WO2006030192A1

WO2006030192A1 - Polyolefins

Info

Publication number: WO2006030192A1
Application number: PCT/GB2005/003521
Authority: WO
Inventors: Vernon Charles Gibson; Grant Berent Jacobsen; David John Jones; Richard James Long
Original assignee: Ineos Europe Limited
Priority date: 2004-09-14
Filing date: 2005-09-13
Publication date: 2006-03-23
Also published as: GB0420399D0

Abstract

Process for making a copolymer by copolymerising (1) ethylene with (2) at least one aliphatic C3-C20 alpha-olefins and (3) at least one C4 to C30 conjugated or non-conjugated diene, by contacting with a catalyst comprising (a) a transition metal compound of Formula (A), and (b) an activating quantity of a suitable activator, groups R1 and R2 are -Ra, -ORb, -NRcRd, and NHRe: groups Ra, Rb, Rc, Rd, and Re, and group R3 are (i) aliphatic hydrocarbon, (ii) alicyclic hydrocarbon, (iii) aromatic hydrocarbon, (iv) alkyl substituted aromatic hydrocarbon (v) heterocyclic groups or (vi) heterosubstituted derivatives of said groups (i) to (v); 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; n is 1 or 2, 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. The process is useful for making elastomeric polymers.

Description

POLYOLEFINS

The present invention relates to olefin copolymers and to methods for their manufacture.

The use of certain transition metal compounds to polymerise 1 -olefins, for example, ethylene or propylene, is well established in the prior art. The earliest catalysts for the catalysed polymerisation and copolymerisation of 1 -olefins were the well-known Ziegler-Natta catalysts based on transition metal halide, eg titanium or vanadium chloride and an alkyl aluminium compound. More recently the use of certain metallocene catalysts (for example biscyclopentadienylzirconiumdichloride activated with alumoxane) has provided catalysts with potentially high activity. The use of metallocene based catalysts in the manufacture of EPM and EPDM elastomeric copolymers has been disclosed in, for Example, US Patent 6545088 (Dow Global Technologies Inc).

An object of the present invention is to provide an improved process for manufacturing a copolymer, preferably an elastomeric copolymer, based on copolymerised units of ethylene, propylene and a diene. The present invention provides a process for making a copolymer comprising copolymerising (1) ethylene with (2) at least one comonomer selected from the group consisting of aliphatic C₃-C₂₀ alpha-olefins and (3) at least one diene selected from C₄ to C₃₀ conjugated and nonconjugated dienes, comprising contacting the monomer with a catalyst comprising (a) a transition metal compound having the following Formula A, and

(b) an activating quantity of a suitable activator, 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) 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; n is 1 or 2, 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.

Preferably the copolymers of the present invention are so-called "elastomeric" copolymers.

The copolymers made by the process of the present invention comprise 30 to 85, preferably 40 to 80 and more preferably 50 to 75, weight percent of copolymerised ethylene units; 14 to 70, preferably 19 to 60 and more preferably 24 to 55, weight percent of copolymerised units the at least one comonomer selected from the group consisting of aliphatic C₃-C₂₀ alpha-olefins; and 0.1 to 20, preferably 0.5 to 15, more preferably 1 to 12 weight percent of copolymerised units of the at least one diene selected from C₄ to C₃₀ conjugated and nonconjugated dienes. Accordingly, the quantities of monomers fed to the copolymerisation reaction are preferably such as to provide copolymers, preferably elastomeric copolymers, having a composition of ^■ copolymerised units falling within these defined ranges. The quantities can be determined by simple trial and error experimental testing to determine the reactivity ratios of the relevant comonomers.

Examples of the aliphatic C₃-C₂₀ alpha-olefins include propene, 1-butene, 4- methyl- 1-pentene, 1-hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1- hexadecene, 1-octadecene and 1-eicosene. The alpha-olefin can also contain a cyclic structure such as cyclohexane or cyclopentane, resulting in an alpha-olefin such as 3- cyclohexyl-1-propene (allyl-cyclohexane) and vinyl-cyclohexane. Although not alpha- olefins in the classical sense of the term, certain cyclical olefins such as norbornene and related olefins can be used in place of some or all of the alpha-olefins.

Examples of non-conjugated dienes include aliphatic dienes such as 1,4- pentadiene, 1,4-hexadiene, 1,5-hexadiene, 2-methyl-l,5-hexadiene, 1,6-heptadiene, 6- methyl-l,5-heptadiene, 1,6-octadiene, 1,7-octadiene, 7-methyl-l,6-octadiene, 1,13- tetradecadiene, 1,19-eicosadiene, and the like; cyclic dienes such as 1,4-cyclohexadiene, bicyclo[2.2.1]hept-2,5diene, 5-ethylidene-2 -norbornene, 5-methylene-2-norbornene, 5- vinyl-2-norbornene, bicyclo[2.2.2]oct-2,5-diene, 4-vinylcyclohex-l -ene, bicyclo[2.2.2]oct-2,6-diene, l,7,7-trimethylbicyclo[2.2.1]hept-2,5-diene, dicyclopentadiene, methyltetrahydroindene, 5-allylbicyclo[2.2.1]hept-2-ene, 1,5- cyclooctadiene, and the like; aromatic dienes such as 1,4-diallylbenzene, 4-allyl-lH- indene; and trienes such as 2,3-diisopropenylidiene-5-norbornene, 2-ethylidene-3- isopropylidene-5 -norbornene, 2-propenyl-2,5-norbornadiene, 1,3,7-octatriene, 1,4,9- decatriene, and the like; with 5-ethylidene-2-norbornene a preferred nonconjugated diene. Examples of conjugated dienes include butadiene, isoprene, 2,3- dimethylbutadiene-1,3, l,2-dimethylbutadiene-l,3, l,4-dimethylbutadiene-l,3, 1- ethylbutadiene-1,3, 2-phenylbutadiene-l,3, hexadiene-1,3, 4-methylpentadiene-l,3, 1,3- pentadiene (CH3CH-CH-CH-CH2; commonly called piperylene), 3 -methyl- 1,3- pentadiene, 2,4dimethyl-l,3-pentadiene, 3-ethyl-l,3-pentadiene, and the like; with 1,3- pentadiene a preferred conjugated diene.

Examples of copolymers, eg elastomeric copolymers, that can be made by the process of the present invention are ethylene/propylene/5-ethylidene-2-norbornene; ethylene/1 -octene/5-ethylidene-2-norbornene; ethylene/propylene/1 ,3-pentadiene; and ethylene/ 1 -octene/1 ,3-pentadiene; ethylene/propylene/1 , 7-octadiene: ethylene/propylene/1 -octene/diene or ethylene/propylene/mixed dienes, wherein the diene is preferably selected from those recited above; e.g. ethylene/propylene/5- ethylidene-2-norbornene/piperylene (ie trans-l,3-pentadiene). In addition, the elastomers made using the process of this invention can include minor amounts, e.g. 0.05-0.5 percent by weight, of long chain branch enhancers, such as 2,5-norbornadiene (also known as bicyclό[2,2,l]hepta-2,5diene), diallylbenzene, 1,7- octadiene (H₂C-CH(CH₂)₄CH-CH₂), and 1,9-decadiene (H₂C-CH(CH₂)₆CH-CH₂).

In the catalyst employed in the process of the present invention 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 anthracenyl. 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°)R^d'- , -N(R^C)- , -N(R°)-R^d'-N(R^C)- , -Si(R^c)₂-R^a'-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, the catalyst employed in the process of the present invention can comprise a transition metal complex wherein n = 2 and the R¹ groups on the two units

are linked to form R⁵ 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°)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 is preferably a Group 3 to 11 transition metal, more preferably Group 5 to 7 transition metal. Most preferably M is vanadium. M can also be a Group 3 to 6 transition metal.

. In a preferred embodiment of the present invention the polymerisation catalyst comprises (1) the recited transition metal complex having Formula A wherein the monovalent groups R¹ and R² are independently selected from -R^a, -OR^b, -NR°R^d, and -NHR^e: the monovalent groups R^a, R^b, R°, 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

(2) the recited activator compound, 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 is selected from the divalent groups -R^a- , -O-R - , -O-R^b'-O- , -N-(R^c)R^d'- , -N(R⁰)- , -N(R^C)-R^d'-N(R^C)- , -Si(R^c)₂-R^al-Si(R°)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).

Examples of groups suitably used as the divalent group R⁵ are -CH₂-, -CH₂CH₂-, -CH₂CHiCH₂-, trans- 1,2-cyclopentane, trims'- 1,2-cyclohexane, 2,3-butane, 1,1'- biphenyl, l,l'-binaρhthyl, -N(Me)-, -N(Et)-, l,l'-biphenol 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°, 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. It can also be selected from Groups 3 to 6. M is preferably vanadium.

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 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 activator compound employed in the catalyst system for use in the process of the present invention is suitably selected from organoaluminium compounds and organoboron compounds and may for example comprise 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. Catalysts activating supports of this type are further described later in this specification. 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]₈ 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 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]borate, trityltetra(pentafluorophenyl)bόrate 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.

EP1238989 discloses the use of activators (Lewis acids) selected from (b-1) ionic-bonding compounds having a CdCl₂ type or a CdI₂ type of layered crystal structure;

(b-2) clays, clay minerals, or ion-exchange layered compounds; (b-3) heteropoly-compounds; and (b-4) halogenated lanthanoid compounds.

The process of the present invention can employ the catalysts as hereinbefore defined activated in the manner of manner of EP 1238989 if desired. Such Lewis acids are those compounds which capable of receiving at least one electron pair and is capable of forming an ion pair by reaction with the transition metal complex. The Lewis acid includes the afore-mentioned (b-1) ionic-bonding compounds having a layered crystal structure of a CdCl₂ type or CdI₂ type (b-2) clay . clay minerals, or ion-exchange layered compounds, (b-3) heteropoly compounds, and (b-4) halogenated lanthanoid compounds. The Lewis acid further includes SiO₂, Al₂O₃, natural and synthetic zeolites which have Lewis acid points formed by heating or a like treatment, and complexes and mixtures thereof.

US Patent 6399535 discloses a coordinating catalyst system capable of polymerising olefins comprising: (I) as a pre-catalyst, at least one non-metallocene, non-constrained geometry, bidentate ligand containing transition metal compound or tridentate ligand containing transition metal compound capable of (A) being activated upon contact with the catalyst support- activator agglomerate of (II) or (B) being converted, upon contact with an organometallic compound, to an intermediate capable of being activated upon contact with the catalyst support-activator agglomerate of (II), wherein the transition metal is at least one member selected from Groups 3 to 10 of the Periodic table; in intimate contact with

(II) catalyst support-activator agglomerate comprising a composite of (A) at least one inorganic oxide component selected from SiO₂, Al₂O₃, MgO, AlPO₄, TiO₂, ZrO₂, and Cr₂O₃ and (B) at least one ion containing layered material having interspaces between the layers and sufficient Lewis acidity, when present within the catalyst support- activator agglomerate, to activate the pre-catalyst when the pre-catalyst is in contact with the catalyst support-activator agglomerate, said layered material having a cationic component and an anionic component, wherein said cationic component is present within the interspaces of the layered material, said layered material being intimately associated with said inorganic oxide component within the agglomerate in an amount sufficient to improve the activity of the coordinating catalyst system for polymerizing ethylene monomer, expressed as Kg of polyethylene per gram of catalyst system per hour, relative to the activity of a corresponding catalyst system employing the same pre- catalyst but in the absence of either Component A or B of the catalyst support-activator agglomerate; wherein the amounts of the pre-catalyst and catalyst support-activator agglomerate which are in intimate contact are sufficient to provide a ratio of micromoles of pre-catalyst to grams of catalyst support-activator agglomerate of from about 5:1 to about 500:1. The layered material can be, for example, a smectite clay. The process of the present invention can employ a catalyst system with a catalyst support-activator agglomerate as described in US 6399535 if desired. . The activator (b) in the process of the present invention can comprise 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, the average particle size of the support being in the range 3 to 80 micrometres (μm),

Catalyst-activating hydrocarbon-insoluble supports of this type preferably contain a Mg/Al ratio in the range 40 to 150 and has a molar ratio of hydrocarbyloxy to Al in the range 0.2 to 2.0. They are 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 AlR_nX_3-11 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. Examples of organoaluminium compounds that can be employed to make catalyst-activating hydrocarbon-insoluble supports are R₃Al, R₂AlX and RAlX₂ wherein R is preferably C₁ 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. Examples of alcohols that can be employed to make catalyst-activating hydrocarbon-insoluble supports are R¹OH wherein R¹ 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. In the preparation of such supports, the magnesium halide is preferably dissolved completely in the alcohol, heating or refluxing the mixture if necessary. Any undissolved magnesium halide is preferably separated before reacting the solution with the organoaluminium compound. Reacting the solution with the organoaluminium compound using quantities having the afore-recited Mg/Al ratios produces a solid having the desired chemical characteristics. 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. In addition to the 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 promotor, 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 a conventional support material. Suitable support materials are, 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 as the transition metal component of the catalyst system used in the process of the present invention:

Preferably the transition metal in the complex is vanadium. Examples of such complexes are shown in the following formulae wherein the "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:

Examples of preferred titanium compounds are those having the formulae:

Particularly preferred complex compounds are those based on vanadium 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. The catalyst system used in the process 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 can also be used in conjunction with other catalysts producing only 1 -olefins, either inside or outside the polymerisation reactor, hi this way it is possible to generate, for example, 1 -olefins having even numbers of carbon atoms by oligomerisation of ethylene. The produced 1 -olefins can form part or all of the aliphatic C₃-C₂₀ alpha-olefins monomer used in the process of the present invention. 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 catalyst used in the present invention can be formed in situ in the presence of support material, or support material can be pre-impregnated or premixed, simultaneously or sequentially, with one or more of the catalyst components. The catalyst can if desired be supported on a heterogeneous catalyst, for example, a magnesium halide supported Ziegler Natta catalyst, a Phillips type (chromium oxide) supported catalyst or a supported metallocene catalyst. Formation of the supported catalyst can be achieved for example by treating the defined transition metal compounds with alumoxane in a suitable inert diluent, for example a volatile hydrocarbon, slurrying a particulate support material with the product and evaporating the volatile diluent. The produced supported catalyst is preferably in the form of a free-flowing powder. The quantity of 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 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 fluidised 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. In 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. In 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.

The process of the present invention can be operated, if desired, using process conditions 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. In 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 process of the present invention can be operated 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 has been extensively described in the prior art and reference may be made to the prior art methods for analogously suitable methods readily adaptable to use of the catalyst of the present invention. For example, see EP 751965, US 5442019, US5672665, US5747612, US 5753786, EP 830393, US 5672666, EPl 171486, EP885247, EPl 182216, US6284849. US2004/0127655, WO04/060938, US2004/0138391, WO, 04/060921, WO04/060922, WO04/060929, WO04/060930, and WO04/060931.

Methods for operating gas phase polymerisation processes are well known in the art. Such methods generally involve agitating (e.g. by stirring, vibrating or fluidising) 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/or 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.

When using 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.

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". Example 1 Synthesis of 2-Methoxymethoxy-3-tert-butylphenyl lithium.nEt?O (n = 0.5-1.0), "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-butyllithium (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 Hz, IH, Ax-H), 7.35 (d, ³J_HH = 7.5 Hz, IH, Ar-H), 7.25-7.18 (m, IH, Ar-H), 5.33 (s, 2H, OCH₂O), 2.97 (q, ³J_ΗΗ = 7.0 Hz,

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

6nH, OCH₂CH₃).

Example 2

Synthesis of N,N-diisopropyl-P-phenyI phosphonamidous 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. All 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

¹H NMR (250 MHz, CDCl₃): δ 7.82-7.75 (m, 2H, Ar-H), 7.17-7.02 (m, 3Η, Ar-H), 3.24 (br s, 2Η, NCH(CHs)₂), 2.00-0.55 (br m, 12H, NCH(CH₃)₂). ³¹P NMR (101 MHz, CDCl₃): δ 131.9. Example 3 Synthesis of (2-Methoxymethoxy-3-fe/Y-butyl-phenyr)phenylphosphme 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 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; H, 7.28; Found: C, 67.83; H, 7.39.

¹H NMR (400 MHz, CDCl₃): δ 8.22 (d, ¹J_H? = 499 Hz, IH, PH), 7.70-7.57 (m, 3H, H_(4,B)), 7.56-7.52 (m, IH, H_(D)), 7.49-7.40 (m, 3H, H₍₆,_c)), 7.15 (dt, J = 7.7 Hz, J = 2.4

Hz, IH₅ H₍₅J), 5.28-5.23 (m, 2H₅ OCH₂O), 3.53 (s, 3H₅ OCH₃), 1.41 (s, 9Η, C(CH₃)₃).

¹³C(¹H) NMR (101 MHz, CDCl₃): δ 158.1 (Ar-Q₂;), 144.5 (d, ³J_CP = 5.4 Hz₅ Ar-Q₃;),

132.9 (Ax-Cf₄J), 132.1 (Ar-Qr,;), 131.7 (d, ²J_CP = 10.2 Hz, Ar-Q₆;), 131.5 (d, ¹JcP = 103

Hz₅ Ax-C_(A)), 131.7 (d, ²J_CP = 10.9 Hz₅ Ar-Qg), 128.5 (d, ³J_CP = 13.3 Hz₅ Ar-Q₂;), 127.3 (d, ¹Jc_P = 99.3 Hz₅ Ar-Qy;), 124.4 (d, ³J_CP = 13.6 Hz₅ Ar-Q₅;), 102.4 (OCH₂O), 57.7

(OCH₃), 35.3 (C(CHs)₃), 30.9 (C(CH₃)₃).

³¹P(¹H) NMR (101 MHz, CDCl₃): δ 17.9 (s).

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

MS(CI;m/z):637[2M+Hf₅319 [M+H]⁺.

IR(NaCl;cm^"1):3057w₅2959s,291Om₅2872m,283Ow,2330brm(P-H), 1572m, 1483m, 1464m, 1438s, 1427m, 1391s,1362w, 1269w, 1233m, 1196s, 1164s(P=O), 1127s, 111Ow, 1077s,948s,924s,793m,745s,707m,693s. Example 4

Synthesis of 1.2-Ethanediylbis[(2-methoxymethoxy-3-te^-butyl-phenvnphenyl- 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: C, 68.87; H, 7.30; Found: C, 68.92; H, 7.39.

¹H NMR (400 MHz, CDCl₃): δ 7.68-7.60 (br m, 4H₃ Ar-H), 7.55-7.40 (br m, 16H, Ar-

H), 7.40-7.32 (br m, 4H, Ar-H), 7.08-6.95 (br m, 2Η + 2Η + 4H, Ar-H), 5.26 (dd, 2 ^ZJτΗP _ = 88.2 Hz, ⁴JH_H = 4.1 Hz, 4H, rac-OCH₂O), 5.16 (dd, ²J_HP = 87.7 Hz, ⁴JHH = 4.1 Hz, 4H, meso-OCH₂O), 3.43 (s, 6H, rac-OCH₃), 3.23 (s, 6Η, meso-OCH₃), 3.10-2.91 (m, 2H, rac-PCH₂), 2.60-2.37 (m, 4H, meso-?CH₂), 2.08-1.95 (m, 2H, rac-PCH₂), 1.35 (s, 18H₅ WC-C(CHj)₃), 1.32 (s, 18Η, WeTO-C(CHj)₃).

¹³C(¹H) NMR (101 MHz, CDCl₃): δ 158.6 (d, ²J_CP = 10.7 Hz, rac + meso Ar-Q₂;), 145.2-145.1 (m, rac + meso Ar-Qy), 132.7 {raclmeso Ar-Q_/;), 132.6 {mesolrac Ar- Cf₄J), 131.8 {raclmeso Ax-C_(Dj), 131.7 {mesolrac Ar-Qr,;), 131.7 (d, ¹Jc_P = 157 Hz, raclmeso Ar-C(A)), 131.4 (d, ¹Jc_P - 157 Hz, mesolrac Ax-C(A)), 131.4-131.0 (m, rac + meso Ax-C(_Q, rac + meso Ax-C_(B)), 128.5-128.3 (m, rac + meso Ar-Qg), 127.9 (d, ¹JcP = 49.8 Hz, raclmeso Ax-C_m), 127.6 (d, ¹J₀P = 49.2 Hz, mesolrac Ar-Q₇;), 123.9-123.7 (m, rac + meso Ar-Q₅;), 102.5 (rac-OCH₂O), 102.4 {meso-OCH₂O), 57.7 {rac- OCH₃), 57.4 (meso-OCH₃), 35.4 (rac/meso-C(CH₃)₃), 35.4 (mesø/røc-C(CH₃)₃), 30.9 (rac-C(CH₃)₃), 30.8 {meso-C{CR₃)3), 23.4-21.8 (m, rac + meso PCH₂). /

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

JJR. (KBx; 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, 789m₅ 764m, 742s, 714m, 700m, 689m, 599w,

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

Example 5

Synthesis of 2,2Ml_*2-Ethanediylbis(phenylphosphinylidene)1bis(6-fert- butvDphenoL, "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 me5O-"Compound 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

¹H NMR (500 MHz, CDCl₃): δ 11.29 + 11.28 (2 x s, 2H, OH), 7.77-7.72 (m, 4H₅ Ar-H), 7.55 (t, ³J_HH = 7.2 Hz, 2H, Ar-H), 7.52-7.46 (m, 4H, Ar-H), 7.42-7.37 (m, 2H, Ar-H), 6.91-6.82 (m, 2Η, Ar-H), 6.80-6.74 (m, 2Η, Ar-H), 2.68-2.49 (m, 4Η, CH₂), 1.40 + 1.39 (2 x s, 9H, C(CHO₃).

³¹P(¹H) NMR (202 MHz, CDCl₃): δ 46.8 (s, meso), 46.7 (s, rac). MS (FAB; /n/fe): 575 [M]⁺, 301 [M-P(Ph)(O)(CBu)C₆H₃OH)]⁺. IR (KBr; cm^'1): 3063w, 2990m, 2961s, 2906m, 2868m, 2827w, 1571w, 1484w₅ 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 6 Synthesis of 2,2'-[l,2-ethanedivIbis(phenyIphosphinidene)1bis(6-ter/-butyl)phenol, "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 OfAlH₃. 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 6O⁰C 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 7røe,yø-"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, 12H, Ar-H_β,B,c,DJ). 7.16 (pt, J = 5.9 Hz, 2H, OH), 6.98-6.94 (m, 2H, Ai-Hf₅₎), 6.82 (pt, J = 7.6 Hz, 2H, Av-H₍₄j), 2.22-2.08 (m, 4Η, PCH₂), 1.42 (s, 18H₅ C(CHs)₃)-

¹³C(¹H) NMR (101 MHz, CDCl₃): δ 158.7 (pt, J = 10.3 Hz, Ar-Q₇;), 136.5 (Ar-Q₂Z₄;), 136.0 (Ar-Q₂^;), 131.8 (pt, J = 8.6 Hz, Ar-Q₂;), 130.3 (Ar-Q₅;), 129.0 (Ar-Q₅;), 128.6 (d, ³J_HH = 3.9 Hz, Ar-Qc;), 128.6 (Ar-Q_x,;), 120.9 (Ar-Q₁₅;), 120.4 (Ar-Q₄;), 34.9 (C(CHa)₃), 29.5 (C(CH₃)₃), 22.8 (PCH₂). ³¹P(¹H) NMR (101 MHz, CDCl₃): δ -43.47.

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

IR (KBr; cm^'1): 3393br (OH), 3073w, 3050w, 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: C₅ 75.39; H, 7.51.

¹H NMR (400 MHz, CDCl₃): δ 7.32-7.29 (m, 12H, AX-H_(3ΛC,D))- 7.18 (pt, J = 5.9 Hz,

2H, OH), 6.94-6.91 (m, 2H, Ax-H₍₅₎), 6.82 (pt,^' J = 7.6 Hz₅ 2H, Ai-Hf₄)), 2.21-2.04 (m,

4H₅ PCH₂), 1.41 (s, 18H₅ C(CHs)₃).

¹³C(¹H) NMR (101 MHz, CDCl₃): δ 158.9 (pt, J = 10.4 Hz₅ Ar-Q;;), 136.5 (Ar-Q₂₇₄)), 136.2 (Ar-C_(2/A)), 131.7 (pt, J = 8.5 Hz, Ar-Q₃;), 130.3 (Ar-Q₅;), 129.0 (Ar-Q₅;), 128.6 ^'

(Ar-Q₀ + Ar-Q₁,;), 120.4 (Ar-Q,;), 120.2 (Ar-Q₆;), 34.9 (C(CH₃)₃), 29.5 (C(CH₃)₃),

22.6 (PCH₂).

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

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

IR (KBr; cm^"1): 3398br (OH)₅ 307Ow, 3049w, 3002w, 2956m, 291Ow, 2868w, 1576m, 1570m, 1481w, 1436m, 1434m, 1419s, 1408s, 1390m, 1363w, 1358w, 1305w, 1267m, 1226m, 1196s, 1189s, 1173m, 115Om₅ 114Im₅ 1114m, 1093m, 1076m, 1025w₅ 100Ow₅ 858w, 818w, 784w, 747s, 74Is₅ 693s, 566w, 491m, 442m. Example 7

Synthesis of Fmc-2,2MlJl-Ethanediylbis(phenylphosphinideneVlbis(6-fert- butvDphenoxidel zirconium(IV) dichloride, "Compound 7"

"Compound 7" was prepared by addition of a toluene solution of VO(O¹¹Pr)₃ to a toluene solution of the ligand "compound 6" (prepared in Example 6)

To a slurry of NaH (0.2 g, excess) in thf (50ml) was added a solution of the ligand "Compound 6" prepared in Example 6 (0.77 g, 1.42 mmol) in thf (tetrahydrofuran) and the mixture stirred at room temperature for 5 min and then refmxed for 30 min. The cooled solution was filtered into a solution of ZrCl₄(thf)₂ (0.82 g, 1.42 mmol) in thf (20 ml). The mixture was stirred for 12 h and the solvent then removed under vacuum. The residue was extracted with toluene and the solvent removed under vacuum. The colourless product was triturated with pentane, filtered, and dried under vacuum to give rac-OPPOZrCl₂ (0.90 g, 1.28 mmol, 90 % yield). ¹H NMR (250 MHz, CDCl₃): 7.55-

7.48 (m, 4H₅ Ar-H), 7.41-7.36 (m, 8H, Ar-H), 7.08-7.02 (m, 2H, Ar-H), 6.89 (pt, J = 7.6

Hz, 2H, Ar-H), 2.58-2.50 (m, 2H, CH₂), 1.91-1,88 (m, 2H, CH₂), 1.41 (s, 9Η, C(CH₃)₃).

³¹P NMR (101 MHz, CDCl₃): 1.34 (s). The structural Formula of "Compound 7" as determined by X-ray diffraction is shown in Figure 1 of the Drawings.

Compound 7, preferably together with an activator, can be used to copolymerise monomers in accordance with the present invention.

Example 8 Synthesis oπmc^^Ml^-EthanediylbisfohenylphosphinidenellbisCβ-fert- butvDphenoxidel vanadium(V) 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 røc-"Compound 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, Ar-H),^" 7.60-7.48 (m, 2Η, Ar-H), 7.40-7.27 (m, 8Η, Ar-H), 7.02-6.90 (m, 2Η, Ar-H), 6.79-6.71 (m, 2Η, Ar-H), 5.49-5.38

(m, 1Η, OCH₂), 5.29-5.19 (m, 1Η, 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(CH₃)₃), 1.32 (s, 9Η,

C(CHa)₃), 0.89 (t, ³JΗΗ = 7.3 Hz, 3H, CH₂CH₃).

The X-ray diffraction crystal structure of "Compound 8" is illustrated in Figure 2 of the Drawings.

Example 9

Synthesis of fmeyQ-2,2'-fl,2-Ethanediylbis(phenylphosphinidene)lbis(6-te^- butvDphenoxidel vanadiumfV) oxypropoxide, "Compound 9".

To a solution of vanadium(V) oxytripropoxide (57.8 mg, 0.237 mmol) in toluene (10 ml) cooled to -78⁰C was added a solution of meso-"Compound 6" (126 mg, 0.232 mmol) in toluene (20 ml) dropwise The mixture was allowed to warm to room temperature over 12 h giving a dark red-brown solution. The solvent was removed under vacuum and the residue washed with pentane (10 ml) and dried under vacuum to give 9 as a brown solid (103 mg, 0.154 mmol, 66 % yield).

Analysis

¹H NMR (250 MHz, C₆D₆): δ 8.03-7.90 (m, 2H₅ Ar-H), 7.90-7.77 (m, 2H, Ai-H), 7.41 (d, J = 7.3 Hz, IH, Ar-H), 7.29 (d, J = 6.7 Hz₅ IH, Ar-H), 7.08-6.98 (m, 2H, Ar-H)₅

6.89-6.75 (m, 5H₅ Ar-H), 6.55-6.50 (m, IH₅ Ar-H)₅ 5.03-4.97 (m, 2Η, OCH₂CH₂), 2.34-

1.92 (m, 4H₅ PCH₂), 1.74-1.67 (s + m₅ 11Η, C(CH₃)₃ + OCH₂CH₂), 1.31 (s, 9H₅

C(CHs)₃), 0.95 (t, ³J_ΗΗ = 7.3 Hz, 3H, CH₂CH₃).

Example 10 Copolymerisation of ethylene, propylene and 5-ethylidene-2-norbornene to make

EPDM

A 500ml dried Fischer-Porter Vessel was fitted with a flame dried mechanical stirrer and flushed with N₂ for 45min. Toluene (200ml) was introduced. The vessel was flushed with propylene (1 bar for 8 min). The vessel was warmed to 5O⁰C and the propylene pressure increased to 2 bar. Dimethylaluminiumchloride (2mmol) and ethyl trichloroacetate (lmmol) were added to the vessel, followed by 5-ethylidene-2- norbornene (2.4ml). The vessel was transferred to an ethylene supply and 0.2 bar ethylene introduced. A toluene solution of "Compound 8" was added (lμmol) and the ethylene pressure increased immediately to 2 bar. After 20 min the polymerisation was terminated by addition of 2ml 2M HCl. The polymer was precipitated by addition of acidified MeOH and then filtered, washed with MeOH and dried to constant weight under vacuum at 5O⁰C. Polymer yield = 5.16 g Activity = 15,480 g/mmol.h

The IR spectrum of a thin film the copolymer is shown in Figure 3 of the Drawings.

There are three important bands in the spectra - - 1650 cm-1 (v C=C) - shows the 5-ethylidene-2-norbornene incorporated;

-1460 cm-1 (δ CΗ2, δ CH3) - due mainly to the deformation vibrations of the PE backbone;

-1375 cm-1 (δ CH2, δ CH3)- indicative for the presence of Me-branches

Claims

Case 10183 (2)Claims

1. A process for making a copolymer comprising copolymerising (1) ethylene with (2) at least one comonomer selected from the group consisting of aliphatic C₃-C₂₀ alpha- olefins and (3) at least one diene selected from C₄ to C₃₀ conjugated and nonconjugated dienes, comprising contacting the monomer with a catalyst comprising

(a) a transition metal compound having the following Formula A, and

(b) an activating quantity of a suitable activator,

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) 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; n is 1 or 2, 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.

2. A process as claimed in Claim 1 wherein the copolymers comprise 30 to 85, preferably 40 to 80 and more preferably 50 to 75, weight percent of copolymerised ethylene units; 14 to 70, preferably 19 to 60 and more preferably 24 to 55, weight percent of copolymerised units of the at least one comonomer selected from the group consisting of aliphatic C₃-C₂₀ alpha-olefms; and 0.1 to 20, preferably 0.5 to 15, more preferably 1 to 12 weight percent of copolymerised units of the at least one diene selected from C₄ to C₃₀ conjugated and nonconjugated dienes.

3. A process as clamed in Claim 1 or 2 wherein the aliphatic C₃-C₂₀ alpha-olefm is selected from propene, 1-butene, 4-methyl-l-pentene, 1-hexene, 1-octene, 1-decene, 1- dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene and 1-eicosene, 3-cyclohexyl-l- propene and vinyl-cyclohexane.

4. A process as claimed in any one of the preceding Claims wherein the diene is selected from 1,4-pentadiene, 1,4-hexadiene, 1,5-hexadiene, 2-methyl-l,5-hexadiene, 1,6-heptadiene, 6-methyl-l,5-heptadiene, 1,6-octadiene, 1,7-octadiene, 7-methyl-l,6- octadiene, 1,13-tetradecadiene, 1,19-eicosadiene, 1,4-cyclohexadiene, bicyclo[2.2.1]hept-2,5diene, 5-ethylidene-2-norbornene, 5-methylene-2-norbornene, 5- vinyl-2-norbornene, bicyclo[2.2.2]oct-2,5-diene, 4-vinylcyclohex-l-ene, bicyclo[2.2.2]oct-2,6-diene, 1 ,7,7-trimethylbicyclo[2.2. l]hept-2,5-diene, dicyclopentadiene, methyltetrahydroindene, 5-allylbicyclo[2.2.1]hept-2-ene, 1,5- cyclooctadiene, 1,4-diallylbenzene, 4-allyl-lH-indene, 2,3-diisopropenylidiene-5- norbornene, 2-ethylidene-3-isopropylidene-5-norbornene, 2-propenyl-2,5- norbornadiene, 1,3,7-octatriene, 1,4,9-decatriene, butadiene, isoprene, 2,3- dimethylbutadiene-1,3, l,2-dimethylbutadiene-l,3, l,4-dimethylbutadiene-l,3, 1- ethylbutadiene-1,3, 2-phenylbutadiene-l,3, hexadiene-1,3, 4-methylpentadiene-l,3, 1,3- pentadiene, 3-methyl-l,3-pentadiene, 2,4-dimethyl-l,3-pentadiene, 3-ethyl-l,3- pentadiene.

5. A process as claimed in any one of the preceding Claims wherein the copolymer is selected from ethylene/propylene/5-ethylidene-2-norbornene; ethylene/ l-octene/5- ethylidene-2-norbornene; ethylene/propylene/1 ,3 -pentadiene; and ethylene/1 -octene/1, 3- pentadiene; and ethylene/propylene/1, 7-octadiene.

6. A process as claimed in any one of the preceding Claims wherein the copolymer includes 0.05-0.5 percent by weight, of a long chain branch enhancer selected from 2,5- norbornadiene, diallylbenzene, 1,7-octadiene, and 1,9-decadiene.

7. A process as claimed in any one of the preceding Claims wherein the catalyst is

(1) a transition metal complex having the recited 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) 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

(2) an activator compound, 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

-O-R^b'-O- , -N-(R^c)R^d'- , -N(R⁰)- , -N(R^C)-R^d'-N(R^C)- , -Si(R°)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).

8. A process as claimed in any one of the preceding Claims wherein M is a Group 3 to 7 transition metal.

9. A process as claimed in any one of the preceding Claims wherein M is a Group 3 to 6 transition metal.

10. A process as claimed in any one of the preceding Claims wherein E is phosphorus.

11. A process as claimed in any one of the preceding Claims wherein the anionic group X is selected from chloride, bromide, a hydrocarbyl group, a carboxylate, an oxide, an amide, an alkoxide, an acetylacetonate and a hydroxyl.

12. A process as claimed in any one of the preceding Claims wherein the activator (b) is selected from organoaluminium compounds and organoboron compounds or mixtures thereof.

13. A process as claimed in any one of the preceding Claims wherein the activator is 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.

14. A process as claimed in Claim 12 wherein the activator is selected from trimethylaluminium, triethylaluminium, tributylaluminium, tri-n-octylaluminium, ethylaluminium dichloride, diethylaluminium chloride, tris(pentafluorophenyl)aluminium, alumoxanes, 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]borate, trityltetra(pentafluorophenyl)borate and tris(pentafluorophenyl) boron.

15. A process as claimed in any one of the preceding Claims wherein in addition to the one or more defined transition metal catalysts the catalyst comprises an additional catalyst suitable for polymerising 1 -olefins.

16. A process as claimed Claim 15 wherein the additional catalyst is selected from conventional Ziegler-Natta catalyst systems, metallocene-based catalysts, or heat activated supported chromium oxide catalysts.

17. A process as claimed in any one of the preceding Claims wherein the polymerisation conditions are bulk phase, solution phase, slurry phase or gas phase.

18. A process as claimed in any one of the preceding Claims wherein the catalyst is supported on a support material prior to its introduction into the polymerisation zone. 19 A process as claimed in Claim 18 wherein the support material is selected from silica, alumina, zirconia, talc, kieselguhr, magnesia, magnesium chloride and polymers.