WO2006030199A1

WO2006030199A1 - Polymerisation catalysts

Info

Publication number: WO2006030199A1
Application number: PCT/GB2005/003529
Authority: WO
Inventors: Vernon Charles Gibson; Grant Berent Jacobsen; David John Jones; Richard James Long
Original assignee: Ineos Europe Limited
Priority date: 2004-09-15
Filing date: 2005-09-13
Publication date: 2006-03-23
Also published as: GB0420559D0

Abstract

A catalyst system comprising (1), complex of Formula (A); wherein groups Rl and R2 are -Ra, -ORb, -NRcRd, or -NHRe: M is a Group 3 to 11 or a lanthanide metal; E is phosphorus or arsenic; X is an anionic group, L is a neutral donor group; y and z are zero or integers, and with the proviso that (A) when M is vanadium, n = 1 or 2 and (B) when M is not vanadium n = 2 and the Rl groups are linked to form R5 such that Formula (A) becomes Formula (B), and wherein the divalent group R5 is selected from the divalent groups -Ra-,-O-Rb’-,-O-Rb’-O-,-N-(Rc)Rd'-,-N(Rc)-,-N(Rc)-Rd’-N(Rc)-,-Si(Rc)2-Ra’-Si(Rc)2-, and -Si(Rc)2- ;the monovalent groups Ra, Rb, Rc, Rd, Re, and the divalent group R3 , Ra’, Rb’, and Rd’ are independently selected from (i) aliphatic hydrocarbon, (ii) alicyclic hydrocarbon, (iii) aromatic hydrocarbon, (iv) alkyl substituted aromatic hydrocarbon (v) heterocyclic groups and (vi) heterosubstituted derivatives of said groups (i) to (v); (2) a a solid particulate catalyst-activating support, insoluble in hydrocarbons, comprising at least magnesium and aluminium atoms and hydrocarbyloxy groups containing 1 to 20 carbons atoms, the molar ratio of Mg/Al being in the range 1.0 to 300 and the molar ratio of hydrocarbyloxy groups to aluminium atoms being in the range 0.05 to 2.0, and optionally, (3) an additional activator selected from aluminium alkyl activators and boron compound activators.

Description

POLYMERISATION CATALYSTS

The present invention relates to transition metal-based catalyst systems and to their use in the polymerisation and copolymerisation of olefins.

The use of certain transition metal compounds to polymerise 1 -olefins, for example, ethylene or propylene, 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 three decades, advances in the technology have led to the development of Ziegler-Natta catalysts which have such high activities 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, or, in the case of propylene, in bulk.

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 copolymerismg ethylene with higher 1 -olefins vising 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.

Polypropylenes are also commercially produced in a variety of different types and grades. Homopolymerisation of propylene with transition metal based catalysts leads to the production of grades with a wide variety of applications. Copolymers of propylene with ethylene or terpolymers with ethylene and higher 1 -olefins are also useful materials.

In recent years the use of certain metallocene catalysts (for example biscyclopentadienylzirconiumdichloride activated with alumoxane) has provided catalysts with potentially high activity. Other derivatives of metallocenes have been shown to be potentially useful for producing polypropylene with good activity, molecular weight and tacticity control. However, metallocene catalysts of this type suffer from a number of disadvantages, for example, high sensitivity to impurities when used with commercially available monomers, diluents and process gas streams, the need to use large quantities of expensive alumoxanes to achieve high activity, difficulties in putting the catalyst on to a suitable support and synthetic difficulties in the production of more complex catalyst structures suitable for polymerising propylene in a tactic manner. An object of the present invention is to provide a novel transition metal catalyst system which can be used for polymerising unsaturated monomers. A further object of the present invention is to provide a process for polymerising monomers, for example, olefins, and especially for polymerising ethylene alone or propylene alone, or for copolymerising ethylene with higher 1 -olefins with high activity.

One aspect of the present invention provides a novel transition metal catalyst system comprising (1) transition metal complex having the following Formula A: Fonnula A

wherein the monovalent groups R¹ and R² are independently selected from -R^a, -OR^b, -NR^cR^d, and -NHR^e: the monovalent groups R^a, R^b, R⁰, R^d, and R^e, and the divalent group R³ are independently selected from (i) aliphatic hydrocarbon, (ii) alicyclic hydrocarbon, (iii) aromatic hydrocarbon, (iv) alkyl substituted aromatic hydrocarbon (v) heterocyclic groups and (vi) heterosubstituted derivatives of said groups (i) to (v); M is a metal from Group 3 to 11 of the Periodic Table or a lanthanide metal; E is phosphorus or arsenic; X is an anionic group, L is a neutral donor group; y and z are independently zero or integers such that the number of X and L groups satisfy the valency and oxidation state of the metal M, and with the proviso that

(A) when M is vanadium, n = 1 or 2 and

(B) when M is not vanadium n = 2 and the R¹ groups on the two units

are linked to form R such that Formula A becomes Formula B.

Formula B

and wherein the divalent group R⁵ is selected from the divalent groups -R^a- , -O-R^b- , -O-R^b'-O- , -N-(R^c)R^d'- , -N(R⁰)- , -N(R^C)-R^d'-N(R^C)- , -Si(R^c)₂-R^a'-Si(R^c)₂- , and -Si(R^c)₂- ; the divalent groups R^{a '}, R^b', and R^d' being independently selected from divalent (i) aliphatic hydrocarbon, (ii) alicyclic hydrocarbon, (iii) aromatic hydrocarbon, (iv) alkyl substituted aromatic hydrocarbon (v) heterocyclic groups and (vi) heterosubstituted derivatives of said groups (i) to (v),

(2) a catalyst-activating support which is a solid particulate substance, insoluble in hydrocarbons, comprising at least magnesium and aluminium atoms and hydrocarbyloxy groups containing 1 to 20 carbons atoms, the molar ratio of Mg/ Al being in the range 1.0 to 300 and the molar ratio of hydrocarbyloxy groups to aluminium atoms being in the range 0.05 to 2.0, and optionally,

(3) an additional activator selected from aluminium alkyl activators and boron compound activators.

Preferably the average particle size of the support material is in the range 3 to 80 micrometres (μm), more preferably 5 to 60 micrometres.

The monovalent groups R^a, R^b, R^c, R^d, and R^e, and the divalent group R³ are defined above as (i) aliphatic hydrocarbon, (ii) alicyclic hydrocarbon, (iii) aromatic hydrocarbon, (iv) alkyl substituted aromatic hydrocarbon (v) heterocyclic groups, (vi) heterosubstituted derivatives of said groups (i) to (v). These defined groups preferably contain 1 to 30, more preferably 2 to 20, most preferably 2 to 12 carbon atoms. Examples of suitable monovalent aliphatic hydrocarbon groups are methyl, ethyl, ethenyl, butyl, hexyl, isopropyl and tert-butyl. Examples of suitable monovalent alicyclic hydrocarbon groups are adamantyl, norbornyl, cyclopentyl and cyclohexyl. Examples of suitable monovalent aromatic hydrocarbon groups are phenyl, biphenyl, naphthyl, phenanthrenyl and anthacenyl. Examples of suitable monovalent alkyl substituted aromatic hydrocarbon groups are benzyl, tolyl, mesityl, 2,6- diisopropylphenyl and 2,4,6-triisopropyl. Examples of suitable monovalent heterocyclic groups are 2-pyridinyl, 3-pyridinyl, 2-thiophenyl, 2-furanyl, 2-pyrrolyl, 2-quinolinyl. As regards the divalent group R³, this, for example, can be selected from any of the aforementioned monovalent groups wherein one of the hydrogen atoms on the said monovalent group is replaced by a valency bond to form the second bond on the divalent group R . Suitable substituents for forming heterosubstituted derivatives of said groups R^a, R^b, R^c, R^d, R^e and R³ are, for example, chloro, bromo, fluoro, iodo, nitro, amino, cyano, alkoxy, mercapto, hydroxyl and silyl. Examples of alkoxy groups are methoxy, ethoxy, phenoxy (i.e. -OC₆H₅), tolyloxy (i.e. -OC₆H₄(CH₃)), xylyloxy, mesityloxy. Examples of amino groups are dimethylamino, diethylamino, methylethylamino. Examples of mercapto groups are thiomethyl, thiophenyl. Examples of silyl groups are trimethylsilyl and triethylsilyl. Examples of suitable heterosubstituted derivatives of said groups (i) to (v) are 2-chloroethyl, 2-bromocyclohexyl, 2-nitrophenyl, 4-ethoxyphenyl, 4-chloro-2- pyridinyl, 4-dimethylaminophenyl and 4-methylaminophenyl. R¹ and R² can, if desired, form a single integral divalent group R⁴, wherein R⁴ is independently selected from the divalent groups -R^a'- , -O-R^b'- , -O-R^b'-O- , -N-(R^c)R^d'- , -N(R^C)- , -N(R^C)-R^d'-N(R^C)- , -Si(R^c)₂-R^al-Si(R^c)₂- , and -Si(R^c)₂- ; and wherein the divalent groups R^a', R^b', and R^d' are independently selected from divalent (i) aliphatic hydrocarbon, (ii) alicyclic hydrocarbon, (iii) aromatic hydrocarbon, (iv) alkyl substituted aromatic hydrocarbon (v) heterocyclic groups and (vi) heterosubstituted derivatives of said groups (i) to (v), and R^c is as defined above.

Although R¹ and R² can form integral unit R⁴ it is preferred that they are separate groups. Preferably R¹ and R² are separate, identical groups. Preferably, R¹ and R² are separate, identical aliphatic hydrocarbon, alicyclic hydrocarbon, aromatic hydrocarbon or alkyl substituted aromatic hydrocarbon groups.

When n = 2, there are two phosphorus or arsenic-containing ligands on the transition metal M. Under these circumstances there are two separate R¹ groups ( R¹' and R¹ ) and two separate R² groups (R² and R² ). It is preferred that at least one of the pairs of these groups, R¹ and R¹ or R²' and R²" are linked. For example, R¹' and R^1" can be linked to form R⁵ as illustrated in Formula B below.

Formula B

The divalent group R⁵ is preferably selected from the divalent groups recited above for the divalent group R⁴. Thus a preferred feature of the present invention provides a novel transition metal catalyst system comprising

(1) a transition metal complex of Formula A wherein n = 2 and the R¹ groups on the two units

are linked to form R such that Formula A becomes Formula B below,

Formula B

and wherein the divalent group R⁵ is selected from the divalent groups -R^a- , -O-R^b- , -O-R^b'-O- , -N-(R^c)R^d'- , -N(R⁰)- , -N(R^C)-R^d'-N(R^C)- , -Si(R^c)₂-R^a'-Si(R^c)₂- , and -Si(R°)₂- ; the divalent groups R^a', R^b', and R^d' being independently selected from divalent (i) aliphatic hydrocarbon, (ii) alicyclic hydrocarbon, (iii) aromatic hydrocarbon, (iv) alkyl substituted aromatic hydrocarbon (v) heterocyclic groups and (vi) heterosubstituted derivatives of said groups (i) to (v), M being preferably a Group 3 to 11 transition metal, more preferably Group 5 to 7 transition metal and most preferably vanadium,

Examples of groups suitably used as the divalent group R⁵ are -CH₂-, -CH₂CH₂-, -CH₂CH₂CH₂-, tr<ms-l,2-cyclopentane, trans- 1,2-cyclohexane, 2,3-butane, I₅I'. biphenyl, l,l'-binaphthyl, -N(Me)-, -N(Et)-, l,l'-biρhenol and -Si(Me)₂-. The divalent group R³ is defined above as independently selected from (i) aliphatic hydrocarbon, (ii) alicyclic hydrocarbon, (iii) aromatic hydrocarbon, (iv) alkyl substituted aromatic hydrocarbon (v) heterocyclic groups and (vi) heterosubstituted derivatives of said groups (i) to (v);. It is preferred that R³ is an alkyl substituted or heterosubstituted aromatic hydrocarbon group. More preferably R³ is an alkyl substituted or heterosubstituted divalent 1,2-phenylene group. The 1,2-phenylene group preferably has the said alkyl substitutuent or hetero atom in the position ortho to the ring-carbon atom bonded to the oxygen atom in Formula A. The 1,2-phenylene group is optionally substituted in one of more of the other remaining positions of the 1,2- phenylene group. When any of the defined monovalent groups R^a, R^b, R^C, R^d, and R^e, and the divalent groups R^a', R^b , R^d', R³ _, R⁴, and R⁵ are heterocyclic, the atom or atoms present in the rings as the heteroatom can be, for example, oxygen, nitrogen, sulphur, phosphorus or silicon.

E is preferably phosphorus. M is a metal selected from Groups 3 to 11 of the Periodic table, more preferably selected from Groups 3 to 7. M is preferably titanium, vanadium or chromium. M is most preferably vanadium. For some purposes M is preferably a Group 5 to 7 transition metal for example a Group 3 to 6 transition metal.

The anionic group X can be, for example, a halide, preferably chloride or bromide; or a hydrocarbyl group, for example, methyl, benzyl or phenyl; a carboxylate, for example, acetate or acetylacetate; an oxide; an amide, for example diethyl amide; an alkoxide, for example, methoxide, ethoxide or phenoxide; an acetylacetonate; or a hydroxyl. Or, for example, X can be a non-coordinating or weakly-coordinating anion, for example, tetrafluoroborate, a fluorinated aryl borate or a triflate. The anionic groups X may be the same or different and may independently be monoanionic, dianionic or trianionic.

The neutral donor group L can be, for example, a solvate molecule, for example an ether, for example, diethyl ether or THF (tetrahydrofuran); an amine, for example, diethyl amine, trimethylamine or pyridine; a phosphine, for example trimethyl phosphine or triphenyl phosphine; an olefin; water; a conjugated or non-conjugated diene. The value of y in Formula A and B depends on the value of n, the charge on the anionic group X and the oxidation state of the metal M. For example, if M is titanium in oxidation state +4 and n is 2, then y is 2 if X is a monoanionic group (eg. chloride) or y is 1 if X is a dianionic group (eg. oxide); if M is titanium in oxidation state +4 and n is 1 , then y is 3 if all X groups are monoanionic groups (eg. chloride) or y is 2 if one X group is a dianionic group (eg. oxide) and the other is monoanionic. It is preferred that n is 2.

. The phrase "being insoluble in a hydrocarbon solvent" means that less than 2.0 wt%, preferably less than 1.0 wt% of the solid is soluble on boiling the solid in n- hexane at 1 bar pressure for 1 hour. Any soluble part present in the support can be removed, for example, by boiling the product in an inert solvent (eg a volatile hydrocarbon) and decanting or filtering the solid particulate product.

The hydrocarbyloxy groups present in the catalyst-activating hydrocarbon- insoluble support (2) can be, for example alkoxy, aryloxy, cycloalkoxy or substituted derivatives thereof, for example chloroalkoxy. Thus the C₁ to C₂₀ hydrocarbyloxy group in the carrier component can be for example methoxy, ethoxy, n-propoxy, i-propoxy, n- butoxy, sec-butoxy, t-butoxy or any other straight or branched chain alkoxy group containing 1 to 20 carbon atoms. Also suitable are, inter alia, benzoyloxy, phenylethoxy, phenoxy, ethylphenoxy, naphthoxy, and halogenated alkoxy derivatives and similar alkoxy compounds. The catalyst-activating hydrocarbon-insoluble support (2) present in the catalyst system of the present invention preferably contains a Mg/Al ratio in the range 1 to 300, more preferably 30 to 250 for example 30 to 200, most preferably 40 to 150. It has a molar ratio of hydrocarbyloxy to aluminium (OR/A1) in the range 0.05 to 2.0, more preferably 0.2 to 2.0, for example, 0.1 to 1.8 most preferably 0.2 to 1.0 The average particle size of the support is preferably 3 to 60 microns.

The support is preferably prepared by at least partially dissolving a magnesium halide, preferably magnesium dichloride, in an alcohol containing 1 to 20 carbons atoms and contacting the product with an organoaluminium compound having the formula AlRnX3-n wherein X is halogen or hydrogen and n is 1 to 3. Supports of this type are disclosed in WO 2004/037870 and for details of their preparation this disclosure provides useful information. The magnesium halide is preferably dissolved completely in the alcohol before reacting with the organoaluminium compound, heating or refluxing the mixture if necessary. Any undissolved magnesium halide is preferably separated before reacting the solution with the organoaluminium compound. The solution thus prepared by dissolving the magnesium halide in the alcohol can be directly reacted with the organoaluminium compound, or if desired, some or all of the residual alcohol can be removed, for example by evaporation techniques to leave a solid or semisolid product before reacting with the organoaluminium compound.

The reaction between the alcohol and the magnesium halide can be carried out in the presence of an inert diluent, eg a volatile liquid hydrocarbon, if desired. The reaction is preferably carried out with heating, eg at 50 to 15O⁰C and with agitation, eg stirring. The product of reacting the alcohol and the magnesium halide can be a solution, a slurry or a solid. Preferably the product is a solution in the alcohol or in a hydrocarbon diluent. Examples of alcohols that can be employed to make the catalyst-activating hydrocarbon- insoluble support are RlOH wherein Rl is aliphatic, alicyclic or aralkyl, for example, methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, tert butyl, n-pentyl, n-hexyl, n-octyl, n-decyl, cyclohexyl, ethylcyclohexyl and benzyl

Examples of organoaluminium compounds that can be employed to make the catalyst-activating hydrocarbon-insoluble support are R3A1, R2A1X and RA1X2 wherein R is preferably Cl to C20 hydrocarbyl, and X is chlorine or bromine, preferably chlorine. R is preferably selected from methyl, ethyl, propyl, isopropyl, n-butyl, sec- butyl, tert butyl, n-pentyl, n-hexyl, n-octyl and n-decyl.

Reacting the solid or preferably the solution with the organoaluminium compound using quantities having the afore-recited Mg/ Al ratios produces a solid having the desired chemical characteristics. The organoaluminium compound is preferably employed as a solution in a hydrocarbon solvent, for example, hexane, decane, xylene or toluene. The reaction is preferably performed by adding a solution of the organoaluminium compound to the product of reacting the magnesium halide with the alcohol. The reaction is preferably carried out with stirring. The reaction is generally exothermic and thus cooling can be employed if desired. The reaction can be carried out over a period of time for example from 5 minutes to 5 hours. The mole ration of aluminium to magnesium employed in this reaction is suitably 0.1 to 50, preferably 0.5 to 30, more preferably 1 to 20, and most preferably 2 to 10. The shape and size of the particles formed in the solid product are variable depending on the conditions used in their formation. To obtain particles of regular shape and uniform size it is desirable to use conditions that favour controlled and relatively slow/mild reaction and slow temperature change. Such conditions can involve, for example continuous or gradual addition of a solution of the organoaluminium compound to a solution of the magnesium halide/alcohol reaction product. Using such conditions it is generally relatively easy to obtain a product having narrow particle size distribution and of generally regular spherical or granular shape. The particle size of the product can be adjusted if desired by conventional methods, for examples, milling, sieving, pressing and the like. The catalyst-activating hydrocarbon-insoluble support and its preparation are suitably protected to exclude air and moisture. Preferably the preparation and storage are in an inert gas atmosphere.

The optional additional activator compound (3) employed in the catalyst system of the present invention is suitably selected from organoaluminium compounds and organoboron compounds. Suitable organoaluminium compounds include trialky- or triaryl-aluminium compounds, for example, trimethylaluminium, triethylaluminium, tributylaluminium, tri-n-octylaluminium, ethylaluminium dichloride, diethylaluminium chloride, methylaluminium dichloride, dimethylaluminium chloride, tris(pentafluorophenyl)aluminium and alumoxanes. Alumoxanes 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 alumoxanes are generally believed to be mixtures of linear, cyclic and cage compounds. The cyclic alumoxanes can be represented by the formula [R¹⁶AlO] _s and the linear alumoxanes by the formula R¹⁷(R¹⁸A1O)_S wherein s is a number from about 2 to 50, and wherein R¹⁶, R¹⁷, and R¹⁸ represent hydrocarbyl groups, preferably C₁ to C₆ alkyl groups, for example methyl, ethyl or butyl groups.

Examples of suitable organoboron compounds are diniethylphenylammoniumtetra(ρlienyl)borate, trityltetra(phenyl)borate, triphenylboron, dimethylphenylammonium tetra(pentafluorophenyl)borate, sodium tetrakis[(bis-3,5-trifluoromethyl)phenyl]borate, H⁺(OEt₂)[(bis-3₅5- trifluoromethyl)phenyl]borate₅ trityltetra(pentafluoroplienyl)borate and tris(pentafluorophenyl) boron. Mixtures of organoaluminium compounds and organoboron compounds may be used.

In the preparation of the catalysts of the present invention the quantity of activating compound selected from organoaluminium compounds and organoboron compounds 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 0.1 to 20,000 atoms, preferably 1 to 2000 atoms of aluminium or boron per atom of M present in the compound of Formula A or B. In addition to the catalyst-activating hydrocarbon-insoluble support and the optional activator compound, it can be advantageous to employ catalytic quantities of certain halogenated compounds that are capable of promoting catalyst activity. Promotors of this type are especially useful in the case that the transition metal in the complex is vanadium. US Patent.5191042 discloses that certain vanadium-based catalysts activated with organoaluminium compounds can be promoted using a variety of halogenated organic compounds, for example, carbon tetrachloride, hexachloroethylene, benzylbromide, benzylchloride and 2,3- or 1,3-dichloropropylene. Other examples of halogenated organic compounds that can be used in this manner are ethyl trichloroacetate, chloroform (CHCl₃) and n-butylchloride. US Patent.5191042 also refers to the disclosure of Cooper (T. A Cooper, Journ. Am. Chem. Soc, 4158 (1973), which defines in Table 1 an organic halide activity index based on the ability of the halide to oxidize certain vanadium compounds under standard conditions. For example, carbon tetrachloride is assigned a reactivity of 1 in tetrahydrofuran at 20 °C, and other listed halogenated organic compounds have reactivities of from about 0.02 to greater than 200 relative to carbon tetrachloride. When it is desired to use a halogenated promoter, it is preferred to use those having a Cooper Index ranging from about 0.01 up to about 30. The use of such promoters, especially in combination with vanadium-based catalysts is generally well known in the art, and for details of use of the such promoters reference may be made to US Patent.5191042 and to other prior art in this field. In the present invention it is possible to employ any halogenated organic compound as a promoter, but the compounds mentioned above are preferred.

The catalyst of the present invention can, if desired, be utilised on an additional support material, for example, silica, alumina, or zirconia, magnesia, magnesium chloride or a polymer or prepolymer, for example polyethylene, polystyrene, or poly(aminostyrene).

The following are examples of transition metal complexes that can be employed in the catalyst system of the present invention. In these complexes "VGp" represents a moiety selected from >VC1, >V=O(C1) and >V=O(OR^f ), wherein R^f is suitably a hydrocarbyl group, preferably an alkyl group containing 1 to 20 carbons atoms, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl:

Particularly preferred complex compounds for use in the catalysts system are those having the formulae

The group "R^f" is suitably an alkyl group, preferably an alkyl group containing 1 to 20 carbons atoms, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl. The catalyst system of the present invention can if desired comprise more than one of the defined transition metal compounds.

In addition to said one or more defined transition metal compounds, the catalyst system employed in the process of the present invention can also include one or more other catalysts for polymerising 1 -olefins. Examples of suitable types of catalysts are transition metal catalysts, for example, transition metal compounds of the type used in conventional Ziegler-Natta catalyst systems, metallocene-based catalysts, so-called "non-metallocene" or "post metallocene" catalysts, for example phenoxyimine or pyridyl-bisimine complexes of transition metals, especially late transition metals, and heat activated supported chromium oxide catalysts (e.g. Phillips-type catalyst). The catalyst or catalyst system of the present invention can also used in conjunction with other catalysts producing only 1 -olefins, either inside or outside the polymerisation reactor, and in this way make copolymers of ethylene or propylene and these 1 -olefins. Suitable catalysts for producing 1 -olefins may produce only 1-butene, only 1-hexene or a distribution (for example, a Schulz-Flory distribution) of 1 -olefins. If desired the catalysts can be formed in situ in the presence of the defined hydrocarbon-insoluble catalyst-activating support (2) or the said support material can be pre-impregnated or premixed, simultaneously or sequentially, with one or more of the catalyst components.

The quantity of the defined hydrocarbon-insoluble catalyst-activating support material employed can vary widely, for example from 100,000 to 1 grams per gram of metal present in the transition metal compound.

The present invention further provides a process for the polymerisation and copolymerisation of 1 -olefins, cycloolefins or dienes comprising contacting the monomeric olefin under polymerisation conditions with the catalyst system system of the present invention. Suitable monomers for use in making homopolymers using the polymerisation process of the of the present invention are, for example, ethylene, propylene, butene, hexene, and styrene. Preferred monomers are ethylene and propylene.

Suitable monomers for use in making copolymers using the polymerisation process of the present invention are ethylene, propylene, 1 -butene, 1 -hexene, 4- methylpentene-1, 1-octene, methyl methacrylate, methyl acrylate, butyl acrylate, acrylonitrile, vinyl acetate, vinyl chloride, styrene and dienes, such as butadiene or hexadiene and cycloolefms, such as norbornene.

A particularly preferred process in accordance with the present invention is the copolymerisation of ethylene and or propylene with comonomers selected from 1 - olefins, acrylic acid esters, vinyl esters and vinyl aromatic compounds. Examples of suitable comonomers are 1 -butene, 1 -hexene, 4-methylpentene-l, methyl methacrylate, methyl acrylate, butyl acrylate, acrylonitrile, vinyl acetate, and styrene.

Preferred polymerisation processes are the homopolymerisation of ethylene or the homopolymerisation of propylene or copolymerisation of ethylene with one or more of propylene, butene, hexane-1 and 4-methylpentene-l.

Also preferred is a process for the copolymerisation of ethylene and or propylene with comonomers selected from 1 -butene, 1 -hexene, 4-methylpentene-l, methyl methacrylate, methyl acrylate, butyl acrylate, acrylonitrile, vinyl acetate, and styrene, diene, cyclic olefin, norbornene and substituted norbornene.

The polymerisation conditions can be, for example, bulk phase, 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 fiuidised or stirred bed conditions.

Slurry phase polymerisation conditions or gas phase polymerisation conditions are particularly useful for the production of high-density grades of polyethylene. In these processes the polymerisation conditions can be batch, continuous or semi- continuous, hi the slurry phase process and the gas phase process, the catalyst is generally fed to the polymerisation zone in the form of a particulate solid. This solid can be, for example, an undiluted solid catalyst system formed from the complex of Formula A or B and an activator, or can be the solid complex alone, hi the latter situation, the activator can be fed to the polymerisation zone, for example as a solution, separately from or together with the solid complex. Preferably the catalyst system or the transition metal complex component of the catalyst system employed in the slurry polymerisation and gas phase polymerisation is supported on a support material. Most preferably the catalyst system is supported on a support material prior to its introduction into the polymerisation zone. Suitable support materials are, for example, magnesium chloride, silica, alumina, zirconia, talc, kieselguhr, or magnesia. Impregnation of the support material can be carried out by conventional techniques, for example, by forming . a solution or suspension of the catalyst components in a suitable diluent or solvent, and slurrying the support material therewith. The support material thus impregnated with catalyst can then be separated from the diluent for example, by filtration or evaporation techniques.

In the slurry phase polymerisation process the solid particles of catalyst, or supported catalyst, are fed to a polymerisation zone either as dry powder or as a slurry in the polymerisation diluent. Preferably the particles are fed to a polymerisation zone as a suspension in the polymerisation diluent. The polymerisation zone can be, for example, an autoclave or similar reaction vessel, or a continuous loop reactor, eg of the type well know in the manufacture of polyethylene by the Phillips Process. When the polymerisation process of the present invention is carried out under slurry conditions the polymerisation is preferably carried^'out at a temperature above 0°C, most preferably above 15⁰C. The polymerisation temperature is preferably maintained below the temperature at which the polymer commences to soften or sinter in the presence of the polymerisation diluent. If the temperature is allowed to go above the latter temperature, fouling of the reactor can occur. Adjustment of the polymerisation within these defined temperature ranges can provide a useful means of controlling the average molecular weight of the produced polymer. A further useful means of controlling the molecular weight is to conduct the polymerisation in the presence of hydrogen gas which acts as chain transfer agent. Generally, the higher the concentration of hydrogen employed, the lower the average molecular weight of the produced polymer. The use of hydrogen gas as a means of controlling the average molecular weight of the polymer or copolymer applies generally to the polymerisation process of the present invention. For example, hydrogen can be used to reduce the average molecular weight of polymers or copolymers prepared using gas phase, slurry phase or solution phase polymerisation conditions. The quantity of hydrogen gas to be employed to give the desired average molecular weight can be determined by simple "trial and error" polymerisation tests. Methods for operating gas phase polymerisation processes are well known in the art. Such methods generally involve agitating (e.g. by stirring, vibrating or fmidising) a bed of catalyst, or a bed of the target polymer (i.e. polymer having the same or similar physical properties to that which it is desired to make in the polymerisation process) containing a catalyst, and feeding thereto a stream of monomer at least partially in the gaseous phase, under conditions such that at least part of the monomer polymerises in contact with the catalyst in the bed. The bed is generally cooled by the addition of cool gas (e.g. recycled gaseous monomer) and/όr volatile liquid (e.g. a volatile inert hydrocarbon, or gaseous monomer which has been condensed to form a liquid). The polymer produced in, and isolated from, gas phase processes forms directly a solid in the polymerisation zone and is free from, or substantially free from liquid. As is well known to those skilled in the art, if any liquid is allowed to enter the polymerisation zone of a gas phase polymerisation process the quantity of liquid is small in relation to the quantity of polymer present in the polymerisation zone. This is in contrast to "solution phase" processes wherein the polymer is formed dissolved in a solvent, and "slurry phase" processes wherein the polymer forms as a suspension in a liquid diluent.

The gas phase process can be operated under batch, semi-batch, or so-called "continuous" conditions. It is preferred to operate under conditions such that monomer is continuously recycled to an agitated polymerisation zone containing polymerisation catalyst, make-up monomer being provided to replace polymerised monomer, and continuously or intermittently withdrawing produced polymer from the polymerisation zone at a rate comparable to the rate of formation of the polymer, fresh catalyst being added to the polymerisation zone to replace the catalyst withdrawn form the polymerisation zone with the produced polymer.

In the polymerisation process of the present invention the process conditions are preferably gas phase fluidised or stirred bed polymerisation conditions.

A problem that can occur in the gas and slurry phase polymerisation of olefins is that of fouling of the reactor walls, any stirrer that may be present and spalling or agglomeration of the polymer due, for example, to the presence of static electricity. The problem can be reduced or eliminated by judicious use of suitable antistatic agents. One example of a family of antistatic agents suitable for use in the polymerisation of olefins are commercially available under the trade name "STADIS". When using the catalysts of the present invention under gas phase polymerisation conditions, the catalyst, or one or more of the components employed to form the catalyst can, for example, be introduced into the polymerisation reaction zone in liquid form, for example, as a solution in an inert liquid diluent. Thus, for example, the transition metal component, or the activator component, or both of these components can be dissolved or slurried in a liquid diluent and fed to the polymerisation zone. Under these circumstances it is preferred the liquid containing the component(s) is sprayed as fine droplets into the polymerisation zone. The droplet diameter is preferably within the range 1 to 1000 microns. EP-A-0593083, the teaching of which is hereby incorporated into this specification, discloses a process for introducing a polymerisation catalyst into a gas phase polymerisation. The methods disclosed in EP- A-0593083 can be suitably employed in the polymerisation process of the present invention if desired.

The catalyst or catalysts of the present invention can be employed, if desired, using processes analogous to those disclosed in WO02/46246 and US6605675. For example, a catalyst component slurry and a catalyst component solution can be combined before or during introduction into the polymerisation reactor. The properties of polymers produced using such methods can be advantageously controlled thereby. The catalysts of the present invention can also be employed in the process disclosed in US6610799. hi this process, mixtures of two or more supported catalysts can be utilised containing differing amounts of catalyst components wherein the concentrations of the individual catalyst components can be independently controlled within the polymerisation reactor.

The catalyst of the present invention can be used in conventional commercial polymerisation facilities and its use can be sandwiched between production runs using other commercial catalyst systems of the supported or unsupported type, eg, using

Ziegler Natta catalysts, metallocene catalysts, heat activated chromium oxide catalysts and late transition metal catalyst systems. Transitioning between catalyst systems of these types

The invention is illustrated in the following Examples.

Example 1.1 Synthesis of 2-Methoxymethoxy-3-tert-butylphenyl lithmm.nEfrO (n = 0.5-1.01.

"Compound 1"

To an ether solution (150 ml) of l-tert-butyl-2-methoxymethoxybenzene (23.4 g,

120 mmol) cooled to O⁰C was added n-butyllithiurn (2.5 M in hexanes, 48 ml, 120 mmol). The mixture was stirred overnight at room temperature giving a yellow solution and colourless precipitate. All volatiles were removed under vacuum. The crude product was triturated with pentane (50 ml) for 3 h and then filtered. The product was washed with pentane (2 x 10 ml) and dried under vacuum to give "compound 1" as a colourless powder (22.1 g, 80.5 mmol, 67 % yield) . The value of "n" was determined by IH

NMR. Analysis:

¹H NMR (250 MHz, CDCl₃): δ 7.92 (d, ³J_HH = 5.0 Hz₅ IH, Ar-H)₅ 7.35 (d, ³J_HH = 7.5

Hz, IH, Ar-H), 7.25-7.18 (m, 1Η, Ar-H)₅ 5.33 (s, 2H₅ OCH₂O)₅ 2.97 (q, ³J_ΗΗ = 7.0 Hz,

4nH, OCH₂CH₃), 2.80 (s, 3H₅ OCH₃), 1.60 (s, 9Η, C(CH₃)₃), 0.82 (t, ³JΗΗ = 7.0 Hz,

6nH, OCH₂CH₃).

Example 1.2

Synthesis of N,N-diisopropyl-P-phenvI phosphonamidoiis chloride, "Compound 2" To a solution of dichlorophenylphosphine (33.9 ml, 250 mmol) in dry toluene

(600 ml) was added diisopropylamine (70.8 ml, 505 mmol). The resultant slurry was stirred for 15 h and then filtered over Celite. AU volatiles were removed under vacuum to give "Compound 2" as a yellow oil which partially crystallised over time (59.1 g, 243 mmol, 97 % yield).

Amalysis

¹HNMR (250 MHz₅ CDCl₃): δ 7.82-7.75 (m, 2H, Ar-H), 7.17-7.02 (m, 3Η, Ar-H), 3.24 (br s₅ 2Η, NCH(CH₃)₂)₅ 2.00-0.55 (br m₅ 12H₅ NCH(CH₃)₂). ³¹P NMR (101 MHz₅

CDCl₃): δ 131.9.

Example 1.3 Synthesis of (2-Methoxymethoxy-3-terf-butyl-phenyl)phenylphosphine oxide, "Compound 3"

To a solution of "Compound 2" (92.6 g, 380 mmol) in ether (500 ml) cooled to 78⁰C was added a slurry of "Compound 1" (89.0 g, 371 mmol) in ether (300 ml). The mixture was allowed to warm to room temperature and then stirred for 1 h. Water (800 ml) was added followed by 2 M HCl (100 ml) and the mixture stirred for 2 h. The reaction was monitored by in situ ³¹P NMR with further portions of 2M HCl (50 ml) added every 1 h until the signal at 32.0 ppm was not observed. The organic phase was separated, washed with water (2 x 300 ml), dried (Na₂SO₄), and the solvent removed giving "Compound 3" as a pale yellow oil (112 g, 352 mmol, 95 % yield). If necessary the product could be further purified by column chromatography (silica gel, ether (R_f = 0.29}).

"Compound 3"

Analysis

Calculated, for C₁₈H₂₃O₃P: C, 67.91; H₅ 7.28; Found: C, 67.83; H, 7.39.

¹HNMR (400 MHz, CDCl₃): δ 8.22 (d, ¹JHP = 499 Hz, IH, PH), 7.70-7.57 (m, 3H,

Hz, J = 2.4 Hz, IH, H(_Sj), 5.28-5.23 (m, 2H, OCH₂O)₅ 3.53 (s, 3H, OCH₃), 1.41 (s, 9Η, C(CH₃)₃). ¹³C(¹H) NMR (101 MHz₅ CDCl₃): δ 158.1 (Ar-Cf₂)), 144.5 (d, ³J_CP = 5.4 Hz, Ar-Qy), 132.9 (Ar-Q₄;), 132.1 (Ar-Cp;), 131.7 (d, ²J_CP = 10.2 Hz, Ar-Q₉), 131.5 (d, ¹Jc_? = 103 Hz, Ax-C_(A)), 131.7 (d, ²J_CP = 10.9 Hz, Ar-Q₇;), 128.5 (d, ³J_CP = 13.3 Hz, Ar-Q₅;), 127.3 (d, ¹JcF = 99.3 Hz₅ Ar-Q₇;), 124.4 (d, ³J_CP = 13.6 Hz, Ar-Q₅;), 102.4 (OCH₂O), 57.7 (OCH₃), 35.3 (C(CHs)₃), 30.9 (C(CHa)₃). ³¹P(¹H) NMR (101 MHz, CDCl₃): δ 17.9 (s).

³¹P NMR (101 MHz, CDCl₃): δ 17.9 (dm, ¹Jp_n = 499 Hz).

MS (CI; m/z): 637 [2M + H]⁺, 319 [M + H]⁺.

IR(NaCl;cm^"1):3057w,2959s,2910m,2872m,^'283Ow,2330brm(P-H), 1572m,

1483m, 1464m,1438s,1427m,1391s, 1362w, 1269w, 1233m, 1196s, 1164s(P=O),

1127s, 1110w, 1077s,948s,924s,793m,745s,707m,693s.

Example1.4

Synthesis of l,2-Ethanediylbis[(2-methoxymethoxy-3-te^-butyl-phenyllphenyl- phosphine oxide, "Compound 4"

To a solution of "Compound 3" (25.01 g, 70.7 mmol) cooled to -78⁰C was added n-butyllithium (2.5 M in hexanes; 27.7 ml, 69.3 mmol) dropwise. The solution was stirred for 30 min at -78⁰C and then at room temperature for 2 h. The solution was cooled to O⁰C and a slurry of ethylene glycol di-p-tosylate (12.57 g, 34.0 mmol) in tetrahydrofuran added. The mixture was stirred at room temperature for 1 h and then at 5O⁰C for 2 h. After cooling the solvent was removed under vacuum and the residue dissolved in dichloromethane (250 ml) and water (250 ml). The layers were separated and the aqueous fraction extracted with dichloromethane (3 x 100 ml). The combined organic fractions were washed with water (3 x 100 ml), dried (Na₂SO₄), filtered and the solvent removed. The crude product was recrystallised from hot hexane and dried under vacuum to give "Compound 4" as a colourless solid (12.62 g, 19.0 mmol, 54 % yield) [If the product was found to contain ethylene glycol di-p-tosylate it could be removed by extraction with ether, followed by ethanol].

"Compound 4"

Analysis

Calculated for C₃₈H₄₈O₆P₂: C₅ 68.87; H, 7.30; Found: C₅ 68.92; H, 7.39. ¹HNMR (400 MHz₅ CDCl₃): δ 7.68-7.60 (br m, 4H₅ Ar-H)₅ 7.55-7.40 (br m, 16H₅ Ar- H), 7.40-7.32 (br m, 4H₅ Ar-H)₅ 7.08-6.95 (br m₅ 2Η + 2Η + 4H₅ Ar-H)₅ 5.26 (dd, ²JΗ_P = 88.2 Hz₅ ⁴JHH = 4.1 Hz₅ 4H₅ rac-OCH₂O), 5.16 (dd, ²J_ΗP = 87.7 Hz₅ ⁴J_HH = 4.1 Hz₅ 4H₅ 7WeSO-OCH₂O)₅ 3.43 (s, 6Η, rαc-OCH₃), 3.23 (s, 6H₅ meso-QCHi), 3.10-2.91 (m, 2H₅ rac-PCH₂), 2.60-2.37 (m, 4Η, meso-PCH₂), 2.08-1.95 (m, 2H₅ rac-?CH₂), 1.35 (s, 18H, røe-C(CH₃)₃), 1.32 (s, 18H₅ meso-C(CH₃)₃). ¹³C(¹H) NMR (101 MHz₅ CDCl₃): δ 158.6 (d, ²J_Cp = 10.7 Hz₅ rac + rneso Ar-Q₂;), 145.2-145.1 (m, rac + meso Ar-Cp;), 132.7 (rac/meso Ar-C^;), 132.6 (meso/rac Ar- Cf₄)), 131.8 (rac/meso Ar-Cp;), 131.7 (meso/rac Ar-Qr,;), 131.7 (d, ¹J₀P = 157 Hz₅ rac/meso Ax-CfA)), 131.4 (d, ¹Jc? - 157 Hz₅ meso/rac Ax-C(AJ), 131.4-131.0 (m, rac + meso Ar-Q^;, rac + meso Ar-Qg;), 128.5-128.3 (m, rac + meso Ar-Qc;), 127.9 (d, ¹Jc_P = 49.8 Hz₅ rac/meso Ar-Qi;), 127.6 (d, ¹J_0P = 49.2 Hz, meso/rac Ar-Q;;), 123.9-123.7 (m, rac + meso Aτ-C₍₅j), 102.5 (rac-OCH₂O), 102.4 (meso-OCH₂O), 57.7 (rac- OCH₃), 57.4 (meso-OCHi), 35.4 (rac/meso-C(CU₃)₃), 35.4 (meso/rac-C(CH₃)₃), 30.9 (røc-C(CH₃)₃)₅ 30.8 (meso-C(CH₃)₃), 23.4-21.8 (m, rac + meso PCH₂).

³¹P(¹H) NMR (162 MHz₅ CDCl₃): δ 35.7 (s, meso), 35.4 (s, rac).

IR(KBr;cm¹):3063w₅299Om₅296Is₅2906m,2868m₅2827w₅1571w, 1484w₅146Iw₅ 1449w, 1435m, 1423m, 1412m, 1386s, 1364w, 1269w, 1232m, 1193s, 1177s(P=O), 1152s, 1123s, 1084s,943m,915s,835w,789m,764m,742s,714m,700m,689m,599w, 566w,549m,518s,484w₅466w.

Example1.5

Synthesis of 2,2'-π,2-EthanediyIbis(phenyIphosphinvIidene)lbis(6-fer/- biityPphenoL, "Compound 5"

"Compound 4" (10.53 g, 15.9 mmol) was dissolved in 9:1 AcOH:H₂O and heated to reflux for 2.5 h. After cooling, ethyl acetate (200 ml) and H₂O (200 ml) was added. The suspension was filtered giving a fraction of meso-"Corapound 5". The aqueous fraction of the filtrate was separated and extracted with ethyl acetate (3 x 50 ml). The combined organic fractions were washed with H₂O (75 ml), aqueous NH₃ (2 x 75 ml), H₂O (2 x 75 ml), dried (Na₂SO₄), filtered and the solvent removed under vacuum. The colourless precipitate was triturated with hot hexane and filtered to give a sample of rac enriched "Compound 5". The two portions of "Compound 5" were combined (8.14 g, 15.6 mmol, 98 % yield).

Analalysis. Calculated for C₃₄H₄₀O₄P₂: C, 71.07; H, 7.02; Found: C, 71.08; H, 6.97.

Compound 5

¹HNMR (500 MHz, CDCl₃): δ 11.29 + 11.28 (2 x s, 2H, OH), 7.77-7.72 (m, 4H, Ax-H), 7.55 (t, ³J_HH = 7.2 Hz, 2H, Ar-H), 7.52-7.46 (m, 4H, Ai-H), 7.42-7.37 (m, 2H, Ar-H),

6.91-6.82 (m, 2H, Ar-H), 6.80-6.74 (m, 2H, Ar-H), 2.68-2.49 (m, 4H, CH₂), 1.40 + 1.39

(2 x s, 9H, C(C#₃)₃).

³¹P(¹H) NMR (202 MHz, CDCl₃): δ 46.8 (s, mesό), 46.7 (s, rac).

MS (FAB; m/z): 575 [M]⁺, 301 [M-P(Ph)(O)(('Bu)C₆H₃OH)]⁺. IR (KBr; cm^"1): 3063w, 2990m, 2961s, 2906m, 2868m, 2827w, 1571w, 1484w, 1461w,

1449w, 1435m, 1423m, 1412m, 1386s, 1364w, 1269w, 1232m, 1193s, 1177s (P=O),

1152s, 1123s, 1084s, 943m, 915s, 835w, 789m, 764m, 742s, 714m, 700m, 689m, 599w,

566w, 549m, 518s, 484w, 466w.

Example 1.6 Synthesis of 2,2Ml,2-ethanedivIbis(phenvIphosphinidene)Ibis(6-fer^butyr)phenoI,

"Compound 6"

All solvents during the work-up were thoroughly degassed. Concentrated H₂SO₄

(0.82 ml, 15.5 mmol) was slowly added dropwise to a slurry OfLiAlH₄ (1.18 g, 31.0 mmol) in thf (50 ml) at O⁰C. The suspension was then stirred for 15 h, allowed to settle, and filtered to generate a thf solution Of AlH₃. This was then added to a thf (tetrahydrofuran) (10 ml) solution of "Compound 5" (1.78 g, 3.1 mmol) at O⁰C. The mixture was then heated to 60⁰C for 2 h. After cooling the reaction was deactivated by slow addition of water, followed by AcOH. The mixture was extracted with ethyl acetate (5 x 50 ml). The combined organic fractions were washed with water (3 x 50 ml), dried (Na₂SO₄), filtered, and the solvent removed to give a diastereotopic mix'of "Compound 6". The mixture of products was triturated in methanol (25 ml) and then filtered to give insoluble meso-"Compound 6" as a colourless powder (0.739 g, 1.36 mmol, 44 % yield).

"Compound 6"

Analysis. Calculated for C₃₄H₄₀O₂P₂: C, 75.26; H, 7.43. Found: C, 75.33; H, 7.34.

¹H NMR (400 MHz, CDCl₃): δ 7.32-7.29 (m, 12H₅ Ar-H_(3tB,c,D))- 7.16 (pt, J = 5.9 Hz, 2H, OH), 6.98-6.94 (m, 2H, Ar-H^)₅ 6.82 (pt, J = 7.6 Hz, 2H, Ai-Hf₄)), 2.22-2.08 (m, 4H, PCH₂), 1.42 (s, 18H, C(CH₃)₃).

¹³C(¹H) NMR (101 MHz, CDCl₃): δ 158.7 (pt, J = 10.3 Hz, Ar-Q₇;), 136.5 (Ar-Q₂^;), 136.0 (Ar-Cf_2ZAj), 131.8 (pt, J = 8.6 Hz, Ar-Q₅;), 130.3 (Ar-Qj,), 129.0 (Ar-Q₅;), 128.6 (d, ³J_HH = 3.9 Hz₅ Ar-Qg)₅ 128.6 (Ar-Q₁,;), 120.9 (Ar-Q₅;), 120.4 (Ar-Q,;), 34.9 (C(CHa)₃), 29.5 (C(CH₃)₃)₅ 22.8 (PCH₂). ³¹P(¹H) NMR (101 MHz₅ CDCl₃): δ -43.47.

MS (FAB; m/z): 543 [M] ⁺, 285 [M - F(PhX(¹Bu)C₆H₃OK)Y. IR (KBr; cm^"1): 3393br (OH), 3073w, 305Ow, 2996w, 2957m, 2906m, 2869m, 1586m, 1578m, 1570m, 1483m, 1433s, 1423s, 1418s, 1390s, 1364m, 1358m, 1329s, 1304w, 1273m, 1229s, 1198s, 1188s, 1164m, 1150m, 1114m, 1093m, 1082m, 1026w, 999w, 862w, 821m, 786m, 751s, 746s, 739s, 707m, 691s, 587w, 569m, 525w, 514m, 493m, 446m.

The solvent was removed from the methanol filtrate to give rac-6 as a colourless powder (0.528 g, 0.97 mmol, 32 % yield).

Anal. Calcd for C₃₄H₄₀O₂P₂: C, 75.26; H, 7.43. Found: C, 75.39; H, 7.51.

¹H NMR (400 MHz, CDCl₃): δ 7.32-7.29 (m, 12H, Av-H_mc,_Dj). 7.18 (pt, J = 5.9 Hz,

2H, OH), 6.94-6.91 (m, 2H, Ar-ifø), 6.82 (pt, J = 7.6 Hz, 2H, te-H₍₄₎), 2.21-2.04 (m,

4H, PCH₂), 1.41 (s, 18H, C(CH₃)₃). ¹³C(¹H) NMR (101 MHz, CDCl₃): δ 158.9 (pt, J = 10.4 Hz, Ar-Q;;), 136.5 (Ar-Q₂₇₄)),

136.2 (Ar-Q₂^;), 131.7 (pt, J = 8.5 Hz, Ar-Q₃;), 130.3 (Ar-Q₃;), 129.0 (Ar-Q₅;), 128.6

(Ar-Qc; + Ar-Q₁,;), 120.4 (Ar-Q₄;), 120.2 (Ar-Q₆;), 34.9 (C(CHa)₃), 29.5 (C(CHa)₃),

22.6 (PCH₂).

³¹P(¹H) NMR (101 MHz, CDCl₃): δ -43.29

MS (FAB; m/z): 543 [M] ⁺, 285 [M - P(Ph)(OBu)C₆H₃OH)I⁺.

IR (KBr; cm^"1): 3398br (OH)₅ 3070w, 3049w, 3002w, 2956m, 291Ow, 2868w, 1576m, 1570m, 1481w, 1436m, 1434m, 1419s, 1408s, 1390m, 1363w, 1358w, 1305w, 1267m, 1226m, 1196s, 1189s, 1173m, 1150m, 1141m, 1114m, 1093m, 1076m, 1025w, 100Ow, 858w, 818w, 784w, 747s, 741s, 693s, 566w, 491m, 442m. Example 1.7

Synthesis of frflc-2,2'-fl,2-Ethanediylbis(phenylphosphinidene)lbis(6-fe^- butvDphenoxidel vanadiumfSQ oxypropoxide, "Compound 8" To a solution of vanadium(V) oxytripropoxide (50.5 mg, 0.206 mmol) in toluene

(10 ml) cooled to O⁰C was added a solution of rac-"Comρound 6" (110 mg, 0.203 mmol) in toluene (20 ml) dropwise giving immediate formation of a deep red solution. The mixture was stirred at room temperature for 2 h and the solvent then removed under vacuum. The residue was washed with pentane (10 ml) and dried under vacuum to give "Compound 8" as a deep purple solid (88.3 mg, 0.132 mmol, 65 % yield). Analysis

¹H NMR (250 MHz, CDCl₃): δ 7.81-7.74 (m, 2H, Av-H), 7.60-7 AS (m, 2H, Ar-H),

7.40-7.27 (m, 8H, Ar-H), 7.02-6.90 (m, 2H, Ar-H), 6.79-6.71 (m, 2H, Ar-H), 5.49-5.38

(m, IH, OCH₂), 5.29-5.19 (m, IH, OCH₂CH₂), 2.81-2.28 (m, 2H, PCH₂), 2.09-1.96 (m.

1Η, PCH₂), 1.82- 1.71 (m, 3Η, PCH₂ + OCH₂CH₂), 1.39 (s, 9Η, C(CHj)₃), 1.32 (s, 9Η, C(CHs)₃), 0.89 (t, ³JΗΗ = 7.3 Hz, 3H, CH₂CH₃).

Example 1.8 - Ethylene polymerisation with "Compound 8" supported on the catalyst system of the present invention.

A IM Solution OfMgCl₂ /2-ethylhexanol adduct in decane ("Solution 1") was prepared by refluxing of 9.5 g anhydrous MgCl₂ in a mixture of 45 ml 2-ethylhexanol and 45 ml decane for 2 hours under nitrogen atmosphere. To a toluene solution of

MgCl₂ /(2-ethyl-hexan-l-ol)₃ (800 μmol) was added trimethylaluminium (2.4 mmol) at

60°C and stirred for 5 min. Dimethylaluminium chloride (1.0 mmol) was then added followed by l.Oμmol of "Compound 8"

Polymerisation Conditions: Catalyst loading = 1.0 μmol

Ethylene pressure = 1.3 bar

Cocatalyst = DMAC 1.0 mmol (2.0mmol total) + ethyltrichloroacetate (1.0 mmol)

Temperature = 60 ⁰C Time = 20 min

Results:

Polymer yield = 4.77 g

Activity = 11,007 g/mmol.h.bar

Claims

Claims:

1. A catalyst system comprising

(1) transition metal complex having the following Formula A:

Formula A

wherein the monovalent groups R¹ and R² are independently selected from -R^a, -OR^b,

-NR^cR^d, and -NHR^e: the monovalent groups R^a, R^b, R^c, R^d, and R^e, and the divalent group R³ are independently selected from (i) aliphatic hydrocarbon, (ii) alicyclic hydrocarbon, (iii) aromatic hydrocarbon, (iv) alkyl substituted aromatic hydrocarbon (v) heterocyclic groups and (vi) lieterosubstituted derivatives of said groups (i) to (v); M is a metal from Group 3 to 11 of the Periodic Table or a lanthanide metal; E is phosphorus or arsenic; X is an anionic group, L is a neutral donor group; y and z are independently zero or integers such that the number of X and L' groups satisfy the valency and oxidation state of the metal M, and with the proviso that

(A) when M is vanadium, n = 1 or 2 and

(B) when M is not vanadium n = 2 and the R¹ groups on the two units

are linked to form R⁵ such that Formula A becomes Formula B.

Formula B

and wherein the divalent group R⁵ is selected from the divalent groups -R^a - , -O-R^b - , -O-R^b'-O- , -N-(R^c)R^d'- , -N(R^C)- , -N(R^C)-R^d'-N(R^C)- , -Si(R^c)₂-R^a'-Si(R^c)₂- , and -Si(R°)₂- ; the divalent groups R^a', R^b', and R^d' being independently selected from divalent (i) aliphatic hydrocarbon, (ii) alicyclic hydrocarbon, (iii) aromatic hydrocarbon, (iv) alkyl substituted aromatic hydrocarbon (v) heterocyclic groups and (vi) heterosubstituted derivatives of said groups (i) to (v),

(2) a catalyst-activating support which is a solid particulate substance, insoluble in hydrocarbons, comprising at least magnesium and aluminium atoms and hydrocarbyloxy groups containing 1 to 20 carbons atoms, the molar ratio of Mg/Al being in the range 1.0 to 300 and the molar ratio of hydrocarbyloxy groups to aluminium atoms being in the range 0.05 to 2.0, and optionally,

2. A catalyst system as claimed in Claim 1 wherein E is phosphorus.

3. A catalyst system as claimed in Claim 1 or 2 wherein M is a metal selected from Groups 3 to 7 of the Periodic Table.

4. A catalyst system as claimed in any one of the preceding Claims wherein M is titanium, vanadium or chromium.

5. A catalyst system as claimed in any one of the preceding Claims wherein M is vanadium.

6. A catalyst system as claimed any one of the preceding Claims wherein the anionic group X is selected from a halide, a hydrocarbyl group, a carboxylate, an oxide,; an amide, an alkoxide, an acetylacetonate, a hydroxyl and a non-coordinating or weakly-coordinating anion selected from tetrafluoroborate, a fiuormated aryl borate and a triflate.

7. A catalyst system as claimed any one of the preceding Claims wherein the anionic groups X are monoanionic, dianionic or trianionic.

8. A catalyst system as claimed in any one of the preceding Claims wherein the transition metal complex is the Formula B compound.

9. A catalyst system as claimed any one of the preceding Claims wherein the complex compound B has a Formula selected from

wherein the group "R" is an alkyl group containing 1 to 20 carbons atoms.

10. A catalyst system as claimed any one of the preceding Claims wherein the neutral donor group L is a solvate molecule selected from an ether, an amine, a phosphine, an olefin, water and a conjugated or nonconjugated diene.

11. A catalyst system as claimed any one of the preceding Claims wherein the catalyst-activating hydrocarbon-insoluble support (2) has a Mg/ Al ratio in the range 40 to 150

12. A catalyst system as claimed any one of the preceding Claims wherein the catalyst-activating hydrocarbon-insoluble support (2) and has a molar ratio of alkoxy to Al in the range 0.2 to 2.0.

13. A catalyst system as claimed any one of the preceding Claims wherein the hydrocarbyloxy groups present in the catalyst-activating hydrocarbon-insoluble support are selected from methoxy, ethoxy, n-propoxy, i-propoxy, n-butoxy, sec-butoxy, t- butoxy, benzoyloxy, phenylethoxy, phenoxy, ethylphenoxy, naphthoxy, and halogenated alkoxy derivatives thereof.

14. A catalyst system as claimed in any one of the preceding Claims wherein the activator compound (3) is selected from organoaluminium compounds and organoboron compounds.

15. A catalyst system as claimed in Claim 14 wherein the activator compound (3) is selected from trimethylaluminium, triethylaluminium, tributylaluminium, tri-n- octylaluminium, ethylaluminium dichloride, diethylaluminium chloride, methylaluminium dichloride, dimethylaluminium chloride, tris(pentafluorophenyl)aluminium, alumoxanes, dimethylphenylammoniumtetra(phenyl)borate, trityltetra(phenyl)borate, triphenylboron, dimethylphenylammonium tetra(pentafluorophenyl)borate, sodium tetrakisfCbis-S^-trifluoromethy^phenyllborate^^^'COEt^tCbis-S^- trifluoromethyl)phenyl]borate, trityltetra(pentafluorophenyl)borate and tris(pentafluorophenyl) boron.

16. A catalyst system as claimed in any one of the preceding Claims wherein there is present a promoter comprising a halogenated organic compound.

17. A catalyst system system as claimed in Claim 16 wherein the promoter is selected from carbon tetrachloride, hexachloroethylene, benzylbromide, benzylchloride, ethyl trichloroacetate and 2,3- or 1,3-dichloropropylene, chloroform (CHCl₃) and n- butylchloride.

18. A catalyst system as claimed in any one of the preceding Claims wherein in addition to the defined catalyst there is present one or more other catalysts for polymerising 1 -olefins.

19. A catalyst system as claimed in Claim 18 wherein the one or more other catalysts for polymerising 1 -olefins comprise transition metal compounds.

20. A catalyst system as claimed in Claim 18 or 19 wherein the one or more other catalysts are selected from Ziegler-Natta catalyst systems, metallocene-based catalysts, or heat activated supported chromium oxide catalysts.

21. A process for the polymerisation and copolymerisation of 1 -olefins, cycloolefins or dienes comprising contacting the monomeric olefin under polymerisation conditions with the catalyst system claimed in any one of the preceding Claims.

22. A process as claimed in Claim 21 wherein the process is for the homopolymerisation of 1 -olefins and wherein the monomer is selected from ethylene and propylene.

23. A process as claimed in Claim 21 wherein the process is for the polymerisation of monomer selected from ethylene, propylene, 1-butene, 1-hexene, 4-methylpentene-l, 1-octene, methyl methacrylate, methyl acrylate, butyl acrylate, acrylonitrile, vinyl acetate, vinyl chloride, styrene, butadiene, hexadiene and norbornene.

24. A process as claimed in Claim 21 wherein the process is for the copolymerisation of monomer selected from ethylene, propylene, 1-butene, 1-hexene, 4- methylpentene-1, 1-octene, methyl methacrylate, methyl acrylate, butyl acrylate, acrylonitrile, vinyl acetate, vinyl chloride, styrene, butadiene, hexadiene and norbornene.

25. A process as claimed in any one of Claims 21 to 24 wherein the process is carried out under gas phase, slurry phase or solution phase polymerisation conditions.

26. A process as claimed in any one of Claims 21 to 25 wherein the process is carried in the presence of hydrogen gas to modify the average molecular weight of the produced polymer.