethylaluminum, in the suspending agent initially introduced into the polymerization reactor and then to react the aluminum compound with water.

20 Besides the above-outlined processes for the preparation S'.of aluminoxanes, there are others which can be used.

Irrespective of the manner of preparation, all aluminoxana solutions have in common a varying content of unreacted trialkylaluminum, which is in free form or in .25 the form of an adduct. This content has an effect, as yet not explained accurately, on the catalytic effectiveness, which varies depending on the metallocene compound employed.

It is possible to pre-activate the metallocene using an aluminoxane of the formula II and/or III before using the polymerization reaction. This considerably increases the polymerization activity and impro--is the grain morphology.

I

r i 10 The preactivation of the transition-metal compound is carried out in solution. It is preferred here to dissolve the metallocene in a solution of the aluminoxane in an inert hydrocarbon. Suitable inert hydrocarbons are aliphatic or aromatic hydrocarbons. Toluene is preferably used.

The concentration of the aluminoxane in the solution is in the range from about 1% by weight to the saturation limit, preferably from 5 to 30% by weight, in each case relative to the total solution. The metallocene can be employed in the same concentration, but it is preferably employed in an amount of from 10-4 1 mole per mole of aluminoxane. The pre-activation time is 5 minutes to hours, preferably 5 to 60 minutes. The pre-activation is 15 carried out at a temperature of from -78 C to 100 C, preferably 0 to 70 0

C.

4* S A significantly longer preactivation is possible, but normally has neither an activity-increasing nor activityreducing effect, but may be entirely appropriate for storage purposes.

e *6 The polymerization is carried out in a known manner in solution, in suspension or in the gas phase, continuously or batchwise, in one or more steps, at a temperature of from -60 to 200 0 C, preferably -30 to 120 0 C, in particular 50 to 90 0

C.

The overall pressure in the polymerization system is to 200 bar. The polymerization is preferably carried out in the industrially particularly interesting pressure range of from 5 to 60 bar. The metallocene compoundhes used here in a concentration, relative to the transition metal, of from 10 3 to 10-8, preferably 10-4 to 10 7 mole of transition metal per dma-of solvent or per dm 3 of reactor volume. The aluminoxane tsAused in a concentration of from 10" to 10 mole, preferably 10 5 to 10-2 mole per dm 3 of solvent or per dm 3 of reactor volume. In 11 principle, however, higher concentrations are also possible.

If the polymerization is carried out as a suspension or solution polymerization, a solvent which is inert towards Ziegler catalysts is used, i.e. an aliphatic or aromatic hydrocarbon. Aliphatic hydrocarbons are preferred, such as, for example, butane, pentane, hexane, heptane, isooctane, cyclohexane, methylcyclohexane or petroleum or hydrogenated diesel oil fractions.

Besides homopolymerization of ethylene, the catalyst systems according to the invention are employed for the j copolymerization of ethylene with a 1-olefin having 3 to 20 car.,,n atoms. Examples of such 1-olefins are propylene, S. 1-butene, 1-hexene, 4-methyl-l-pentene and 1-octene.

The molecular weight of the polymer can be regulated in a known manner, preferably using hydrogen.

The polymerization can have any desired duration, since the catalyst system to be used according to the invention only exhibits a slight time-dependent decrease in poly- *i merization activity.

Depending on the structure of the complex, the use of these complexes gives, with high activities, polyethylene and ethylene-1-olefin copolymers having a narrow moleculari weight distribution (polydispersity) in a broad molecularweight range, in particular products having high molecular weights which are suitable for processing by injection molding and extrusion and in particular have high stretching capacity of the polymer melt, and permits the production of very varied grain morphologies of the product, such as high and low bulk densities, extremely small and extremely large mean grain diameters and various grain shapes. The variety of grain morphologies which can be achieved opens up various possibilities for the use of such polyethylene powders in sintering processes.

r- 12 The examples below are intended to illustrate the invention.

The abbreviations have the following meanings: VN viscosity number in cm 3 /g, weight average molecular weight in g/mol, w/M molecular weight distribution determined by gel permeation chromatography (GPC), d 50 mean grain diameter in pm.

The pressure data in the examples are in bar of superatmospheric pressure.

The densities of the copolymers have been determined in accordance with DIN 53479, method A.

All the operations below were carried out under a protective gas using absolute solvents.

*0 Example 1: Preparation of dimethylsilylbis(l-indenyl) 80 cm 3 (0.20 mol) of a 2.5 molar solution of n-butyllithium in hexane were added with ice cooling to a solution of 30 g (0.23 mol) of indene (technical grade, -91%) 20 which has been filtered through aluminum oxide. The batch was stirred for a further 15 minutes at room temperature, and the orange solution was added via a hollow needle over the course of 2 hours to a solution of 13.0 g (0.10 mol) of dimethyldichlorosilane in 30 cm 3 of diethyl ether. The orange suspension was stirred overnight and washed by shaking three times with 100-150 cm 3 of water. The yellow organic phase was dried twice over sodium sulfate and evaporated in the reaction evaporator.

The orange oil which remained was kept at 40"C for 4 to 5 hours in an oil-pump vacuum and freed from excess indene, during which a white precipitate deposited.

Addition of 40 cm 3 of methanol and crystallization at 0 C gave a total of 20.4 g of the compound r 13dimethylsilylbis(l-indenyl) as a white to beige powder (2 diastereomers). M.p. 79-81"C.

Example 2: Preparation of rac-dimethylsilylbis(l-indenyl) zirconium dichloride (metallocene A) 15.5 cm 3 (38.7 mmol) of a 2.5 molar hexane solution of butyllithium were added slowly at room temperature to a solution of 5.6 g (19.4 mmol) of dimethylsilylbis(1indenyl) in 40 cm 3 of THF. 1 hour after completion of the addition, the deep red solution was added dropwise over the course of 4-6 hours to a suspension of 7.3 g (19.4 mmol) of ZrC1 4 .2THF in 60 cm 3 of THF. After the mixture had been stirred for 2 hours, the orange precipitate was filtered off with suction via a glass frit and 15 recrystallized from CH 2 C1 2 to give 1.0 g of the metallocene A in the form of orange crystals, which gradually decompose from 200 0

C.

Correct elementary analyses. The El mass spectrum exhibited M* 448. 1 H NMR spectrum (CDCl 3 7.04-7.60 8, arom. 6.90 (dd, 2, p-Ind 6.08 2, a-Ind H), 1.12 6, SiCH 3 Example 3: Preparation of rac-diphenylsilylbis (1-indenyl) zirconium 1* dichloride (metallocene B) 5 A solution of 20 g (48.5 mmol) of (CsH 5 2 Si(Ind) 2 prepared ifrom (C 6

H

5 2 SiC12 and indenyllithium analogously to Example 1, in 200 cm 3 of diethyl ether was reacted at 0°C with cm 3 (100 mmol) of butyllithium (2.5 molar in hexane).

After the mixture had been stirred at room temperature for 2 hours, the solvent was stripped off, and the residue was stirred with 100 cm 3 of hexane and filtered off. The dilithio salt was dried in an oil-pump vacuum and added to a suspension of 11.3 g (48.5 mmol) of ZrCl 4 in 150 cm 3 of CH 2 ClI at -78 0 C. The mixture was stirred I 14 overnight and allowed to warm to room temperature. The red solution was concentrated, and the precipitate which deposited was filtered off via a frit. Extraction with toluene gave 2.0 g of metallocene B as an orange powder. Correct, elementary analyses. 'H NMR spectrum (CDCl 3 6.9-8.2 18, arom. 7.03 (dd, 2, p-Ind H), 6.30 2, a-Ind H).

Example 4: Preparation of rac-dimethylsilylbis 3-methylindenyl) zirconium dichloride (metallocene G) A solution of 4.89 g (15.5 mmol) of (CH 3 2 Si(MeInd) 2 S prepared analogously to Example 1 from (CH 3 2 SiCl 2 and 3methyl indenyl lithium, was reacted with 12.5 cm 3 (30.5 mmol) of butyllithium and 5.84 g (15.5 mmol) of 15 ZrCl 4 .2THF analogously to Example 2. After the solvent had been stripped off, the residue was extracted with tolu- S ene. The precipitate which deposited from toluene on concentration and cooling was recrystallized from CHCl 3 to give 800 mg of metallocene G in the form of orange-red crystals. Correct elementary analyses. H NMR S spectrum (CDC1 3 7.0-7.5 8, arom. 5.71 2, a-Ind 2.30 6, Ind CH 3 1.07 6, SiCH 3 a 1 V S.4 'St.

Example Preparation of dimethylsilylbis( -(3-trimethylsilyl)- .25 cyclopentadienyl) zirconium dichloride (metallocene K) S. A solution of 3.9 g (11.7 mmol) of (CH 3 2 Si[(CH 3 3 SiCp] 2 prepared from Li 2

(CH

3 2 Si(Cp)z] and (CH 3 3 SiC1, was reacted analogously to Example 2 with 9.4 cm 3 (23.4 mmol) of butyllithium and 4.4 g (11.7 mmol) of ZrC1 4 .2THF. After the solvent had been stripped off, the residue was extracted with diethyl ether. The residue remaining after the diethyl ether had been stripped off was recrystallized from CHC1 3 to give 0.8 g of the complex as beige crystals. Correct elementary analyses. 1H NMR spectrum (CDCl 3 6.95 (dd, 2, CpH), 6.12 2, CpH), 5.96 2,

I

;i 15 CpH), 0.72 6, Si(CH 3 2 0.25 9, Si(CH 3 3 The NMR spectrum showed that metallocene K was in the form of an isomer mixture (43% of the rac-isomer, 57% of the mesoisomer).

Example 6: Preparation of isopropyl(l-indeiyl)cyclopentadienylzirconium dichloride (metallocene P) 19 cm 3 (47.3 mmol) of butyllithium (2.5 molar in hexane) were added at room temperature to a solution of 6.0 g (47 mmol) of indene in 100 cm 3 of diethyl ether.

After 1 hour, this solution was added to a solution of 6,6-dimethylfulvene in 100 cm 3 of diethyl ether at -78C.

After the mixture had been stirred at room temperature for 16 hours, the orange solution was diluted with 400 cm 3 *15 of diethyl ether, and 100 cm 3 of water were added. The yellow organic phase was then washed twice with water, dried over Na 2

SO

4 and evaporated. The brown oil remaining was chromatographed on 400 g of silica gel 60. Using hexane 7% of methylene chloride, a total of 7.2 g (68%) of the compound isopropyl(l-indenyl)cyclopentadienyl were eluted as a yellow oil (2 isomers). 28 cm 3 (70 mmol) of butyllithium (2.5 rnolar in hexane) were added at 0°C to a solution of 7.1 g (32 mmol) of this compound in 100 cm 3 of diethyl ether. After the mixture had been stirred at room temperature for 2 hours, the yellow precipitate was filtered off via a glass frit and washed with hexane/di- *4 ethyl ether After the precipitate had been dried in an oil-pump vacuum the pale yellow powder was added at -78 0 C to a suspension of 7.5 g (32 mmol) of ZrCl 4 in 100 cm 3 of methylene chloride. The mixture was slowly warmed to room temperature, stirred at room temperature for 30 minutes and filtered via a glass frit, and the solid was washed several times with methylene chloride.

The yellow filtrate was concentrated until crystallization occurred. At -35"C, a total of 2.4 g of the complex rac-[(CH 3 2 C(Ind)Cp]ZrCl 2 crystallized in the form of yellow-orange crystals. Correct elementary analyses.

16 1H NMR spectrum (CDCl 3 6.90-7.75 4, arom. 6.85 (dd, 1, p-Ind-H), 6.52 2, Cp-H), 6.12 1, a-Ind-H), 5.82, 5.70 (2 x q, 2 x 1, Cp-H), 2.20; 1.95 (2 x s, 2 x 3, CH 3 Example 7: Preparation of diphenylmethylene (9-fluorenyl) cyclopentadienylzirconium dichloride (metallocene Q) 12.3 cm 3 (30.7 mmol) of a 2.5 molar hexane solution of n-butyllithium were slowly added at room temperature to a solution of 5.10 g (30.7 mmol) of fluorene in 60 cm 3 of THF. After 40 minutes, 7.07 g (30.7 mmol) of diphenylfulvene were added to the orange solution, and the mixture s* was stirred overnight. 60 cm 3 of water were added to the dark red solution, whereupon the solution became yellow, 15 and the solution was extracted using ether. The ether phase, dried over MgSO,, was concentrated and left to crystallize at -35 0 C, to give 5.1 g of 1,1-cyclopentadienyl(9-fluorenyl)diphenylmethane as a beige powder.

0 2.0 g (5.0 mmol) of the compound were dissolved in 20 cm 3 of THF, and 6.4 cm 3 (10 mmol) of a 1.6 molar solution of butyllithium in hexane were added at 0 C. After the mixture had been stirred at room temperature for 15 minutes, the solvent was stripped off, and the red residue was dried in an oil-pump vacaum and washed several times with hexane. After the residue had been dried in an oil-pump Svacuum, the red powder was added at -78"C to a suspension of 1.16 g (5.0 mmol) of ZrCl 4 The batch was slowly warmed and stirred for a further 2 hours at room temperature.

The pink suspension was filtered via a G3 frit. The pink residue was washed with 20 cm 3 of CH 2 C1 2 dried in an oilpump vacuum and extracted with 120 cm 3 of toluene. Stripping off of the solvent and drying in an oil-pump vacuum gave 0.55 g of the zirconium complex (metallocene Q) in the form of a pink crystal powder.

17 The orange-red filtrate of the reaction batch was evaporated and left to crystallize at -35 A further 0.34 g of the complex crystallizes from CH 2 Cl 2 Total yield 1.0 g Correct elementary analyses. The mass spectrum exhibited M" 556. 1 H NMR spectrum (100 MHz, CDCl 3 6.90-8.25 (in, 16, Flu-H, Ph-H), 6.40 (mn, 2, Ph-H), 6.37 2F Cp-H), 5.8G 2, Cp-H).

Examples 8-18: The inetallocenes C, D, E, F, H, I, L, M, N, 0 and R of Table 2 were prepared analogously to Examples 1 and 2.

The dimethyl'chlorosilane in Examnple 1 was replaced here by appropriate other dihalogen compounds, which are shown :0 in Table 1. In the case of complexes substituted on the *00 5-meinbered ring (ietallocenes N and an indene cor- 0.15 respondingly substituted on the 5-ineibered ring was employed (analogously to Example In the case of the hafnium. complex inetallocene R, ZrCl 4 in Example 2 was replaced by HfC14.

2 0 9000 *000 0 0 0 0* 0 Table 1 Example 8 9 10 11 12 ,0 2 Metallocene

C

D

E

F

H

I

L

M

N

0

R

Dihalogen compound phenylmethyldichioros ilane phenylvinyldichioros ilane dimethyldichlorogermaiiun cyclotriinethylenedichlorosilar--- 1,1,2,2-tetramethyl-l,2dichiorodis ilane 1, 2-bis (chlorodiiethylsilyl) ethane 1, 2-dibromoethane 1 ,3-dibronopropane 1, 2-dibromoethane 1, 2-dibromoethane dichlorosilane -18- Example 19: Preparation of phenylmethylmethylene(9-fluorenyl)cyclopentadienylhafnium dichloride (metallocene T) The metallocene T was prepared analogously to Example 7.

However, the diphenylfulvene and ZrCl 4 in Example 7 were replaced by phenylmethylfulvene and HfCl 4 Example dm 3 of a petroleum ether (boiling range 100-120 0 C) were introduced at 20°C into a dry 16 dm 3 reactor which had been flushed with nitrogen. The gas space of the reactor was then flushed free from nitrogen by injecting 2 bar of ethylene and releasing the ethylene, and repeating this operation 4 times. 1 bar of hydrogen was then injected, and 30 cm 3 of a toluene solution of methylaluminoxane .15 (10.5% by weight of methylaluminoxane, molecular weight S 750 g/mol according to cryoscopic determination). The reactor contents were heated to 60 0 C over the course of minutes with stirring. The overall pressure was then increased to 7 bar by introducing ethylene with stirring *20 at 250 rpm. At the sacme time, 3.1 mg of metallocene A were dissolved in 20 cm 3 of a toluene solution of methylaluminoxane (concentration and quality as above) and preactivated by being left to stand for 15 minutes. The solution was then introduced into the reactor. The polymerization system was warmed to a temperature of 65 0

C

and then kept at this temperature for 1 hour by means of suitable cooling. The overall pressure was kept at 7 bar i during this time by corresponding supply of ethylene.

160 g of polyethylene were obtained.

The following values were determined on the product: VN 152 cm 3 bulk density: 320 g/dm 3 Examples 21-42: The procedure was in each case analogous to Example but the following parameters were varied: metallocene type -19- S- metallocene quantity (mg) methylaluminoxane solution type (content of methylaluminoxane in by weight, molecular weight M of Sthe methylaluminoxane in g/mol according to cryoscopic determination) amount of methylaluminoxane solution (cm 3 introduced into the reactor amount of hydrogen employed (H 2 in bar, no hydrogen was employed in numerous experiments) overall pressure P (bar) polymerization time t (min) polymerization temperature T o The polymerization parameters which were varied are shown in Table 3, and the polymerization results are shown in 15 Table 4.

Example 43: dm 3 of petroleum ether (boiling range 100-120"C) were introduced at 20"C into a dry 16 dm 3 reactor which had been flushed with nitrogen. The gas space of the reactor was then flushed free from nitrogen by injecting 2 bar of i ethylene and releasing the ethylene, and repeating this operation 4 times. 200 cm 3 of 1-hexane and 30 cm 3 of a toluene solution of methylaluminoxane (10.6% by weight of methylaluminoxane, molecular weight 900 g/mol according to cryoscopic determination) were then added. The reactor was then heated to 60 0 C over the course of 15 minutes with stirring. The overall pressure was then increased to 5 bar by introducing ethylene with stirring at 250 rpm.

At the same time, 1.3 mg of metallocene E were dissolved in 20 cm 3 of a toluene solution of methylaluminoxane (concentration and quality as above) and preactivated by being left to stand for 15 minutes. The solution was then introduced into the reactor. The polymerization system was warmed to a temperature of 80 0 C and then kept at this temperature for 45 minutes by suitable cooling. The overall pressure was kept at 5 bar during this time by appropriate suprly of ethylene.

r i: r 20 4I 380 g of ethylene-1-hexene copolymer were obtained. The following values were determined on the product: VN 182 cm 3 /g density: 0.934 g/cm 3 Example 44: dm 3 of petroleum ether (boiling range 100-120°C) were introduced at 20 0 C into a dry 16 dm 3 reactor which had been flushed with nitrogen. The gas space of the reactor was then flushed free from nitrogen by injecting 2 bar of ethylene and releasing the ethylene, and repeating this operation 4 times. 400 cm 3 of 1-hexane and 30 cm 3 of a toluene solution of methylaluminoxane (10.6% by weight of methylaluminoxane, molecular weight 900 g/mol according to cryoscopic determination) were then added. The reactor was then heated to 60 0 C over the course of 15 minutes S with stirring. The overall pressure was then increased to S 5 bar by introducing ethylene with stirring at 250 rpm.

At the same time, 1.3 mg of metallocene B were dissolved in 20 cm 3 of a toluene solution of methylaluminoxane (concentration and quality as above) and preactivated by being left to stand for 15 minutes. The solution was then introduced into the reactor. The polymerization system was warmed to a temperature of 70°C and then kept at this temperature for 45 minutes by suitable cooling. The overall pressure was kept at 5 bar during this time by appropriate supply of ethylene.

520 g of ethylene-1-hexene copolymer were obtained. The following values were determined on the product: VN 168 cm 3 /g density: 0.924 g/cm 3 Example 200 g of sodium chloride were introduced as a stirring aid in the gas phase at 20°C and under atmospheric pressure into a dry 1.5 dm 3 reactor equipped with paddle stirrer which had been flushed with nitrogen. 5 bar of ethylene were then injected, and the stirrer was set at i 1 i 21 600 rpm. 5 cm 3 of a toluene solution of methylaluminoxane (29.3% by weight of methylaluminoxane having a molecular weight of 1100 g/mol according to cryoscopic determination) were then injected into the reactor by means of a spray nozzle, and the contents were stirred for minutes.

At the same time, 1.1 mg of metallocene B were dissolved in 3 cm 3 of a toluene solution of methylaluminoxane (concentration and quality as above) and preactivated by being left to stand for 15 minutes. This solution was then likewise injected into the reactor by means of a spray nozzle, and the temperature of the system was increased to 80 C. After a polymerization time of minutes, the reactor was decompressed, the contents were removed, and the polymer formed was isolated by dissolving the sodium chloride in water, and filtering off and drying the product.

14.5 g of polyethylene having VN 240 cm 3 /g were obtained.

Example 46: The procedure was as in Example 45, but the 1.1 mg of metallocene B were replaced by 0.9 mg of metallocene E.

10.4 g of polyethylene having a viscosity number VN 230 cm 3 /g were obtained.

".i 22 Table 2 Metal locene Abbi rac-Dimethylsilylbis -indenyl) zirconium dichloride rac-Diphenylsilylbis -indenyl) zirconium dichloride rac-Phenylmethylsilylbis -indenyl) zirconium dichloride rac-Phenylvinylsilylbis -indenyl) zirconium dichloride rac-Dimethylgermylbis -indenyl) zirconium dichloride 1-Silacyclobutylbis (1'-indenyl) zirconium dichloride (isomer mixture: 57% of racisomer, 43% of meso-isomer) rac-Dimethylsilylbis(1-(3-methylindenyl) zirconium dichloride rac-1, 1,2,2-Tetramethyldisilaethylenebis- (1 '-indenyl) zirconium dichloride rac-1,1,4,4-Tetramethyl-1,4-disilabutylenebis- (1 '-indenyl) zirconium dichloride Dimethylsilylbis(1-(3-trimethylsilyl)cyclopentadienyl)zirconium dichloride (isomer mixture: 43% of rac-isomer, 57% of meso-isomer) .25 rac-Ethylenebis (1-indenyl) zirconium dichloride Propylenebis (1-indenyl) zirconium dichloride Ethylenebis -(3-trimethylsilylindenyl) )zirconiun dichloride (isomer mixture: 78% of rac-isomer, 22% of meso-isomer) rac-Ethylenebis (3-allyldimethylsilylindenyl) )-zirconium dichloride Isopropyl -indenyl )cyclopentadienyizirconium d ichloride Diphenylmethylene (9-f luorenyl )cyclopentadienylzirconium dichloride rac-1, 1,2, 2-Tetramethyldisilaethylenebis indenyl )hafnium dichloride Phenylmethylmethylene (9-f luorenyl) cyclopentadienylhafnium dichloride ~eviation

A

B

C

D

E

F

G

H

I

K

L

M

N

0

P

Q

R

T

23 Table 3 Example Metallocene MAO solution Type Amount Content MM Amount in (mg) by (8/moi) reastor weight) cm) a*.

A 4.0 10.5 750 B 3.9 10.6 900 C 7.2 10.7 1200 D 12.2 10.6 900 E 8.0 10.6 900 F 5.9 10.6 900 G 2.5 10.5 750 G 1.3 10.5 750 G 1.2 10.6 900 H- 1.4 9.9 1100 1 48.3 9.9 1100 K 5.3 9.7 1000 L 1.2 10.1 1300 14 7,3 9.9 1100 14 4.3 10.1 1300 N 6.8 9.9 1100 N 3.9 10.1 1300 0 11.6 10.7 1200 P 30.5 10.6 900 Q 5.0 10.6 900 R 6.9 10.1 1300 T 21.6 10.7 1200

H

2 F t T (br 5br 60in 5 60 5 60 5 60 5 60 5 60 5 60 5 60 2 5 60 5 60 5 60 5 60 5 300 6 60 5 120 6 65 0.5 5.5 80 5 60 5 60 5 60 5 60 6 60 24 Table 4 Example Polymer yield (g) Bulk (cm 3 (g/Mol)

S

.45

S

*5e

S.

S

S@

SO S 0*O S

S

*9

S

SO 55 9 5

S

*5

S

a* 300 140 290 140 450 500 240 170 590 1450 590 220 310 480 450 75 150 100 35 323 361 268 319 366 39.2 323 313 36 911 642 162 198 551 624 227 147 230 76 746 1222 711 n. m.

n. m.

n. m.

n. m.

n, m.

n. m.

190000 n. m.

n. m.

720000 480000 n. m.

n. m.

400W4:~ n. m.

120000 n. m.

n. m, n. m.

n. M.

n. m.

n. m.

n. M.

n. m..

n. M.

n. m.

n. m.

n. m.

4.5 n. m.

n. M.

3.5 3.7 n. M.

n. m.

4.0 n. m.

2.3 n. m.

n. m.

n. m.

n. m.

n. m.

n.,m.

dens ity (g/dn 3 210 280 300 310 140 180 170 200 400 210 60 300 140 70 80 120 300 230 200 130 n. m.

n. m.

(Pm) n. m.

n. m.

n. m.

n. m.

n. m.

150 180 n. m.

3500 n. m.

580 n. m.

n. m.

n. m.

n. m.

n. m.

n. m.

n. m.

n. M.

n.m. not measured

Claims (3)

1. A process for the preparation of ethylene polymers having a Mw greater than 50,000 g/mol by polymerization of ethylene or copolymerization of ethylene with 1-olefins having 3 to 20 carbon atoms at a temperature of from -60 to 2000C and a pressure of from 0.5 to 200 bar in solution, in suspension or in the gas phase, in the presence of a catalyst comprising a metallocene as the transition-metal component and an aluminoxane of the formula II R9 f R 9 R 9 AI-O AIl-O-Al R 9 \R9 R n R 9 for the linear type and/or of the formula III Al (III) Sn+2 for the cyclic type, where, in the formulae II and III, R 9 is a Ci-C 6 -alkyl group or phenyl or benzyl, and n is an integer from 2 to 50, which comprises carrying out the polymerization in the presence of a catalyst whose transition-metal component is a compound of the formula I R 3 R 1 R5' (I) R 2 R 4 in which M 1 is titanium, zirconium, vanadium, niobium or tantalum, R 1 and R 2 are identical or different and are a hydrogen atom, a halogen atom, a Ci-Clo-alkyl group, a Ct-Cio-alkoxy group, a C 6 -C 1 o-aryl group, a C 6 -Co-aryloxy group, a C 2 -C0i-alkenyl group, a C 7 -C 40 -arylalkyl group, a C7-C40-a~kyr#\group or -26 a C 8 -C 40 -arylalkenyl group, R 3 and R 4 are identical or different and are a mono- nuclear or polynuclear hydrocarbon radical which, with the central atom ml, is able to form a sandwich structure, R 5 is R 6 rR 6 R 6 R 8 R 6 M2 C C- 17 17 17 R8B R p p p R 6 R8 6 R 6 R 6 R. R 6 64 4 R M CR 17 12 =IBR', =AlR 6 =SO, =SO2, =NR 6 6 6r7 0 4 =CO, =PR 6 or =P(0)R 6 where R R 7 and Ra are ,.identical or different and are a hydrogen atom, a halogen atom, a Cl-Cl-alkyl group, a fluoroalkyl group, a C 6 -C(-fluroaryl group, a C 6 C 10 -aryl group, a C 1 -Cl-alkoxy group, a alkenyl group, a C 7 -C,-arylalkyl group, a BC0 arylalkenyl group or a C 7 -C 4 -alkylaryl group, or v **Rr and R 7 or Rr' and R8, in each case with the atoms connecting them, form a ring, M2 is siiogermanium ortin, and p is the number 1, 2, 3, 4 or
2. A process as claimed in claim 1, wherein the metal- locene employed is rac-dimethylsilylbis(l-indenyl) zirconium dichloride, rac-diphenylsilylbis (1-indenyl) zirconium dichloride, 1-silacyclobutylbis (1'-indenyl) zirconium dichloride, rac-dimethylsilylbis 3-methylindenyl) zirconium -27 dichloride, rac-1,1,2, 2-tetramethyldisilaethylenebis indenyl) zirconium dichloride, dimethylsilylbis( 1- (3-trimethylsilyl )cyclopenta- dienyl)zirconiun dichloride, or diphenylmethylene (9-f luorenyl )cyclopentadienyl- zirconium dichloride. DATED tis 17th day of May 1990. HOECHST AKTIENGESELLSCHAFT a s WATERMARK PATENT TRADEMARK ATTORNEYS V*4 "THE ATRIUM" 290 BURWCOD ROAD HAWTHRON. VIC. 3122. 0. 0 0.*6 046
6.b
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CA2017190A1 (en) 1990-11-20
AU5577190A (en) 1991-01-10
EP0399348A2 (en) 1990-11-28
ZA9003831B (en) 1991-02-27
DE3916555A1 (en) 1990-11-22
EP0700937B1 (en) 2000-02-16
EP0399348B1 (en) 1998-05-20
EP0700937A2 (en) 1996-03-13
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ES2144089T3 (en) 2000-06-01

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