CA2375199A1

CA2375199A1 - Catalyst system on the basis of fulven compounds

Info

Publication number: CA2375199A1
Application number: CA002375199A
Authority: CA
Inventors: Rudiger Beckhaus; Jurgen Heinrichs; Sigurd Becke; Steffen Kahlert
Original assignee: Individual
Current assignee: Bayer AG
Priority date: 1999-05-27
Filing date: 2000-05-16
Publication date: 2000-12-07
Also published as: WO2000073315A1; EP1185541A1; JP2003501493A; DE19924176A1; AU5066700A; EP1185541B1; DE50001107D1

Abstract

The invention relates to a catalyst system on the basis of fulven compounds that are reacted with a transition metal compound in the presence of a reducing agent. They are then reacted with an element H-acidic compound. The invention further relates to the use of the catalyst system for polymerizing and copolymerizing olefins and/or dienes.

Description

' CA 02375199 2001-11-23 .a:

- -Catalyst system based on fnlvene compounds The present invention relates to a catalyst system based on fiilvene compounds which are reacted with a transition metal compound in the presence of a reducing agent and then reacted with an element H-acidic compound, and to the use of the catalyst system for the polymerisation and copolymerisation of olefins and/or dienes.
Metal complexes with cyclopentadienyl ligands have been the focus of considerable research since the discovery of ferrocene. It has long been known to use biscyclopentadienyl metal complexes (metallocenes) mixed with activating cocatalysts, preferably alumoxanes, for polymerising olefins and diolefins (for example EP-A 69 951, 129 368, 351 392,. 485 821, 485 823). Metallocenes have proved to be highly active, specific catalysts for the polymerisation of olefins. Metal complexes with only one cyclopentadienyl ligand (half sandwich complexes) are suitable in combination with cocatalysts as specific polymerisation catalysts (US
5132380, EP 416815, WO 91/04257, WO 96/13529). Numerous novel metallocene catalysts or half sandwich catalysts have accordingly been developed in recent years for polymerising olefinic compounds in order to increase activity, selectivity, control of microstructure, molecular weights and molecular weight distribution.
The MAO-based catalyst systems described above do, however, exhibit disadvantages, as explained in greater detail below. Firstly, aluminoxanes, in particular MAO, cannot be produced with high levels of reproducibility either in situ or in pretreatment. MAO is a mixture of various species containing alkylaluminiums, which are present in equilibrium with one another. The number and structure of the aluminium compounds occurring in MAO is not exactly defined. The polymerisation of olefins with catalyst systems containing MAO is accordingly not always reproducible. Moreover, MAO is not stable in storage and its composition changes on exposure to elevated temperatures. One serious disadvantage is the large excess of MAO which is required for activating metallocenes. The high MAO/metallocene ratio is essential if elevated levels of catalyst activity are to be achieved. This results in a processing disadvantage because the aluminium compound must be removed from the t.

polymer during working up. MAO is moreover a cost-determining factor. Elevated MAO excesses are uneconomic for industrial application.
Polymerisation catalysts containing no alumoxane have accordingly been developed S in recent years in order to overcome these disadvantages. For example, Jordan et al.
have reported in J. Am. Chem. Soc., vol. 108 (1986), 7410 a cationic zirconocene/methyl complex which comprises tetraphenylborate as counterion and polymerises ethylene in methylene chloride. EP-A 277 003 and EP-A 277 004 describe ionic metallocenes which are produced by reacting metallocenes with ionising reagents. EP-A 468 537 describes catalysts with an ionic structure which are obtained by reacting dialkyhnetallocene compounds with tetrakis(pentafluorophenyl)-boron compounds. The ionic metallocenes are suitable as catalysts for polymerising olefins. One disadvantage, however, is the great sensitivity of these catalysts to contaminants, such as for example moisture and oxygen. When performing polymerisation reactions, it is accordingly necessary to take precautions in order to ensure the greatest possible purity of the monomers and solvents used. This is technically very complex and costly.
In order to eliminate these disadvantages, EP-A 427 697 and WO 92/01723 describe processes for polymerising olefins, wherein the combination of metallocene dichlorides with alkylaluminiums and tetrakis(pentafluorophenyl)boron compounds are used as the catalyst system. The combination of metallocenes and alkylaluminiums alone is only slightly active or completely inactive as a polymerisa-tion catalyst.
Prior art processes for the production of ionic cyclopentadienyl metal complexes have the disadvantage that the ionising reagents, for example tetrakis(pentafluorophenyl)-boron compounds are sometimes difficult to synthesise and the use thereof is associated with elevated costs.
Comparatively little is known about metal complexes with fulvene ligands.

'' CA 02375199 2001-11-23 w0 00/73315 PCT/EP00/04425 According to Bercaw et a1, JACS (1972), 94, 1219, thermolysis of bis(rls-penta-methylcyclopentadienyl) dimethyltitanium yields the fulvene complex (rl6-2,3,4,5-tetramethylcyclopentadienyl-1-methylene)(rls-pentamethylcyclopentadienyl) methyl-titanium. Marks et al., JACS (1988), 110, 7701 describe the thermolysis of pentamethylcyclopentadienyl complexes of zirconium and hafnium. Thermolysis of bis(r)5-pentamethylcyclopentadienyl) diphenylzirconium yields the fulvene complex (rl6-2,3,4,5-tetramethylcyclopentadienyl-1-methylene)(rls-pentamethylcyclopenta-dienyl) phenylzirconium.
DE 19 732 804 A1 describes a process for the thermal production of fulvene metal complexes and the use thereof as polymerisation catalysts in conjunction with cocatalysts. Another application describes fulvene metal complexes and a process for the production thereof (DE application 19 756 742.8). Fulvene metal complexes which cannot be produced by the thermal process described above are obtainable at 1 S high yield by reacting a fulvene compound with a suitable transition metal complex in the presence of a reducing agent. Direct introduction of the fulvene ligand makes it easier to obtain many novel fulvene metal complexes. In combination with cocatalysts, specific polymerisation catalysts are obtained, the catalytic activity of which is comparable with the activity of metallocene-based catalysts.
It is disadvantageous that fulvene metal complexes are extremely sensitive to air and moisture. Fulvene metal complexes must accordingly be produced and stored under inert gas conditions.
The object of the present invention was to find a catalyst system which at least in part avoids the disadvantages described above. Another object was to find stable catalysts which are simple to synthesise and easy to handle industrially and may straightforwardly be activated for polymerising olefmic compounds in particular.
Another object was to provide catalysts which, under suitable circumstances, may be activated with alkylaluminiums.

" _4_ It has now surprisingly been found that catalysts based on fulvene metal complexes in combination with H-acidic compounds which contain one or more heteroatoms are particularly suitable for the stated objects.
The present invention provides a catalyst system producible by reacting a) a fulvene compound of the formula ()7 _ ( wherein R1, R2, R3, R4, R5, R6 are identical or different and denote hydrogen, halogen, a cyano group, a Cl to CZO alkyl group, a C~ to Cla fluoroallcyl group, a C6 to Clo fluoroaryl group, C, to Coo alkoxy group, a C6 to CZO aryl group, a C6 to Coo aryloxy group, a C2 to Clo alkenyl group, a C~ to Cao arylalkyl group, a C7 to Cao alkylaryl group, a C8 to CQO arylalkenyl group, a CZ to Coo alkynyl group, a silyl group substituted by CI-Cio hydrocarbon residues, a sulfide group substituted by a C,-C,o hydrocarbon residue, an amino group optionally substituted by C1-Coo hydrocarbon residues, or R1, RZ, R3, R4, R5, R6 each, together with the atoms joining them, form one or more aliphatic or aromatic ring systems which may contain one or more heteroatoms selected from the group (O, N, S) and comprise 5 to 10 carbon atoms WO 00/73315 CA 02375199 2001-11-23 pCT/EP00104425 ~. , . _5_ with b) a transition metal compound of the formula (I)7 Am~l)s~1~1 wherein M' is a metal from group 3, 4, 5 or 6 or from the lanthanides or from the actinides of the periodic system of the elements according to IUPAC, A means an optionally mono- or polybridged anionic ligand, Xl means a hydrogen atom, a C~ to Coo alkyl gmup, a C1 to Clo alkoxy group, a C6 to Coo aryl group, a C6 to Clo aryloxy group, a C2 to Coo alkenyl group, a C~ to C~ arylalkyl group, a C~ to C~ alkylaryl group, a Cg to C~ arylalkenyl group, a silyl group substituted by C1 to Coo hydrocarbon residues, a halogen atom or an amide of the formula NR'z R' denotes hydrogen, a C1 to CZO alkyl group, a C6 to C2o aryl group, a C~ to C~ arylalkyl group, a C~ to C~ alkylaryl group, a silyl group substituted by Cl-Clo hydrocarbon residues, an amino group optionally substituted by Cl-C2o hydrocarbon residues, L means a neutral ligand, s means the number 2, 3, 4, 5 or 6, m represents the numbers 0, 1, 2, 3 or 4 arising from the valency and bond state of M', and n is a number from 0 to 10, in the presence of a reducing agent, and subsequently reacting the product with c) a compound of the formula (III) RsYH (111), wherein Rg means a CI to C3° alkyl group, an optionally substituted C6 to C2° aryl group, a C7 to C4° arylalkyl gmup, a C7 to Cao alkylaryl group, a silyl group substituted by Cl-Cl° hydrocarbon residues, or hydrogen, Y means an oxygen atom, a sulfur atom, a group of the formula NR9, a group of the formula PR9, or a group of the formula C(Rl~=N, wherein R9 and Rl° have the same meaning as R8.
Fulvene compounds which may in particular be considered are those of the formula (I), in which R' to R6 denote a C~-CZ° alkyl group, a C6-CZ° aryl group, a C7-C4° alkylaryl group, in particular hydrogen, methyl, trifluoromethyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert.-butyl, phenyl, pentafluorophenyl, methylphenyl, cyclo hexyl, benzyl and dimethylamino.

WO 00!73315 CA 02375199 2001-11-23 PCT/EP00/04425 ~ ~ _~_ Preferred compounds of the formula (I) are fulvene compounds of the formula (Ia) (ta), or fulvene compounds of the formula (Ib) R'' ~R2 (tb), 1 S wherein Rt, RZ, R3 and R4 have the above-stated meaning.
Particularly preferred compounds of the formula (1) are 6-cyclohexylfulvene, 6-iso-propylfulvene, 6-tert.-butylfulvene, 6-phenylfulvene, 6-(dimethylamino)fulvene, 6,6-bis(dimethylamino)fulvene, 6,6-dimethylfulvene, 6,6-bis(trifluoromethyl)fulvene, 6,6-diphenylfulvene, 6,6-bis(pentafluorophenyl)fulvene, 6,6-pentamethylenefulvene, 6,6-tetramethylenefulvene, 6,6-trimethylenefulvene, 2-(2,4-cyclopentadien-1 ylidene)-1,3-dithiolane, 5-benzylidene-1,2,3-triphenyl-1,3-cyclopentadiene, 1,2,3,4 tetramethylfulvene, 1,2,3,4-tetraphenylfulvene, 2,3-dimethylfulvene, 2,3-diisopropyl fulvene, 2,3-diphenylfulvene, 1,4-dimethyl-2,3-diphenylfulvene and 1,4-diethyl-2,3 diphenylfulvene.
The fulvene compounds of the formula (I) or (Ia) and (Ib) may, for example, be synthesised in accordance with J. Org. Chem., vol. 49, no. 11 (1984), 1849.
Transition metal complexes of the formula (II) which may in particular be considered are those in which ~ CA 02375199 2001-11-23 _8_ Ml is a metal from the group titanium, zirconium, hafnium, vanadium, niobium, tantalum and chromium, A is a pyrazolate of the formula NZC3R113, wherein R" denotes hydrogen, a Cl-Clo alkyl group or a C6 to Clo aryl group, a pyrazolylborate of the formula R'B(N2C3Ri 13)3, an alkoxide or phenolate of the formula OR', a siloxane of the formula OSiR'3, a thiolate of the formula SR', an acetylacetonate of the formula (R'CO)2CR', a diimine of the formula (R'N~R')Z, an amidinate of the formula R'C(NR'z~, a cyclooctatetraenyl of the formula CBHqR'8~ with q meaning 0, 1, 2, 3, 4, 5, or 7, wherein R' has the above-stated meaning, L denotes an ether, a thioether, a cyclic ether or cyclic thioether, an amine or a phosphine, X', R', m, n and s have the above-stated meaning.
Particularly preferred transition metal complexes of the formula (II) are those in which M1 denotes titanium, zirconium and hafnium, X' means fluorine, chlorine or bromine, L denotes diethyl ether or tetrahydrofuran m represents the number 0 s means the numbers 2, 3 or 4 and WO 00/73315 CA 02375199 2001-11-23 pCT/Eppp~p442s - _9_ n means the numbers 0, 1, 2, 3 or 4.
Compounds of the formula (III) which may preferably be considered are compounds of the formula (IIIa), ._ "
YH (Illa) wherein Y has the above-stated meaning and R", R'2, R'3, R'4 and R's are identical or different and denote hydrogen, halogen, a cyano group, a C~ to C2o alkyl group, a C~ to Cio fluoroalkyl group, a C6 to Coo fluoroaryl group, a CI to Clo alkoxy group, a C6 to C2o aryl group, a C6 to Clo aryloxy group, CZ to Clo alkenyl group, a C~ to C4o arylalkyl group, a C~ to C4o alkylaryl group, a C8 to C4o arylalkenyl group, a C2 to Coo alkynyl group, a silyl group substituted by Cl-Clo hydrocarbon residues, a sulfide group substituted by a C1-Coo hydrocarbon residue, an amino group optionally substituted by Ct-CZO hydrocarbon residues, or R", R'2, R'3, R'4, R's each, together with the atoms joining them, form one or more aliphatic or aromatic ring systems which rnay contain one or more heteroatoms selected from the group (O, N, S) and comprise 5 to 10 carbon atoms, or compounds of the formula (IIIb), '' CA 02375199 2001-11-23 N-H (llIb) or compounds of the formula (IIIc), \
C=N-H (IBc) Rio wherein R8, R9 and R'° have the above-stated meaning, or Rg and R9 in the formula (IIIb) together with the nitrogen atom joining them or R8 and Rl° in the formula (IBc) with the carbon atom joining them form one or more optionally substituted aliphatic or aromatic ring systems, which may contain one or more heteroatoms selected from the group (O, N, S).
Preferred compounds of the formula (IIIb) include primary amines, such as for example methylamine, ethylamine, i-propylamine, n-butylamine, tert.-butylamine, cyclohexylamine, trimethylsilylamine, aniline, toluidine, or secondary amines, such as for example dimethylamine, diethylamine, di-i-propylamine, di-n-butylamine, di-tert.-butylamine, diphenylamine, methylphenylamine, tert.-butylmethylamine, tert.-butyl-trimethylsilylamine, bis(trimethylsilyl)amine, N-methylaniline, or aliphatic hetero-cyclic amines, such as for example pyrrolidine, piperidine, 2,2,6,6-tetramethylpiperi-dine, piperazine, or aromatic heterocyclic amines, such as for example pyrrole, pyrazole, imidazole, indole, carbazole.
Preferred compounds of the formula (I>Ic) include aldimines, such as acetaldimine, propionaldimine, pivalinaldimine, benzaldimine, or ketimines, such as methyl tert.-butyl ketimine, dicyclohexyl ketimine and benzophenone imine.

Particularly preferred compounds of the formula (IIIa) are those in which Y
denotes an oxygen atom and R8 have the above-stated meaning. These include monohydric phenols, such as for example 1-naphthol, 2-naphthol, 1-phenanthrol, 2-methylphenol (o-cresol), 4-methylphenol (m-cresol), 6-methylphenol (p-cresol), 2-isopropylphenol, . 2,6-diisopropylphenyl, 2,6-di-t.-butylphenol, 2,6-di-t.-butyl-4-methylphenol (ionol), pentafluorophenol, 3,5-bis(trifluoromethyl~henol, 2-methoxyphenol, guaiacol, anol, 2-methoxy-4-allylphenol (eugenol), isoeugenol, saligenin, carvacrol, thymol, 2-hydroxyacetophenone, 4-hydroxyacetophenone, 2-hydroxydiphenyl, 4-hydroxy-diphenyl, 2-cyclohexylphenol, 4-cyclohexylphenol, aminophenol or polyhydric phenols, such as for example pyrocatechol, resorcinol, hydroquinone, pyrogallol, phloroglucinol.
The present invention also provides a process for the production of the catalyst system. The components of the catalyst system according to the invention a), b) and c) 1 S are reacted in a fixed sequence, wherein components a) and b) are first reacted together. This reaction may be performed in such a manner that component a) is reacted in a suitable solvent with component b) in the presence of a reducing agent.
The molar ratio of a) to b) is in the range from 100:1 to 0.1:1, preferably from 10:1 to 0.5:1. Component a) is particularly preferably used with component b) in a 1:1 molar ratio. The resultant reaction product may be isolated and brought into contact with component c) in a separate reaction step. The molar ratio of b) to c) is preferably in the range from 10:1 to 0.5:1. Component b) is particularly preferably used with component c) in a 1:1 molar ratio. It is optionally also possible to dispense with prior isolation of the reaction product from the reaction of component a) with b).
Examples of suitable reducing agents are alkali metals, alkaline earth metals, aluminium, zinc, alloys of alkali metals, such as for example sodium-potassium alloy or sodium amalgam, alloys of alkaline earth metals, as well as metal hydrides.
Examples of metal hydrides are lithium hydride, sodium hydride, magnesium hydride, aluminium hydride, lithium-aluminium hydride and sodium borohydride. Specific examples of reducing agents are sodium naphthalenide, potassium graphite, alkyllithiums, magnesium butadiene, magnesium anthracene, trialkylaluminium ' CA 02375199 2001-11-23 w0 00/73315 PCT/EP00104425 compounds and Grignard reagents. Preferred reducing agents are alkali metals or alkaline earth metals, Cl-C6 alkyllithium, tri-Cl-C6-alkylaluminium compounds and Grignard reagents, such as for example ethylinagnesium chloride. Particularly preferred reducing agents are lithium, sodium amalgam, magnesium and n-butyl-lithium. Instead of the stated reducing agents, it is also possible to perform reduction electrochemically.
The process for the production of the catalyst system according to the invention proceeds in a suitable reaction medium at temperatures of -100 to +250°C, preferably of -78 to +130°C, particularly preferably of -10 to +60°C.
Suitable reaction media which may be considered are, for example, aliphatic or aromatic hydrocarbons, halogenated hydrocarbons, ethers and cyclic ethers.
Examples of such media are unbranched aliphatic hydrocarbons, such as butane, pentane, hexane, heptane, octane, branched aliphatic hydrocarbons, such as isobutane, isopentane, isohexane, cyclic aliphatic hydrocarbons, such as cyclohexane, methyl-cyclohexane, aromatic hydrocarbons, such as benzene, toluene and xylene.
Ethers, such as dialkyl ethers, dimethoxyethane, are preferred and tetrahydrofuran is particularly preferred. Mixtures of different solvents are also suitable.
The catalyst system is produced with exclusion of air and water under inert gas conditions (protective gas method): Examples of inert gases are nitrogen or argon.
The Schlenk method, as is in general conventionally used for organometallic substances, is a suitable example of a protective gas method.
The present invention also provides the use of the catalyst system for the polymerisation of olefins and/or dimes. The catalyst system according to the invention may also be used as a hydrogenation catalyst. The catalyst system may be used directly without separation of secondary products in dissolved form or as a solid.
The catalyst system may be used alone or in combination with cocatalysts.

Cocatalysts which may be considered for polymerisation reaction are the cocatalysts known in the field of metallocene catalysis, such as polymeric or oligomeric aluminoxanes, Lewis acids and aluminates and borates. Reference is in particular made in this connection to Macromol. Symp. vol. 97, July 1995, pp. 1-246 (for alumoxanes) and to EP 277003, EP 277004, Organometallics 1997, 16, 842-857 (for borates), and EP 573403 (for aluminates).
The molar ratio of component b) of the catalyst system to cocatalyst is in the range from 1:0.1 to 1:10000, preferably from 1:1 to 1:1000.
Suitable cocatalysts are in particular methylaluminoxane, methylalumoxane modified by triisobutylaluminium, isooctylaluminoxane, and diisobutylalumoxane, and ionic compounds containing tetrakis(pentafluorophenyl)aluminate as the anion, such as triphenylmethyl tetrakis(pentafluorophenyl)aluminate, and N,N-dimethylanilinium tetrakis(pentafluorophenyl)aluminate and ionic compounds containing tetrakis(penta-fluorophenyl)borate as the anion, such as triphenylmethyl tetrakis(pentafluorophenyl)-borate, and N,N-dimethylanilinium tetrakis(pentafluorophenyl)borate.
Cocatalysts of the formula (IV) are particularly preferred for activating the catalyst system X3_M2_X2 (~, wherein Mz is an element from group 13 of the periodic system of elements according to IUPAC and X2, X3, X4 are identical or different and denote hydrogen, halogen, a C1 to CZO alkyl group, a C, to Coo fluoroalkyl group, a C6 to Coo fluoroaryl group, a C~ to Cio alkoxy group, a C6 to CZO aryl gmup, a C6 to C2o aryloxy group, a C7 to C~
arylalkyl group or a C~ to C4o alkylaryl group.
Compounds of the formula (I~ include, for example, trialkylaluminium compounds, such as trimethylaluminium, triethylaluminium, triisobutylaluminium, triisooctyl-aluminium, as well as dialkylaluminium compounds, such as diisobutylaluminium hydride, diisobutylaluminium fluoride and diethylaluminium chloride, and substituted triarylaluminium compounds, such as tris(pentafluorophenyl)aluminium, and substituted triarylboron compounds, such as tris(pentafluorophenyl)boron.
Mixtures of different cocatalysts may also be used.
Polymerisation is taken to mean both homo- and copolymerisation of olefins and/or dimes. Compounds in particular used in the polymerisation reaction are Cz-Clo alkmes, such as ethylene, propylene, 1-butme, 1-pmtene and 1-hexme, 1-octme, isobutylene and arylalkenes, such as styrene. Dimes which are used in particular are conjugated dienes, such as 1,3-butadiene, isoprene, 1,3-pentadiene, and non conjugated dimes, such as 1,4-hexadiene, 1,5-heptadiene, 7-methyl-1,6-octadiene, 5,7-dimethyl-1,6-octadiene, 4-vinyl-1-cyclohexene, 5-ethylidene-2-norbornene, vinyl-2-norbornene and dicyclopentadiene.
The catalysts according to the invention are suitable for the production of polyethylene and ethylene (co)polymers, in particular of rubbers based on copolymers of ethylene with one or more of the stated a-olefins and the stated dienes.
The catalyst system according to the invention is fiu-thermore suitable for the polymerisation of cycloolefins, such as norbornene, cyclopentene, cyclohexene, cyclooctane, and the copolymerisation of cycloolefins with ethylene or a-olefins. Mixtures of various catalysts according to the invention may, of course, also be used.
Polymerisation may be performed in the liquid phase, in the presence or absence of an inert solvent, or in the gas phase. Suitable solvents are aromatic hydrocarbons, such as =15-benzene and/or toluene, or aliphatic hydrocarbons, such as propane, hexane, heptane, octane, isobutane, cyclohexane or mixtures of the various hydrocarbons.
It is possible to use the catalyst system according to the invention in supported form.
Suitable support materials which may be mentioned by way of example are inorganic or organic polymeric supports, such as silica, zeolites, carbon black, activated carbon, aluminium oxide, polystyrene and polypropylene.
The catalyst system according to the invention may here be applied onto the support materials in conventional manner. Methods for supporting catalyst systems are described, for example, in US 4 808 561, 4 912 075, 5 008 228 and 4 914 253.
Polymerisation is generally performed at pressures of 1 to 1000, preferably of 1 to 100 bar, and temperatures of -100 to +250°C, preferably of 0 to +150°C.
Polymerisation may be performed continuously or batchwise in conventional reactors.
The present invention also provides the polymers obtainable in this manner.
The following Examples illustrate the invention in greater detail.

Examples General details: The organometallic compounds were produced and handled with exclusion of air and moisture under a protective argon atmosphere (Schlenk method).
All the necessary solvents were absoluted by several hours' boiling over a suitable desiccant and subsequent distillation under argon.
Polymer characterisation: DSC measurements were performed with a Perlan-Elmer instrument with the name Differential Scanning Calorimeter DSC-2 using the following parameters: two heating periods -90°C, to +180°C, heating rate 20 K/min, rapid cooling at 320 K/min to -90°C, nitrogen flushing, initial sample masses of 12.3 mg in standard capsules. Determination of polymer composition by IR
spectroscopy was performed to ASTM D 3900. Intrinsic viscosity was determined in an Ubbelohde capillary viscosimeter (multipoint measurement at three concentrations in o-dichlorobenzene, dissolution time: 6 h at 140°C).
Abbreviations:
THF tetrahydrofiuan RT room temperature HV high vacuum MAO methylaluminoxane TIBA triisobutylaluminium dH enthalpy of fusion (DSC measurement) Tg glass transition temperature (DSC measurement) Example 1 Reaction of 6,6-diphenylfulvene with TiCl2~2 THF in the presence of magnesium 167 mg (0.5 mmol) of TiCy2 THF and 115.1 mg (0.5 mmol) of 6,6-diphenylfulvene were dissolved in 10 ml of THF and combined with 12.16 mg (0.5 mmol) of magnesium. The mixture was stirred overnight at RT, such that the magnesium was ' CA 02375199 2001-11-23 , WO 00/73315 ' PCT/EP00/04425 completely consumed. The resultant dark green solution was diluted with 10 ml of THF. A solution containing 25 pmol of dtanium/ml was obtained.
Example 2 Reaction of ~ the reaction product from Example 1 with 2,6-di-tert.-butyl-4-methylphenol 4 ml of the solution from Example 1 (0.1 mmol of titanium) were combined with a solution of 22.0 mg (0.1 mmol) of 2,6-di-tert.-butyl-4-methylphenol in 2 ml of THF
and stirred for 60 minutes at RT. The solvent was then removed by distillation, the remaining residue dried under HV and combined with 20 ml of toluene. A
suspension containing 5 pmol of titanium/ml was obtained.
Example 3 Polymerisation of ethylene 100 ml of toluene and 7 ml of a 10% solution of methylalumoxane (MAO) in toluene were initially introduced into a 250 ml glass reactor and combined with 2 ml of the suspension from Example 2 (10 ~,mol of titanium). The resultant solution was stirred for 10 minutes at RT and then heated to 40°C. Ethylene was then continuously introduced into the solution through a gas inlet tube at a pressure of 1.1 bar. At a temperature of 40°C and an ethylene pressure of 1.1 bar, the reaction was terminated after 10 minutes' polymerisation by addition of 50 ml of methanol, the resultant polymer filtered out, washed with methanol and dried in a vacuum drying cabinet.
0.7 g of polyethylene were obtained.

' CA 02375199 2001-11-23 w0 00/73315 PCT/EP00/04425 Example 4 Reaction of the reaction product from Example 1 with 3,5-bis(trifluoromethyl~
phenol 4 ml of the solution from Example 1 (0.1 mmol of titanium) were combined with a solution of 23 mg (0.1 mmol) of 3,5-bis(trifluoromethyl~henol in 2 ml of THF
and stirred for 60 minutes at RT. The solvent was then removed by distillation, the remaining residue dried under HV and combined with 20 ml of toluene. A
suspension containing 5 p,mol of titanium/ml was obtained.
Example 5 Polymerisation of ethylene The polymerisation from Example 3 was repeated, except that 2 ml of the suspension from Example 4 (10 pmol of titanium) were used instead of the suspension from Example 2. 1.5 g of polyethylene were obtained.
Example 6 Reaction of the reaction product from Example 1 with pentafluorophenol 4 ml of the solution from Example 1 (0.1 mmol of titanium) were combined with a solution of 18.4 mg (0.1 mmol) of pentafluorophenol in 2 ml of THF and stirred for 75 minutes at RT. The solvent was then removed by distillation, the remaining residue dried under HV and combined with 20 ml of toluene. A suspension containing 5 ~mol of titanium/ml was obtained.

w0 00/73315 PCT/EP00/04425 Example 7 Polymerisation of ethylene The polymerisation from Example 3 was repeated, except that 2 ml of the suspension from Example 6 (10 p.mol of titanium) were used instead of the suspension from Example 2. 1.2 g of polyethylene were obtained.
Example 8 Reaction of the reaction product from Example 1 with 2,6-diisopropylphenol 4 ml of the solution from Example 1 (0.1 mmol of titanium) were combined with a solution of 17.8 mg (0.1 mmol) of 2,6-diisopropylphenol in 2 ml of THF and stirred for 60 minutes at RT. The solvent was then removed by distillation, the remaining residue dried under HV and combined with 20 ml of toluene. A suspension containing 5 p.mol of titanium/ml was obtained.
Example 9 Polymerisation of ethylene The polymerisation from Example 3 was repeated, except that 2 ml of the suspension from Example 8 (10 itmol of titanium) were used instead of the suspension from Example Z. 1.7 g of polyethylene were obtained.

w0 00173315 PCT/EP00/04425 Example 14 Polymerisation of ethylene The polymerisation from Example 9 was repeated, except that 1 ml of a 1 molar TIBA
solution in toluene was used instead of MAO. The polymerisation temperature was 60°C. 2.4 g of polyethylene were obtained.
Example 11 Reaction of 6,6-dimethylfulvene with TiCl4~2 TFIF in the presence of magnesium and subsequent reaction with 2,6-diisopropylphenol 334 mg (1 mmol) of TiCy2 THF' and 106 mg (1 mmol) of 6,6-dimethylfulvene were 1 S dissolved in 10 ml of THF and combined with 24.3 mg (1 mmol) of magnesium.
The mixture was stirred overnight at RT, such that the magnesium was completely consumed. A solution of 178 mg (1 mmol) of 2,6-diisopropylphenol in 2 ml of THF
was then added dropwise and stirred for 2 hours at RT. The solvent was removed by distillation and the remaining residue combined with 40 ml of toluene. A
suspension containing 25 pmol of titanium/ml was obtained.
Example 12 Polymerisation of ethylene 100 ml of toluene and 0.25 ml of triisobutylaluminium (TIBA) were initially introduced into a 250 ml glass reactor and combined with 0.4 ml of the suspension from Example 11 (10 ~.mol of titanium). The resultant solution was heated to 60°C.
Ethylene was then continuously introduced into the solution through a gas inlet tube at a pressure of 1.1 bar. At a temperature of 60°C and an ethylene pressure of 1.1 bar, ' the reaction was terminated after 10 minutes' polymerisation by addition of 50 ml of methanol, the resultant polymer filtered out, washed with methanol and dried in a vacuum drying cabinet. 0.6 g of polyethylene were obtained.
Example 13 Reaction of 6,6-diphenylfulvene with TiC>4~2 THF in the presence of magnesium and subsequent reaction with 2,6-diisopropylphenol 334 mg (1 mmol) of TiCy2 THF and 230 mg (1 mmol) of 6,6-diphenylfulvene were dissolved in 10 ml of THF and combined with 24.3 mg (1 mmol) of magnesium. The mixture was stirred for 2 hours at RT, such that the magnesium was completely consumed. A solution of 178 mg (1 mmol) of 2,6-diisopropylphenol in 2 ml of THF
was then added dropwise and stirred for 2 hours at RT. The solvent was removed by distillation and the remaining residue combined with 40 ml of toluene. A
suspension containing 25 pmol of titanium/ml was obtained.
Example 14 Polymerisation of ethylene 500 ml of n-hexane and 1 ml of TIBA were initially introduced into a 1.4 L
steel autoclave and adjusted to a temperature of 80°C. Ethylene was then apportioned until the pressure inside the autoclave rose to 10 bar. Preactivation of catalyst:
0.4 ml of the suspension from Example 13 was added to a solution of 0.25 ml of TIBA in 5 ml of hexane and stirred for 10 minutes at RT. Polymerisation was started by adding the preactivated catalyst solution (10 pmol of titanium). After 40 minutes' polymerisation at 80°C and 10 bar, the autoclave was depressurised, polymerisation terminated with a 1 % HCl solution in methanol and the mixture stirred for 1 h. The resultant polymer was filtered out, washed with methanol, isolated and dried for 20 h at 60°C under a vacuum. 45.5 g of highly crystalline polyethylene were obtained. The DSC
melting point on 1 St heating was 142.1 °C (dH = 220.4 J/g), that on 2°d heating 135.4°C (dH =
166 J/g).

' WO 00/73315 PCT/EP00/04425 Ezample 15 Copolymerisation of ethylene and 1-hegene The polymerisation from Example 14 was repeated, except that 10 ml of 1-hexene were also initially introduced into the autoclave. Polymerisation was performed for 30 minutes at 80°C and 10 bar. 43.3 g of an ethylene/1-hexene copolymer were obtained.
Example 16 Copolymerisation of ethylene and propylene 500 ml of hexane and 1 ml of TIBA were initially introduced into a 1.4 L steel autoclave equipped with a mechanical stirrer, manometer, temperature sensor, temperature controller, catalyst lock and monomer apportioning devices for ethylene and propylene. The internal temperature was adjusted to 60°C with a thermostat. 12 g of ethylene and 27 g of propylene were then apportioned (ratio by weight 3:7).
Polymerisation was started by adding 0.2 ml of the suspension from Example 13 (5 pmol of titanium). Using a semi-batch method, ethylene and propylene were continuously apportioned in a 3:7 ratio by weight such that the internal pressure remained a constant 7 bar at 60°C. After 30 minutes' polymerisation, the autoclave was depressurised and the highly viscous reaction solution diluted with 1 litre of toluene, stirred into 3 litres of methanol and stirring continued for a further 2 hours.
The precipitated polymer was washed with methanol, isolated and dried for 20 h at 60°C under a vacuum, wherein 24.3 g of an ethylene/propylene copolymer were obtained. IR investigation revealed a composition of 80.2 wt.% ethylene and 19.9 wt.% propylene. Intrinsic viscosity in o-dichlorobenzene was 5.94 dl/g. A
Tg of -48.0°C (2"d heating) was determined by the DSC method.

Example 17 Copolymerisation of ethylene and propylene The polymerisation from Example 16 was repeated, except that ethylene and propylene were apportioned in a ratio by weight of 1:4. After 30 minutes' polymerisation, 18.3 g of an ethylene/propylene copolymer were obtained. IR
investigation revealed a composition of 74.8 wt.% ethylene and 25.2 wt.%
propylene.
Intrinsic viscosity in o-dichlorobenzene was 3.6 dl/g. A Tg of -47.5°C
(2"d heating) was determined by the DSC method.
Example 18 Copolymerisation of ethylene and propylene The polymerisation from Example 16 was repeated, except that ethylene and propylene were apportioned in a ratio by weight of 1:9. After 20 minutes' polymerisation, 11.0 g of an ethylene/propylene copolymer were obtained. 1R
investigation revealed a composition of 54.7 wt.% ethylene and 45.3 wt.%
propylene.
Intrinsic viscosity in o-dichlorobenzene was 3.2 dl/g. A Tg of -55.0°C
(2"a heating) was determined by the DSC method.

on a ~O
0o O o0 O °v d.
,'~ ~1 V1 °1 l~ ~ ~O
O '" O ''' N O ,tea ~ 01 ~D N
U
U ~ ~ M M
wr O
n d~.~~V V~~~ U
H vy. °r O U
o0 00 ~
'" O O O O

w ° °

o_ _~~ o o ~ ~ °
M M O
~r Cdr ~, ,.." ' O _ '~ .rr" .-. ...~ .r ~ ..r t1' 00 O ,-. U O ~ ~ ~ v ~ °O" N '~' .-r .s"U" O y,0 O ~ O O M b~4 ..., O ~ ~. Cl~ ~. r.r Q' ~ '~ ~ ~ ~ _N
O °, '~ '~ '~ t3' a~
. a ~' ~ ~, ~G ~O ~O A
c~, '~ '~ N N N ~ W ~ ~ t~ l~ I~
N ~ M
-~ G ~'J C
" ~U,' C~ U~" .U~' U ~ .O~ U
U o 0 0 ~H ~. ~~~~~~~ ~~d~ ø,~ ~ovovo o °' w s~. s~. p, p. .~., .a. ° ~ o °~ o ° °~' ° ~~~~.~cv'o oN ~o° °
p O y0 ~D VO VO VO ~D ~ O '".' y~ ~ . ~ O O
O O .~ W r ~O
v ;,.; '-'~ ,", N W o 00 00 ono ~~~~~~~ ono' .b~ ~o°oa°, A. U v~ U x x x x x ~ U U U r° ~ W
W W W W W W ts.
p, °' N ø, M V1 l~ 01 ~ ~ ~ ~O l~ 00 x .--y-r rr H H W

Claims

1. Composition producible by reacting a) a fulvene compound of the formula (I) wherein R1, R2, R3, R4, R5, R6 are identical or different and denote hydrogen, halogen, a cyano group, a C1 to C20 alkyl group, a C1 to C10 fluoroalkyl group, a C6 to C10 fluoroaryl group, C1 to C10 alkoxy group, a C6 to C20 aryl group, a C6 to C10 aryloxy group, a C2 to C10 alkenyl group, a C7 to C40 arylalkyl group, a C7 to C40 alkylaryl group, a C8 to C40 arylalkenyl group, a C2 to C10 alkynyl group, a silyl group substituted by C1-C10 hydrocarbon residues, a sulfide group substituted by a C1-C10 hydrocarbon residue, an amino group optionally substituted by C1-C10 hydrocarbon residues, or R1, R2, R3, R4, R5, R6 each, together with the atoms joining them, form one or more aliphatic or aromatic ring systems which may contain one or more heteroatoms selected from the group (O, N, S) and comprise 5 to 10 carbon atoms with b) a transition metal compound of the formula (II) A m(X1)s L n M1 (II), wherein M1 is a metal from group 3, 4, 5 or 6 or from the lanthanides or from the actinides of the periodic system of the elements according to IUPAC, A means an optionally mono- or polybridged anionic ligand, X1 means a hydrogen atom, a C1 to C10 alkyl group, a C1 to C10 alkoxy group, a C6 to C10 aryl group, a C6 to C10 aryloxy group, a C2 to C10 alkenyl group, a C7 to C40 arylalkyl group, a C7 to C40 alkylaryl group, a C8 to C40 arylalkenyl group, a silyl group substituted by C1 to C10 hydrocarbon residues, a halogen atom or an amide of the formula NR72, R7 denotes hydrogen, a C1 to C20 alkyl group, a C6 to C20 aryl group, a C7 to C40 arylalkyl group, a C7 to C40 alkylaryl group, a silyl group substituted by C1-C10 hydrocarbon residues, an amino group optionally substituted by C1-C20 hydrocarbon residues, L means a neutral ligand, s means the number 2, 3, 4, 5 or 6, m represents the numbers 0, 1, 2, 3 or 4 arising from the valency and bond state of M1, and n is a number from 0 to 10, in the presence of a reducing agent, and subsequently reacting the product with c) a compound of the formula (III) R8YH (III), wherein R8 means a C1 to C30 alkyl group, an optionally substituted C6 to C20 aryl group, a C7 to C40 arylalkyl group, a C7 to C40 alkylaryl group, a silyl group substituted by C1-C10 hydrocarbon residues, or hydrogen, Y means an oxygen atom, a sulfur atom, a group of the formula NR9, a group of the formula PR9, or a group of the formula C(R10)=N, wherein R9 and R10 have the same meaning as R8.

2. Composition according to claim 1, wherein M1 is a metal from the group titanium, zirconium, hafnium, vanadium, niobium, tantalum and chromium.

3. Composition according to one or more of claims 1 to 2, wherein Y means an oxygen atom.

4. Composition according to one or more of claims 1 to 3, wherein the reducing agent is lithium, sodium amalgam, magnesium, or n-butyllithium.

5. Process for the production of a composition according to one or more of claims 1 to 4, characterised in that components a), b) and c) are reacted in a fixed sequence, wherein components a) and b) are first reacted together and are then reacted with c).

6. Process according to claim 5, characterised in that the molar ratio of component a) to component b) is in the range from 100:1 to 0.1:1.

7. Process according to one or more of claims 5 to 6, characterised in that the molar ratio of component b) to component c) is in the range from 10:1 to 0.5:1.

8. Composition producible by reacting the catalyst system according to one or more of claims 1 to 4 with a compound of the formula (IV) wherein M2 is an element from group 13 of the periodic system of elements according to IUPAC and X2, X3, X4 are identical or different and denote hydrogen, halogen, a C1 to alkyl group, a C1 to C10 fluoroalkyl group, a C6 to C10 fluoroaryl group, a C1 to C10 alkoxy group, a C6 to C20 aryl group, a C6 to C20 aryloxy group, a C7 to C40 arylalkyl group or a C7 to C40 alkylaryl group.

9. Use of the composition according to one or more of claims 1 to 4, optionally in combination with a cocatalyst for the polymerisation of olefins and/or dienes.

10. Use of the composition according to claim 8 for the polymerisation of olefins and/or dienes.

11. Polymers producible in a polymerisation process in the presence of a composition according to one or more of claims 1 to 4 and/or claim 8.