WO1999042492A1

WO1999042492A1 - Polymerisation catalyst component

Info

Publication number: WO1999042492A1
Application number: PCT/GB1999/000362
Authority: WO
Inventors: Vernon Charles Gibson; Sergio Mastroianni; Staffan Stromberg
Original assignee: Bp Chemicals Limited
Priority date: 1998-02-20
Filing date: 1999-02-04
Publication date: 1999-08-26
Also published as: GB9803492D0; AU2434799A; EP1054909A1; ZA991314B

Abstract

A catalyst activator composition useful for the polymerisation of 1-olefins is disclosed, comprising the reaction product of a component (A) comprising a compound having the general formula: R3M wherein R is a hydrocarbyl group and M is a Group III metal, and a component (B) comprising a compound of Formula (I) or a tautomer thereof, wherein Y and Z are each independently O or NR5, X is (CR3R4)n or NR?6; R1, R2 and R5¿ are each independently C¿1?-C6 hydrocarbyl or halohydrocarbyl; R?3, R4 and R6¿ are each independently hydrogen or C¿1?-C6 hydrocarbyl or halohydrocarbyl; and n is 0 or an integer of from 1 to 6; or an aluminium, boron or gallium complex of the compound of Formula (I).

Description

POLYMERISATION CATALYST COMPONENT

The present invention relates to novel polymerisation catalyst components, and especially to organometallic components used as activators for certain catalyst systems based on transition metal compounds, and to the use of such activators in polymerisation catalysts. The use of certain transition metal compounds to polymerise 1-olefins, for example, ethylene, is well established in the prior art. The use of Ziegler-Natta catalysts, for example, those catalysts produced by activating titanium halides with organometallic compounds such as triethylaluminium, is fundamental to many commercial processes for manufacturing polyolefins. Over the last twenty or thirty years, advances in the technology have led to the development of Ziegler-Natta catalysts which have such high activities that that olefin polymers and copolymers containing very low concentrations of residual catalyst can be produced directly in commercial polymerisation processes. The quantities of residual catalyst remaining in the produced polymer are so small as to render unnecessary their separation and removal for most commercial applications. Such processes can be operated by polymerising the monomers in the gas phase, or in solution or in suspension in a liquid hydrocarbon diluent. Polymerisation of the monomers can be carried out in the gas phase (the "gas phase process"), for example by fluidising under polymerisation conditions a bed comprising the target polyolefin powder and particles of the desired catalyst using a fluidising gas stream comprising the gaseous monomer. In the so-called "solution process" the (co)polymerisation is conducted by introducing the monomer into a solution or suspension of the catalyst in a liquid hydrocarbon diluent under conditions of temperature and pressure such that the produced polyolefin forms as a solution in the hydrocarbon diluent. In the "slurry process" the temperature, pressure and choice of diluent are such that the

1 produced polymer forms as a suspension in the liquid hydrocarbon diluent. These processes are generally operated at relatively low pressure (for example 10-50 bar) and low temperature (for example 50 to 150°C). Commodity polyethylenes are commercially produced in a variety of different types and grades. Homopolymerisation of ethylene with transition metal based catalysts leads to the production of so-called "high density" grades of polyethylene. These polymers have relatively high stiffness and are useful for making articles where inherent rigidity is required. Copolymerisation of ethylene with higher 1-olefins (eg butene, hexene or octene) is employed commercially to provide a wide variety of copolymers differing in density and in other important physical properties.

Particularly important copolymers made by copolymerising ethylene with higher 1- olefins using transition metal based catalysts are the copolymers having a density in the range of 0.91 to 0.93. These copolymers which are generally referred to in the art as "linear low density polyethylene" are in many respects similar to the so called "low density" polyethylene produced by the high pressure free radical catalysed polymerisation of ethylene. Such polymers and copolymers are used extensively in the manufacture of flexible blown film.

An important feature of the microstructure of the copolymers of ethylene and higher 1-olefins is the manner in which polymerised comonomer units are distributed along the "backbone" chain of polymerised ethylene units. The conventional Ziegler-Natta catalysts have tended to produce copolymers wherein the polymerised comonomer units are clumped together along the chain. To achieve especially desirable film properties from such copolymers the comonomer units in each copolymer molecule are preferably not clumped together, but are well spaced along the length of each linear polyethylene chain.

In recent years the use of certain transition metal-containing organic complex compounds has provided catalysts with potentially high activity and capable of providing an improved distribution of the comonomer units. Examples of these types of catalyst are the so-called "metallocene" types of catalysts, for example, those based on biscyclopentadienylzirconiumdichloride, and the non- metallocene types which include a very large variety of organic transition metal- based complex catalysts. Both the "metallocene" and the "non-metallocene" types of catalysts, however, generally require the use of special organometallic compounds to convert them into "active" polymerisation catalysts. The most commonly used of these special organometallic compounds (generally referred to as "activators" or "co-catalysts") are those of the alkylaluminium type, especially the so-called "aluminoxanes". Aluminoxanes are commercially available compounds generally prepared by controlled partial hydrolysis of trialkylaluminium compounds. However, the commercially available aluminoxanes are expensive and generally suffer from a number of disadvantages the most important of which are the variability of performance when employed to activate the transition metal complex, and the need to use large quantities to achieve reasonable catalyst activity.

Patent Application WO97/23288 discloses the formation of an aluminoxane precursor composition, useful in the formation of polymerisation catalysts, by reaction of a trialkylaluminium compound and a compound selected from the group consisting of the alcohols, ketones and the carboxylic acids. However, when an organic ketone such as benzophenone is used, it is still found necessary to add methylalumoxane to provide a catalytically useful composition. An object of the present invention is to provide a novel catalyst activator composition suitable for activating organometallic complex polymerisation catalysts, especially organometallic complex transition metal-based catalysts.

The present invention provides a catalyst activator composition comprising the reaction product of a component (A) comprising a compound having the general formula R₃M wherein R is a hydrocarbyl group and M is a Group III metal, and a component (B) comprising a compound of Formula (I)

Formula (I)

or a tautomer thereof, wherein Y and Z are each independently O or NR⁵, X is (CR³R⁴)_n or NR⁶; R¹, R² and R⁵ are each independently Cι-C₆ hydrocarbyl or halohydrocarbyl; R³, R⁴ and R⁶ are each independently hydrogen or C!-C₆ hydrocarbyl or halohydrocarbyl; and n is 0 or an integer of from 1 to 6; or an aluminium, boron or gallium complex of the compound of Formula (I) or tautomer thereof.

When in the form of a complex, the compound of formula (I) or a tautomer thereof is in anionic form, with one of R³, R⁴ or R⁶ having been abstracted as a proton. Preferably component (B) is an organic diketone or an aluminium or gallium or boron complex of an organic diketone.

In component (A) the hydrocarbyl (R) groups in the compound of formula

R₃M can be the same or different and are preferably Ci to Cι₂ hydrocarbyl, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, n-hexyl, n-heptyl, n- octyl, phenyl and 4-methylphenyl. R is most preferably methyl. The Group DI metal M can be for example aluminium, gallium or boron. Aluminium is preferred.

The compound of Formula (I) preferably has the formula

wherein R¹ to R⁴ are each independently hydrocarbyl, or halohydrocarbyl groups containing 1 to 6 carbon atoms and n is zero or an integer from 1 to 4. In the case that one or more of the groups R¹ , R², R³ and R⁴ are halohydrocarbyl, the halogen can be one or more of fluorine, chlorine, bromine and iodine, chlorine and fluorine being preferred. Thus, for example, suitable halohydrocarbyl groups are fluoromethyl, difluoromethyl, trifluoromethyl, chloromethyl, dichloromethyl, chloroethyl, dichloroethyl and trichloroethyl. The organic diketone can be, for example, penta-2,4-dione (ie., acetylacetone), hexa-3,5-dione, or 1,1,1,5,5,5- hexafluoro-penta-2,4-dione. It is most preferably acetylacetone. In the case that the compound of Formula (I) is a ketone and is employed in the form of an aluminium, gallium or boron complex, it is preferred that one of R³ and R⁴ is H. Preferred aluminium, boron or gallium complexes have the formula Al(diketonate)₃, Ga(diketonate)₃,B(diketonate)₃, B(diketonate)Et₂ or B(acetylacetonate)Et₂, preferably Al(acetylacetonate)₃. An example of such a complex is the compound Al(acetylacetonate)₃.

Another aspect of the invention provides a process for the production of a catalyst activator composition, which comprises reacting together a component (A) as defined above, and a component (B) as defined above.

The molar ratio of components (A) and (B) employed in the reaction to make the catalyst activator of the present invention are preferably in the range 100:1 to 1:10, most preferably in the range 100:1 to 2:1. The reaction between components (A) and (B) to make the catalyst activator composition of the present invention can be highly exothermic and is preferably carried out in an inert liquid diluent, for example a liquid hydrocarbon as a moderator. The liquid hydrocarbon can also serve as a useful medium for dispersing or dissolving components (A) and (B) prior to their addition to the reaction, and for storage and transport of the produced activator when the reaction is complete. Examples of suitable hydrocarbons are benzene, toluene, xylene, cyclohexane, tetrahydronaphthalene and decahydronaphthalene.

The reaction between components (A) and (B) can be carried out at any desired temperature. During the initial addition of the components (A) and (B) together, it may be desirable to provide cooling means to remove heat of reaction. Thereafter the reaction mixture is preferably heated, for example, to 50 to 150°C. The reaction time is generally in the range from about 10 minutes to several hours. Preferably reaction conditions are chosen such that the reaction continues for 0.5 to 2 hours at a temperature of 80 to 120°C. The reaction is preferably continued until the concentration of unreacted component (A) in the reaction mixture has fallen to zero or remains at a substantially constant value.

When the reaction has reached the desired state of completion, the produced catalyst activator composition can be used as such, or diluted with a suitable diluent, for example benzene, toluene, xylene, cyclohexane, tetrahydronaphthalene and decahydronaphthalene. If desired, the catalyst activator composition of the present invention can be used supported on a suitable support material, for example, silica, alumina or zirconia, or on a polymer, for example polyethylene. The present invention further provides a process for the preparation of a polymerisation catalyst comprising contacting an organometallic complex polymerisation catalyst precursor, preferably an organometallic complex transition metal-based catalyst precursor, with a catalyst activator composition prepared by reacting together a component (A) comprising a compound having the general formula R₃M wherein R is a hydrocarbyl group and M is a Group III metal, and a component (B) as defined above.

Preferred organometallic complex transition metal-based catalyst precursors suitably used for making the polymerisation catalyst of the present invention are those which form active catalysts with organometallic cocatalysts such as triethylaluminium or aluminoxanes. Preferred transition metal compounds are metallocenes and inorganic compounds or organic complexes of titanium, vanadium, chromium, manganese, iron, cobalt, nickel, platinum, palladium and ruthenium. Many such catalyst precursors, and methods for forming active polymerisation catalysts therefrom, are well known in the art, and analogous techniques are suitably employed in the process of the present invention.

Examples of transition metal-based catalyst precursors include magnesium halide supported Ziegler Natta catalysts, Phillips type (chromium oxide) supported catalysts and supported metallocene catalysts. Other catalysts include supported monocyclopentadienyl constrained geometry type catalysts and supported bidentate α-diimine late transition metal catalysts. Metallocenes may typically be represented by the general formula: (CsR„) _y Z _x (C sRm) M L ₍ ._y.i) where (CsR_x)„ and (C sR_m) are cyclopentadienyl ligands,

R is hydrogen , alkyl, aryl, alkenyl, etc. M is a Group INA metal Z is a bridging group,

L is an anionic ligand, and y is 0, 1 or 2, n and m are 1 -5, x is 0 or 1. The most preferred complexes are those wherein y is 1 and L is halide or alkyl. Typical examples of such complexes are bis (cyclopentadienyl) zirconium dichloride and bis(cyclopentadienyl zirconium dimethyl. In such metallocene complexes the cyclopentadienyl ligands may suitably be substituted by alkyl groups such as methyl, n-butyl or vinyl. Alternatively the R groups may be joined together to form a ring substituent, for example indenyl or fluorenyl. The cyclopentadienyl ligands may be the same or different. Typical examples of such complexes are bis(n-butylcyclopentadienyl) zirconium dichloride or bis (methylcyclopentadienyl) zirconium dichloride.

Examples of monocyclopentadienyl- or constrained geometry complexes may be found in EP 416815A, EP 420436A, EP 418044A and EP 491842A the disclosures of which are incorporated herein by reference. A typical example of such a moncyclopentadienyl complex is (tert-butylamido)(tetramethyl cyclopentadienyl) dimethyl silanetitanium dimethyl.

Further examples of metallocene complexes are those wherein the anionic ligand represented in the above formula is replaced with a diene moiety. In such complexes the transition metal may be in the +2 or +4 oxidation state and a typical example of this type of complex is ethylene bis indenyl zirconium (II) 1,4-diphenyl butadiene. Examples of such complexes may be found in EP 775148 A the disclosure of which is incorporated herein by reference.

Monocyclopentadienyl complexes having diene moieties have also been used for the polymerisation of olefins. Such complexes may be exemplified by (tert-butylamido)(tetramethylcyclopentadienyl) dimetylsilanetitamum (II) penta-

1,3-diene. Such complexes are described in EP 705269A the disclosure of which is incorporated herein by reference.

Other transition metal complexes which may form precursors for the catalysts of the invention are complexes having hetero ring ligands attached to the transition metal, for example O, NR or S ligands. Such complexes are disclosed for example in EP 735057 A and may be illustrated by indenyl zirconium tris(diethylcarbamate).

A preferred transition metal complex has the skeletal unit depicted in

Formula B:

R- N- / M[T] — (T/b).X

Formula B wherein M is Fe[II], Fe[III], Cop], Co[II], Co[III], Mn[I], Mn[II], Mn[III], Mn[IV], Ru[II], Ru[III] orRu[IN]; X represents an atom or group covalently or ionically bonded to the transition metal M; T is the oxidation state of the transition metal M and b is the valency of the atom or group X; R¹, R², R³, R⁴, R⁵, R⁶ and R⁷ are independently selected from hydrogen, halogen, hydrocarbyl, substituted hydrocarbyl, heterohydrocarbyl or substituted heterohydrocarbyl; and when any two or more of R¹ - R⁷ are hydrocarbyl, substituted hydrocarbyl, heterohydrocarbyl or substituted heterohydrocarbyl, said two or more can be linked to form one or more cyclic substituents. A particularly preferred compound of the above type is 2,6-diacetylpyridinebis(2,4,6 trimethyl anil)FeCl₂.

If desired, the catalyst activator composition of the present invention can be used together with conventional organometallic activators for example, organoaluminium compounds and hydrocarbylboron compounds. Suitable organoaluminium compounds include trialkylaluminium compounds, for example, trimethylaluminium, triethylaluminium, tributylaluminium, tri-n-octylaluminium, ethylaluminium dichloride, diethylaluminium chloride and aluminoxanes. Aluminoxanes are well known in the art as typically the oligomeric compounds which can be prepared by the controlled addition of water to an alkylaluminium compound, for example trimethylaluminium. Such compounds can be linear, cyclic or mixtures thereof. Commercially available aluminoxanes are generally believed to be mixtures of linear and cyclic compounds. The cyclic aluminoxanes can be represented by the formula [R⁹AlO]_s and the linear aluminoxanes by the formula R¹⁰(RⁿAlO)_s wherein s is a number from about 2 to 50, and wherein R⁹, R¹⁰, and R¹¹ represent hydrocarbyl groups, preferably Ci to C₆ alkyl groups, for example methyl, ethyl or butyl groups.

Examples of suitable hydrocarbylboron compounds are dimethylphenylammoniumtetra(phenyl)borate, trityltetra(phenyl)borate, triphenylboron, dimethylphenylammonium tetra(pentafluorophenyl)borate, sodium tetrakis[(bis-3,5-trifluoromethyl)phenyl]borate, H⁺(OEt₂)[(bis-3,5- trifluoromethyl)phenyl]bor ate, trityltetra(pentafluorophenyl)borate and tris(pentafluorophenyl) boron.

In the preparation of the catalyst of the present invention the quantity of catalyst activating composition to be employed is easily determined by simple testing, for example, by the preparation of small test samples which can be used to polymerise small quantities of the monomer(s) and thus to determine the activity of the produced catalyst. It is generally found that the quantity employed is sufficient to provide 1 to 20,000 atoms, preferably 1 to 2000 atoms of Group III metal, preferably aluminium, per transition metal atom in the catalyst compound.

The present invention further provides a process for the polymerisation and copolymerisation of 1-olefιns comprising contacting the monomeric olefin under

8 polymerisation conditions with the polymerisation catalyst of the present invention.

The polymerisation conditions can be, for example, solution phase, slurry phase or gas phase. If desired, the catalyst can be used to polymerise ethylene under high pressure/high temperature process conditions wherein the polymeric material forms as a melt in supercritical ethylene. Preferably the polymerisation is conducted under gas phase fluidised bed conditions. Suitable monomers for use in the polymerisation process of the present invention are, for example, ethylene, propylene, butene, hexene, methyl methacrylate, methyl acrylate, butyl acrylate, acrylonitrile, vinyl acetate, and styrene. Preferred monomers for homopolymerisation processes are ethylene and propylene. The catalyst is especially useful for copolymerising ethylene with other 1-olefins such as propylene, 1 -butene, 1 -hexene, 4-methylpentene-l, and octene.

Methods for operating the gas phase fluidised bed process for making polyethylene and ethylene copolymers are well known in the art. The process can be operated, for example, in a vertical cylindrical reactor equipped with a perforated distribution plate to support the bed and to distribute the incoming fluidising gas stream through the bed. The fluidising gas circulating through the bed serves to remove the heat of polymerisation from the bed and to supply monomer for polymerisation in the bed. Thus the fluidising gas generally comprises the monomer(s) normally together with some inert gas (eg nitrogen) and optionally with hydrogen as molecular weight modifier. The hot fluidising gas emerging from the top of the bed is led optionally through a velocity reduction zone (this can be a cylindrical portion of the reactor having a wider diameter) and, if desired, a cyclone and or filters to disentrain fine solid particles from the gas stream. The hot gas is then led to a heat exchanger to remove at least part of the heat of polymerisation. Catalyst is preferably fed continuously or at regular intervals to the bed. At start up of the process, the bed comprises fluidisable polymer which is preferably similar to the target polymer. Polymer is produced continuously within the bed by the polymerisation of the monomer(s). Preferably means are provided to discharge polymer from the bed continuously or at regular intervals to maintain the fluidised bed at the desired height. The process is generally operated at relatively low pressure, for example, at 10 to 50 bars, and at temperatures for example, between 50 and 120 °C. The temperature of the bed is maintained below the sintering temperature of the fluidised polymer to avoid problems of agglomeration. In the gas phase fluidised bed process for polymerisation of olefins it is desirable to provide additional cooling of the bed (and thereby improve the space time yield of the process) by feeding a volatile liquid to the bed under conditions such that the liquid evaporates in the bed thereby absorbing additional heat of polymerisation from the bed by the "latent heat of evaporation" effect. When the hot recycle gas from the bed enters the heat exchanger, the volatile liquid can condense out and can be separated and sprayed into the bed, or recycled to the bed with the recycle gas. It is preferred to reintroduce the condensed liquid into the bed using the process described in our US Patent 5541270. EXAMPLES Preparation of the Activator

The catalyst activators were prepared by reacting together a component (B) of the type shown below with Al(Me)₃ (component A).

R2

\

M /

R2

R1

Component (B)

Table 1 : Components (B) - d Activators

Activator (B) Rl X Y z M n R2

Acl Bl Me CH O O Al 3 -

Ac2 B2 tBu CH O O Al 3 -

Ac3 B3 Ph CH O O Al 3 -

Ac4 B4 Me N O O Al 3 -

Ac5 B5 Me CH N-Me O Al 1 Me

Ac6 B6 Me CH N-Me N-Me Al 1 Me

Ac7 B7 Me CH O O B 1 Et

Synthesis of B

Bl was obtained from Aldrich (number: 20,824-8) B2 was obtained from Aldrich (number: 39,728-8)

10 Example 1: Synthesis of B3

To a solution of dibenzoylmethane (7.40 g, 0.033 mol, Aldrich number: D3,345-4) in toluene was added Al(Me)₃ (1.05 ml, 0.011 mol, Aldrich number: 25,722-2) with venting. The reaction mixture was stirred for 2 hours at room temperature. The yellow precipitate formed was allowed to settle for 1 hour. The solvent was removed and the solid was dried under vacuum. Yield: 7.5 g (98%) Example 2: Synthesis of B4

To a solution of diacetamide (0.76 g, 7.5 mmol, Aldrich number: D3,345- 4) in toluene was added Al(Me)₃ (1.25 ml of 2M solution, 2.5 mmol) with venting. The reaction mixture was gently refluxed for 3 hours. The solvent was removed under vacuum. A slightly yellow powder was obtained. Yield: 0.70 g (85%) Example 3: Synthesis of B5 Ref : H.F. Holtzclaw, J.P. Collman, R.M. Alire, J. Am. Chem. Soc, 1958, 80, 1100.

A methylamine-water solution (8.6 ml, 40% wt, 0.1 mol, Aldrich number: 42,646-6) was added slowly to 2,4-pentanedione (10.3 ml, 0.1 mol, Aldrich number: P775-4) at 0° C. The crystalline material which formed immediately (4- methylamino-3-pentane-2- one) was recrystallised from diethyl ether. Yield: 9.8 g (87%)

To a solution of 4-methylamino-3-pentene-2-one (1.13g, 0.01 mol) in pentane (40 ml), at 0° C, was added Al(Me)₃ (5 ml, 2 M, 0.01 mol) with venting. The reaction mixture was stirred for 1 hour at room temperature. The solution was filtered and solvent removed under vacuum. A viscous oil was obtained. Yield: 1.23 g (73%) Example 4: Synthesis of B6

Ref: (1) S.G. McGeachin, Can. J. Chem., 1968, 46, 1903; (2) B. Qian, D.L. Ward, M.R. Smith, III, Organometallics, 1998, 77, 3074 Triethyloxonium fluoroborate (32.9 ml, 1M in dichloromethane, 0.0329 mol, Aldrich number: 17,623-0) was added to 4-Methylamino-3-pentene-2-one (3.72 g, 0.0329 mol). The resulting solution was stirred for 30 minutes. Methylamine (16.5 ml, 2M in methanol, 0.0330 mol, Aldrich number: 39,504-8) was then added dropwise over a period of 20 minutes. The reaction mixture was stirred for 1 hour. Volatiles were removed under vacuum to obtain a yellow solid.

11 The immonium salt (4-methylamino-3-pentene-2-immonium Fluoroborate) was extracted in hot ethyl acetate. Yield: 1.41 g (20%)

To a solution of 4-methylamino-3-pentene-2-immonium Fluoroborate (1.41 g, 6.6 mmol) in methanol (10 ml) was added sodium methoxide (13.2 ml, 0.5M in methanol, 6.6 mmol, Aldrich number: 40,306-7). The solvent was removed under vacuum and the residue extracted in dichoromethane. This solution was dried under vacuum to afford 2-(methylamino)-4-(methyimino)-2-pentene as a yellow solid. Yield: 0.64 g (77 %)

Al(Me)₃ (2.5 ml, 2 M in toluene, 5 mmol) was added to a solution of 2- (methylamino)-4-(methyimino)-2-pentene (0.64 g, 5 mmol) in pentane (50 ml) at 0 °C with stirring. The mixture was stirred at 0° C for 5 minutes, allowed to warm to room temperature, stirred for an additional hour. After filtration, the filtrate was reduced in volume to approximately 5 ml. Yellow crystals of A6 deposited overnight at -20 °C. The solid was collected by filtration and dried in vacuo. Yield: 0.37 g (41%) Example 5: Synthesis of B7

Ref: B.M. Mikhailov, Y.N. Bubnov, Bull. Acad. Sci. USSR, Div. Chem. Sci., 1960, 1757.

2,4-pentanedione (2.6 ml, 0.025 mol) was added dropwise to triethylborane (25 ml, 1 M solution in hexanes, 25 mmol, Aldrich number: 19.503-0). The reaction mixture was refluxed for 3 hours with venting. Volatiles were removed in vacuo. A green yellow liquid was obtained. Yield: 3.8 g (90%) Syntheses of A Example 6: Synthesis of Acl. Ac2 and Ac3

B (Bl: 1.0 g, 3.09 mmol; B2: 1.78 g, 3.09 mmol; B3: 2.15 g, 3.09 mmol) was charged into a Schlenk tube and dried under vacuum for 30 minutes. Toluene (94 ml) was then added to the solid. Al(Me)₃ (6.0 ml, 61.8 mmol) was added dropwise at 25° C to the solution. The reaction mixture was stirred for 10 minutes at room temperature and then refluxed for 4 hours. The products were yellow solutions ([Al]= 0.65 M). Example 7: Synthesis of Ac4 B4 (0.41g, 1.25 mmol) was charged into a Schlenk tube and dried under

12 vacuum for 30 minutes. Toluene (38 ml) was then added to the solid. Al(Me)₃ (2.4 ml, 25.1 mmol) was added dropwise at 25° C to the solution. The reaction mixture was stirred for 10 minutes and then refluxed for 4 hours. The product was a yellow solution ([Al]= 0.65 M). Example 8: Synthesis of Ac5 and Ac7

B (B5: 1.23 g, 7.3 mmol; B7: 1.22g, 7.3 mmol) was charged into a Schlenk tube. Toluene (65 ml) was added to the viscous oil. Al(Me)₃ (2.4 ml, 51 mmol) was added dropwise at 25° C to the solution. The reaction mixture was stirred for 10 minutes and then refluxed for 4 hours. The products were yellow solutions (Ac5: [Al]= 0.65 M; Ac7: [Al]= 0.57 M. Example 9: Synthesis of Ac6

B6 (0.32g, 1J6 mmol) was charged into a Schlenk tube and dried under vacuum for 30 minutes. Toluene (21 ml) was then added to the solid. Al(Me)₃ (1.2 ml, 12.3 mmol) was added dropwise at 25°C to the solution. The reaction mixture was stirred for 10 minutes and then refluxed for 4 hours. The product was a yellow solution ([Al]= 0.65 M). Polymerisation tests

The polymerisation tests were carried out using the following procedure. The catalyst (either dicyclopentadienylZrCl₂ or 2,6-diacetylpyridinebis(2,4,6- trimethylanil)FeCl₂) was charged into a Schlenk tube and dissolved in 40 ml of toluene, then the activator solution was added. The Schlenk tube was purged with ethylene and the contents were stirred and maintained under 1 bar (absolute) of ethylene throughout the experiment. The polymerisation was terminated by the addition of aqueous hydrogen chloride followed by the addition of methanol. The produced solid polyethylene was filtered off, washed with methanol and dried under vacuum at 40° C. Example 10: Using dicyclopentadienyl ZrCl? as catalyst

13 Table 2: Polymerisation results using zircononcenedichloride with MAO and Acl-

3 and Ac7

Run [Zr] Activator [Al]:[Zr] Reaction PE solid Activity (mmol) time product (g mmor¹ (minutes) fe) h^"1 bar^"1

1 0.01 MAO 600 8 1.50 1125

(Aldrich)_^

2 0.01 Acl 600 8 1.11 832

3 0.013 Ac2 600 8 0.61 352

4 0.01 Ac3 600 8 2.20 1650

5 0.01 Ac7 558 8 0J6 570

Example 11 : Using 2.6-diacetylpyridinebisf2 Aό-trimethylanil. FeC-₂ as catalyst Table 3: Polymerisation results using 2.6-diacetylpyridinebis(2.4.6-trimethylanir, iron dichloride with MAO and Acl-Ac7

Run [Fe] Activator [Al]:[Fe] Reaction PE solid Activity (mmol) time product (g mmor¹ (minutes) fe) h^"1 bar^'1

9 0.001 MAO 600 30 0.62 1240 (Aldrich)

10 0.001 Acl 600 30 0.58 1160

11 0.001 Ac3 600 30 0.83 1660

12 0.001 Ac4 600 30 0.46 920

13 0.001 Ac5 600 30 0.25 500

14 0.001 Ac6 600 30 0.07 140

13 0.001 Ac7 558 30 3.82 7640

14

Claims

Claims:

1. Catalyst activator composition comprising the reaction product of a component (A) comprising a compound having the general formula R₃M wherein R is a hydrocarbyl group and M is a Group III metal, and a component (B) comprising a compound of Formula (I)

=Y

Formula (I)

or a tautomer thereof, wherein Y and Z are each independently O or NR⁵, X is (CR³R⁴)_n or NR⁶; R¹, R² and R⁵ are each independently C╬╣-C₆ hydrocarbyl or halohydrocarbyl; R³, R⁴ and R⁶ are each independently hydrogen or Ci-C╬▓ hydrocarbyl or halohydrocarbyl; and n is 0 or an integer of from 1 to 6; or an aluminium, boron or gallium complex of the compound of Formula (I).

2. Composition according to claim 1 wherein the hydrocarbyl (R) groups in the compound of formula R₃M can be the same or different and are Ci to C₁₂ hydrocarbyl, preferably methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, n- hexyl, n-heptyl, n-octyl, phenyl or 4-methylphenyl.

3. Composition according to claim 2 wherein R is methyl.

15

4. Composition according to any preceding claim wherein the Group III metal M is aluminium, gallium or boron.

5. Composition according to any preceding claim wherein in the compound of Formula (I), one of Y and Z is O and the other is O or NMe.

6. Composition according to claim 5 wherein the compound of formula (I) is an organic diketone having the general formula

wherein R¹ to R⁴ are each independently hydrocarbyl, or halohydrocarbyl groups containing 1 to 6 carbon atoms and n is zero or an integer from 1 to 4.

7. Composition according to claim 6 wherein the organic diketone is employed in the form of an aluminium, gallium or boron complex, n is 1 and R⁴ is H.

8. Composition according to claim 7 wherein the aluminium or gallium complex has the formula Al(diketonate)₃, Ga(diketonate)₃, B(diketonate)₃,

B(diketonate)Et₂ or B(acetylacetonate)Et₂, preferably Al(acetylacetonate)₃.

9. Composition according to any preceding claim supported on silica, alumina or zirconia, or on a polymer.

10. Process for the production of a catalyst activator composition, which comprises reacting together a component (A) as defined in any preceding claim, and a component (B) as defined in any preceding claim.

11. Process according to claim 10 wherein the molar ratio of components (A) and (B) in the reaction is from 100:1 to 1:10, preferably from 100:1 to 2:1.

12. Process according to claim 10 or 11 wherein the reaction is continued until the concentration of unreacted component (A) in the reaction mixture has fallen to zero or remains at a substantially constant value.

13. Catalyst for the polymerisation or copolymerisation of 1-olefins, comprising an organometallic complex polymerisation catalyst precursor and a catalyst activator composition as defined in any of claims 1 to 9 or made by a process according to any of claims 10 to 12.

14. Catalyst according to claim 13 wherein the organometallic complex polymerisation catalyst precursor is a complex of a transition metal compound, and is preferably a metallocene or inorganic compound or organic complex of titanium,

16 vanadium, chromium, manganese, iron, cobalt, nickel, platinum, palladium or ruthenium.

15. Catalyst according to claim 14 wherein the organometallic complex polymerisation catalyst precursor is a complex having the skeletal unit depicted in Formula B:

ΓÇö (T/b).X

Formula B wherein M is Fe[II], Fe[III], Co[I], Co[II], Co[III], Mn[I], Mn[II], Mn[III], Mn[IV], Ru[II], Ru[╧ïl] orRu[IV]; X represents an atom or group covalently or ionically bonded to the transition metal M; T is the oxidation state of the transition metal M and b is the valency of the atom or group X; R¹, R², R³, R⁴, R⁵, R⁶ and R⁷ are independently selected from hydrogen, halogen, hydrocarbyl, substituted hydrocarbyl, heterohydrocarbyl or substituted heterohydrocarbyl; and when any two or more of R¹ - R⁷ are hydrocarbyl, substituted hydrocarbyl, heterohydrocarbyl or substituted heterohydrocarbyl, said two or more can be linked to form one or more cyclic substituents.

16. Process for the preparation of a polymerisation catalyst, comprising performing a process according to any of claims 10 to 12, and then contacting the resultant catalyst activator composition with an organometallic complex polymerisation catalyst precursor as defined in one of claims 14 to 16.

17. Process for the polymerisation or copolymerisation of 1-olefins, comprising contacting the monomeric olefin under polymerisation conditions with a polymerisation catalyst as defined in one of claims 13 to 15, or made by the process of claim 16.

17