Title of Invention	CYCLOPENTADIENYL/PHOSPHINIMINE CATALYST WITH ONE AND ONLY ONE ACTIVATABLE LIGAND
Abstract	A process for the polymerization of ethylene characterized in that said pocess is conducted in the presence of: an organometallic complex defined by the formula: wherein Cp is a cyclopentadienyl-type ligand; L is an activatable Ligand; M is a metal selected from Ti and Zr; and PI is a phosphinimine ligand defined by the formula: wherein each R1 is independently selected from the group consisting of a hydrogen atom, a halogen atom, C1-20 hydrocarbyl radicals which are unsubstituted by or further substituted by a halogen atom, a C1-8 alkoxy radical, an amido radical, a C6-10 aryl or aryloxy radical, a silyl radical of the formula: wherein each R2 is independently selected from the group consisting of hydrogen, a C1-6 alkyl or alkoxy radical, C6-10 aryl or aryloxy radicals, and a germanyl radical of the formula: Ge-(R2)3 wherein R2 is as defined above; and an activator at a temperature of from 75°C to 320°C and a pressure of from 100 psi to 35 mega Pascals.

Title of Invention

CYCLOPENTADIENYL/PHOSPHINIMINE CATALYST WITH ONE AND ONLY ONE ACTIVATABLE LIGAND

Abstract

A process for the polymerization of ethylene characterized in that said pocess is conducted in the presence of: an organometallic complex defined by the formula: wherein Cp is a cyclopentadienyl-type ligand; L is an activatable Ligand; M is a metal selected from Ti and Zr; and PI is a phosphinimine ligand defined by the formula: wherein each R1 is independently selected from the group consisting of a hydrogen atom, a halogen atom, C1-20 hydrocarbyl radicals which are unsubstituted by or further substituted by a halogen atom, a C1-8 alkoxy radical, an amido radical, a C6-10 aryl or aryloxy radical, a silyl radical of the formula: wherein each R2 is independently selected from the group consisting of hydrogen, a C1-6 alkyl or alkoxy radical, C6-10 aryl or aryloxy radicals, and a germanyl radical of the formula: Ge-(R2)3 wherein R2 is as defined above; and an activator at a temperature of from 75°C to 320°C and a pressure of from 100 psi to 35 mega Pascals.

Full Text	CYCLOPENTADIENYL/PHOSPHINIMINE CATALYST WITH ONE AND ONLY ONE ACTIVATABLE LIGANP TECHNICAL FIELD This invention relates to an olefin polymerization catalyst component which is an organometaHic complex having three ligands, namely a cyclopentadienyl ligand, a phosphinimine ligand and only one activatable ligand. BACKGROUND ART Certain "metallocenes". (especially bis-cyclopentadienyl complexes of group 4 metals) are highly productive catalysts for olefin polymerization when used in combination with an appropriate activator (see, for example, United States Patent CUSP") 4,542,199 (Sinn et at) and USP 5,198,401 (Hlatky and Turner). Olefin polymerization catalysts which contain a group 4 metal and one cyclopentadienyl ligand, one phosphinimine ligand and two monoanionic activatable ligands are-disclosed in a commonly assigned patent application (Stephan et al). Thus, the catalysts of Stephan et a/are group 4 metals in the 4+ oxidation state. We have now discovered a new family of olefin polymerization catalysts which contain a group 4 metal, a cyclopentadienyl ligand or phosphinimine ligand and only one activatable ligand. A preferred family of these catalysts contains Ti(lll) and offers an excellent kinetic profile when used in olefin polymerization. DISCLOSURE OF INVENTION The present invention provides a catalyst component for olefin polymerization which is an organometaHic complex defined by the formula: 2 wherein Cp is a cyclopentadienyl-type ligand; L is an activatable ligand; M is a metal selected from Ti and Zr; and PI is a phosphinimine ligand defined by the formula: wherein each R1 is independently selected from the group consisting of a hydrogen atom, a halogen atom, C1-20 hydrocarbyl radicals which are unsubstituted by or further substituted by a halogen atom, a C1-8 alkoxy radical, an amido radical, a C6-10 aryl or aryloxy radical, a silyl radical of the formula: -Si-(R2)3 wherein each R2 is independently selected from the group consisting of hydrogen, a C1-8 alkyl or alkoxy radical, C6-10 aryl or aryloxy radicals, and a germanyl radical of the formula: Ge-(R2)3 wherein R2 is as defined above. BEST MODE FOR CARRYING OUT THE INVENTION 1. Description of Catalyst Component 1.1 Metals The catalyst component of this invention is a group 4 metal selected from titanium and zirconium. 1.2 Phosphinimine Ligand The catalyst component of this invention must contain a phosphinimine ligand which is covalently bonded to the metal. This ligand is defined by the formula: 3 wherein each Ft1 is independently selected from the group consisting of a hydrogen atom, a halogen atom, C1-20 hydrocarbyl radicals which are unsubstituted by or further substituted by a halogen atom, a C1-8 alkoxy radical, a C6-10 aryl or aryloxy radical, an amido radical, a silyl radical of the formula: -Si-(R2)3 wherein each R2 is independently selected from the group consisting of hydrogen, a C1-8 alkyl or alkoxy radical, C6-10 aryl or aryloxy radicals; and a germanyl radical of the formula: Ge-(R2)3 wherein R2 isas defined above. The preferred phosphinimines are those in which each R1 is a hydrocarbyl radical. A particularly preferred phosphinimine is tri-(tertiary butyl) phosphinimine (i.e. where each R1 is a tertiary butyl group). 1.3 Cvclopentadienvl-Type Liqand The term cyclopentadienyl-type ligand (or "Cp ligand") refers to a ligand which is cyclic and forms a delocalized pi-borid with the group 4 transition metal. An exemplary (i.e. illustrative but non-limiting) list of "Cp ligands" includes substituted (or unsubstituted) cyclopentadienyl ligands, substituted (or unsubstituted) indenyf ligands, and substituted (or unsubstituted) fluorenyl ligands. The use of "substituents" on such cyclic ligands is well known and is described, for example, in USP 5,324,800 (Welborn). An exemplary list of substituents for such Cp ligands includes C1-20 hydrocarbyl groups; substituted C1-20 hydrocarbyl groups wherein one or more hydrogen atoms is replaced by a halogen; an amido group, a phosphido group, or an alkoxy group. The substituent may form a bridge with the phosphinimine ligand. For reasons of cost and simplicity, it is especially preferred that the Cp ligand is a cyclopentadienyl or indenyl ligand. 4 1.4 Activatable Liqand The term "activatable ligand" refers to a ligand which may be activated by a cocatalyst (also known as an "activator" to facilitate olefin polymerization. Exemplary activatable ligands are independently selected from the group consisting of a hydrogen atom, a halogen atom, a C1-10 hydrocarbyl radical, a C1-10 alkoxy radicalra C5-10 aryl oxide radical; each of which said hydrocarbyl, alkoxy, and aryl oxide radicals may be unsubstituted by or further substituted by a halogen atom, a C1-8 alkyl radical, a C1-8 alkoxy radical, a C6-10 aryl or aryl oxy radical, an amido radical which is unsubstituted or substituted by up to two C1-8 alkyl radicals; a phosphido radical which is unsubstituted or substituted by up to two C1-8 alkyl radicals. 2. Description of Activators (or "Cocatalvsts") The catalyst components described in part 1 above are used in combination with an "activator" (which may also be referred to by a person skilled in the art as a "cocatalyst") to form an active catalyst system for olefinpolymerization. Simple aluminum alkyls and alkoxides may provide comparatively weak cocatalytic activity under certain mild polymerization conditions. However, the preferred activators are alumoxanes and so-called ionic activators, as described below. 2.1 Alumoxanes The alumoxane activator may be of the formula: (R4)2AIO(R4A!O)mA!(R4)2 wherein each R4 is independently selected from the group consisting of C1-20 hydrocarbyl radicals and m is from 0 to 50, preferably R4 is a C1-4 alkyl radical and m is from 5 to 30. Methylalumoxane (or "MAO") is the preferred alumoxane. Alumoxanes are well known as activators for metallocene-type catalysts. Activation with alumoxane generally requires a molar ratio of aluminum in the activator to (group 4) metal in the catalyst from 20:1 to 1000:1. Preferred ratios are from 50:1 to 250:1. 5 2.2 Ionic Activators Ionic activators are also well known for metallocene catalysts. See, for example, USP 5,198,401 (Hlatky and Turner). These compounds may be selected from the group consisting of: (i) compounds of the formula [R5]+ [B(R7)4]' wherein B is a boron atom, R5 is a cyclic C5-7 aromatic cation or a triphenylmethyl cation and each R7 is independently selected from the group consisting of phenyl radicals which are unsubstituted or substituted with from 3 to 5 substituents selected from the group consisting of a fluorine atom, a C1-4 alkyl or alkoxy radical which is unsubstituted or substituted by a fluorine atom; and a silyl radical of the formula -Si-(R9)3; wherein each R9 is independently selected from the group consisting of a hydrogen atom and a C1-4 alkyl radical; and (ii) compounds of the formula [(R8)tZH]+[B(R7)4]' wherein B is a boron atonv-Ris a hydrogen atom, Z is a nitrogen atom or.phosphorus atom, t is 2 or 3 and R8 is selected from the group consisting of C1-8 alkyl radicals, a phenyl radical which is unsubstituted or substituted by up to three C1-4 alkyl radicals, or one R8 taken together with the nitrogen atom may form an anilinium radical and R7 is as defined above; and (iii) compounds of the formula B(R7)3 wherein R7 is as defined above. In the above compounds preferably R7 is a pentafluorophenyl radical, and R5 is a triphenylmethyl cation, Z is a nitrogen atom and R8 is a C1-4 alkyl radical or R8 taken together with the nitrogen atom forms an anilinium radical which is substituted by two C1-4 alkyl radicals. The "ionic activator" may abstract the activatable ligand so as to ionize the catalyst center into a cation but not to covalently bond with the catalyst and to provide sufficient distance between the catalyst and the ionizing activator to permit a polymerizable olefin to enter the resulting active site. Examples of ionic activators include: triethylammonium tetra(phenyl)boron, 6 tripropylammonium tetra(phenyl)boron, tri(n-butyl)ammonium tetra(phenyl)boron, trimethylammonium tetra(p-tolyl)boron, trimethylammonium tetra(o-tolyl)boron, tributylammonium tetra(pentafluorophenyl)boron, tripropylammonium tetra{o,p-dimethylphenyl)boron, tributylammonium tetra(m,m-dimethylphenyl)boron, tributyiammonium tetra(p-trifluoromethylphenyl)boron; tributylammonium tetra(pentafluorophenyl)boron, tri(n-butyl)ammonium tetra(o-tolyl)boron N.N-dimetriylaniliniuni tetra(phenyl)boron, N,N-diethylanilinium tetra(phenyl)boron, N,N-diethylanilinium tetra(phenyl)n-butylboron, N,N-2,4,6-pentamethyianilinium tetra(pheny!)boron di-(isopropyl)ammonium tetra(pentafluorophenyl)borpn, dicyclohexylammonium tetra(phenyl)boron triphenylphosphonium tetra(prienyl)boron tri(methylphenyl)phosphonium tetra(phenyl)boron, tri(dimethylphenyl)phosphonium tetra(phenyl)boron, tropillium tetrakispentafluorophenyl borate, triphenylmethylium tetrakispentafluorophenyl borate, benzene (diazonium) tetrakispentafluorophenyl borate, tropillium phenyltrispentafluorophenyl borate, triphenylmethylium phenyltrispentafluorophenyl borate, benzene (diazonium) phenyltrispentafluorophenyl borate, tropillium tetrakis (2,3,5,6-tetrafluorophenyl) borate, triphenylmethylium tetrakis (2,3,5,6-tetrafluorophenyl) borate, benzene (diazonium) tetrakis (3,4,5-trifluorophenyl) borate, tropillium tetrakis (3,4,5-trifluorophenyl) borate, benzene (diazonium) tetrakis {3,4,5-trifluorophenyl) borate, tropillium tetrakis (1,2,2-trifluoroetheny!) borate, triphenylmethylium tetrakis (1,2,2-trifluoroethenyl) borate, 7 benzene (diazonium) tetrakis (1,2,2-trifluoroethenyl) borate, tropillium tetrakis (2,3,4,5-tetrafluorophenyl) borate, triphenylmethylium tetrakis (2,3,4,5-tetrafluorophenyl) borate, and benzene (diazonium) tetrakis (2,3,4,5-tetrafluorophenyl) borate Readily commercially available ionic activators include: N,N- dimethylaniliurntetrakispentafluorophenylborate; triphenylmethylium tetrakispentafluorophenylborate; and trispentafluorophenyl borane. 3. Homogeneous or Heterogeneous Catalyst The catalyst system of this invention may be used in a homogeneous form in solution polymerization (where the term "homogeneous" means that the catalyst and cocatalyst/activator are soluble in, or miscible with, the polymerization solvent). However, when the catalyst is employed in a slurry or gas phase polymerization, it is highly preferred to use the catalyst in a heterogeneous or "supported form". It is also highly preferred that the catalyst does not cause reactor fouling. The art of preparing heterogeneous catalysts which do not lead to reactor fouling is not adequately understood, though it is generally accepted that the catalytic material should be very well anchored to the support so as to reduce the incidence of foufing resulting from the deposition of catalyst or cocatalyst which has dissociated from the support. In general, heterogeneous catalysts may be grouped into three main categories: 3.1. Unsupported Alumoxane/Catalvst Mixtures These catalysts may be easily prepared by evaporating the solvent or diluent from a liquid mixture of an alumoxane and the catalyst component. The resulting product is a solid at room temperature due to the comparatively high molecular weight of the alumoxane. There are two disadvantages to this approach, namely cost (i.e. alumoxanes are comparatively expensive - and the alumoxane is used as an expensive "support" material) and "reaction continuity/fouling" (i.e. the alumoxane may partially melt under polymerization conditions, leading to reactor 8 instability/fouling). United States Patent (USP) 4,752,597 (Turner, to Exxon) illustrates this approach for the preparation of a heterogeneous catalyst. 3.2. Metal Oxide Supported Catalysts These catalysts are prepared by depositing the catalyst component and a cocatalyst on a very porous metal-oxide support. The catalyst and cocatalyst are substantially contained within the porestructure of the metal oxide particle. This means that a comparatively large metal oxide particle is used (typically particle size of from 40 to 80 microns). The preparation of this type of supported catalyst is described in USP 4,808,561 (Welborn, to Exxon). 3.3. Filled/Spray Dried Catalysts This method of catalyst preparation is also well known. For example, USPs 5,648,310; 5,674,795 and 5,672,669 (all to Union Carbide) teach the preparation of a heterogeneous catalyst by spray drying a mixture which contains a metallocene catalyst, an alumoxane cocatalyst anda "filler" which is characterized by having a very small particle size (less than one micron) and by being unreactive with the catalyst and cocatalyst. The examples illustrate the use of very fine particle size "fumed" silica which has been treated to reduce the concentration of surface hydroxyls. The resulting catalysts exhibit good productivity. Moreover, they offer the potential to provide a catalyst which is not prone to "hot spots" (as the catalyst may be evenly distributed, at low concentration, throughout the heterogeneous matrix). However, these catalysts suffer from the potential disadvantage of being very friable because they are prepared with a fine, "inert" filler material which does not react with/anchor to the catalyst or cocatalyst. Friable catalyst particles lead to the formation of "fines" in the polyethylene product, and may also aggravate reactor fouling problems. An alternative approach is the preparation of spray dried catalysts using a hydrotalcite as a "reactive" filler (as opposed to the unreactive filler described in the above-mentioned USP to Union Carbide). This method of 9 catalyst preparation is described in more detail in a commonly assigned patent application. Either approach is suitable for use with the catalysts of this invention. 4. Polymerization Processes The catalysts of this invention are suitable for use-in-any. conventional olefin polymerization process/such as the so-called "gas phase", "slurry", "high pressure" or "solution" polymerization processes. The use of a heterogeneous catalyst is preferred for gas phase and slurry processes whereas a homogeneous catalyst is preferred for the solution process. The polymerizationprocess according to this invention uses ethylene and may include other monomers which are copolymerizable therewith such as other alpha olefins (having from three to ten carbon atoms, preferably butene, hexene-or octene) and, under certain conditions, dienes such as hexadiene isomers, vinyl aromatic monomers such as styrene or cyclic olefin monomers such as norbornene. The present invention may also be used to prepare elastomeric co-and terpolymers of ethylene, propylene and optionally one or more diene monomers. Generally, such elastomeric polymers will contain about 50 to abut 75 weight % ethylene, preferably about 50 to 60 weight % ethylene and correspondingly from 50 to 25% of propylene. A portion of the monomers, typically the propylene monomer, may be replaced by a conjugated diolefin. The diolefin may be present in amounts up to 10 weight % of the polymer although typically is present in amounts from about 3 to 5 weight %. The resulting polymer may have a composition comprising from 40 to 75 weight % of ethylene, from 50 to 15 weight % of propylene and up to 10 weight % of a diene monomer to provide 100 weight % of the polymer. Preferred but not limiting examples of the dienes are dicyclopentadiene, 1,4-hexadiene, 5-methylene-2-norbornene, 5-ethylidene-2-norbornene and 5-vinyl-2-norbornene. Particularly preferred dienes are 5-ethylidene-2-norbornene and 1,4-hexadiene. 10 The polyethylene polymers which may be prepared in accordance with the present invention typically comprise not less than 60, preferably not less than 70 weight % of ethylene and the balance one or more C1-10 alpha olefins, preferably selected from the group consisting of 1-butene, 1-hexene and 1 octene. The polyethylene; prepared in accordance with the present invention may be linear low density polyethylene having density from about 0.910 to 0.935 g/cc The present invention might also be useful to prepare polyethylene having a density below 0.910 g/cc - the so-called very low and ultra low density polyethylenes. The most preferred polymerization process of this invention encompasses the use of the novel catalysts(together with a cocatalyst) in a medium pressure solution process. As used herein, the term "medium pressure solution process" refers to a polymerization carried out in a solvent for the polymer at an operating temperature from 100 to 320°C (especially-from.120 to 220oC)-and a total pressure of from 3 to 35 mega Pascals. Hydrogen may be used in this process to control (reduce) molecular weight. Optimal catalyst and cocatalyst concentrations are affected by such variables as temperature and monomer concentration but may be quickly optimized by non-inventive tests. Further details concerning the medium pressure polymerization process are well known to those skilled in the art and widely described in the open and patent literature. The catalyst of this invention may also be used in a slurry polymerization process or a gas phase polymerization process. The typical slurry polymerization process uses total reactor pressures of up to about 50 bars and reactor temperature of up to about 200°C. The process employs a liquid medium (e.g. an aromatic such as toluene or an alkane such as hexane, propane or isobutane) in which the polymerization takes place. This results in a suspension of solid polymer particles in the medium. Loop reactors are widely used in slurry processes. Detailed descriptions of slurry polymerization processes are widely reported in the open and patent literature. 11 In general, a fluidized bed gas phase polymerization reactor employs a "bed" of polymer and catalyst which is fluidized by a flow of monomer which is at least partially gaseous. Heat is generated by the enthalpy of polymerization of the monomer flowing through the bed. Unreacted monomer exits the fluidized bed and is contacted with a cooling system to remove this heat. The cooled monomer is then re-circulated through the polymerization zone together with "make-up" monomer to replace that which was polymerized on the previous pass. As will be appreciated by those skilled in the art, the "fluidized" nature of the polymerization bed helps to evenly distribute/mix the heat of reaction and thereby minimize the formation of localized temperature gradients (or "hot" spots"). Nonetheless, it is essential that the heat of reaction be properly removed so as to avoid softening or melting of the polymer (and the resultant-and highly undesirable - "reactor chunks"). The obvious way to-maintain good mixing and cooling is to have a very high monomer flow through the bed. However, extremely high monomer flow causes undesirable polymer entrainment. An alternative (and preferable) approach to high monomer flow is the use of an inert condensable fluid which will boil in the fluidized bed (when exposed to the enthalpy of polymerization), then exit the fluidized bed as a gas, then come into contact with a cooling element which condenses the inert fluid. The condensed, cooled fluid is then returned to the polymerization zone and the boiling/condensing cycle is repeated. The above-described use of a condensable fluid additive in a gas phase polymerization is often referred to by those skilled in the art as "condensed mode operation" and is described in additional detail in USP 4,543,399 and USP 5,352,749. As noted in the '399 reference, it is permissible to use alkanes such as butane, pentanes or hexanes as the condensable fluid and the amount of such condensed fluid preferably does not exceed about 20 weight per cent of the gas phase. Other reaction conditions for the polymerization of ethylene which are reported in the "399 reference are: 12 Preferred Polymerization Temperatures: about 75°C to about 115°C (with the lower temperatures being preferred for lower melting copolymers - especially those having densities of less than 0.915 g/cc -and the higher temperatures being preferred for higher density copolymers and homopolymers); and Pressure: up to about 1000 psi (with a preferred range of from about 100 to 350 psi for olefin polymerization)'. The '399 reference teaches that the fluidized bed process is well adapted for the preparation of polyethylene but further notes that other monomers may be employed - as is the case in the process of this invention. EXAMPLES The invention will now be illustrated in further detail by way of the following non-limiting examples. For clarity, the Examples have been divided into three parts, namely Part A (Catalyst Component Synthesis), Part B (Solution Polymerization) and Part C (Gas Phase Polymerization). Polymer Analysis Gel permeation chromatography ("GPC") analysis was carried out using a commercially available chromatograph (sold under the name Waters 150 GPC) using 1,2,4-trichlorobenzene as the mobile phase at 140°C. The samples were prepared by dissolving the polymer in the mobile phase solvent in an external oven at 0.1% (weight/volume) and were run without filtration. Molecular weights are expressed as polyethylene equivalents with a relative standard deviation of 2.9% and 5.0% for the number average molecular weight (Mn) and weight average molecular weight (Mw), respectively. Melt index (Ml) measurements were conducted according to ASTM method D-1238-82. Polymer densities were measured using pressed plaques (ASTM method D-1928-90), with a densitometer. The following abbreviations are used in the Examples: "Bu = tertiary butyl (e.g. tBu3 = tri-tertiary butyl) 13 Me = methyl Et = ethyl tH NMR = proton nuclear magnetic resonance 'Pr = isopropyl Ph = phenyl Mw = weight average molecular weight Mn = number average molecular weight PD = polydisperstty (or Mw/Mn) PE = polyethylene Cat = catalyst Hr. = hour M = molar MAO = methyl alumoxane PART A Catalyst Component Synthesis PART A1 (Prior Art) Synthesis 1 of Cyclopentadienyltitanium(IV)(tri-t-butylphosphinimine)dichloride Cyclopentadienyltitanium trichloride (4.025 g, 18.3 mmol) and N-trimethylsily!-tri-tert-buty!phosphinimine (5.47 g, 18.34 mmol) were combined as solids and dry toluene was added. The reaction was heated to 100°C for 1 hour and then allowed to cool to room temperature. The volatiles were removed in vacuo and the resulting yellow solid was isolated. Yield = 7.4 g. 1H NMR (da-toluene, 5 (298K)): 6.39 (singfet, 5H), 1,16 (doublet, J = 13.6 Hz, 27H). Synthesis 2 of Cvclopentadienvltitanium(IV)ftri-t-butylphosphinimineldichloride To a solution of lBu3P=N-H (0.200 g, 0.921 mmol) in dry toluene at room temperature was added a hexane solution of n-BuLi (0.57 mL, 1.6 M, 0.92 mmol). The addition was dropwise and resulted in a slightly turbid solution after 15 minutes of stirring. The lithium salt of the phosphinimine was then added dropwise to a slurry of cyclopentadienyltitanium(IV)trichloride (0.202 g, 0.921 mmol) in toluene. 14 After 4 hours the reaction mixture was filtered through a sintered glass frit and the solvent removed in vacuo to leave the product as a bright green solid. The solid was found to be - 98% pure. Yield = 247 mg, 67.1%. Synthesis 3 of Cvclopentadienyltitanium(IV)ftri-t-butylphosphinimine)dichloride fBu3P=N-H (0.200 g, 0.921 mmol) and cyclopentadienyltitanium(IV)trichloride'(0.202 g,0.921 mmol) were combined as solids and toluene was added. The reaction was allowed to stir for 30 minutes and then triethylamine (1.30 mL, 9.21 mmol, 10 equiv.) was added dropwise. During the addition, the-solution changed from orange to yellow as the sparingly soluble titanium reagent dissolved. The reaction was stirred for an additional 30 minutes and then filtered to remove the precipitated ammonium salt. Removal of the solvent in vacuo gave the product as a yellow crystalline solid. Yield = 336 mg,' 91.3%. Synthesis 4 of Cyclopentadienyltitanium(IV)(tri-t-butvlphosphinimine)dichloride To a solution of lBu3P=N-H (0.347-g, 1.60 mmbl) in toluene was added a hexane solution of n-BuLi (1.0 mL, 1.6 M, 1.6 mmol). The addition was dropwise and resulted in a slightly turbid solution after 15 minutes of stirring. The resulting lithium salt of the phosphinimine was then added dropwise to a stirred slurry of titanocene(IV)dichloride (0.398 g, 1.60 mmol) in toluene. After stirring at room temperature for 48 hours the solvent was removed in vacuo. The resulting brown solid was redissolved in the minimum amount of hot toluene and the solution filtered. Heptane was added to the solution and on standing overnight brown crystals of the product grew. These were isolated by decanting off the mother liquor and washing with heptane. Yield = 135 mg, 21 % (purity = 98%). Synthesis 5 of CvclopentadienvltitaniumflVUtri-t-butvlphosphinimine)dichloride To a solution of 'Bu3P=N-TiCb (0.370 g, 1.00 mmol) in toluene was added cyclopentadiene (0.660 g, 1.32 mL, 10.0 mmol). Triethylamine 15 (1.10 g, 1.39 mL, 10.0 mmol) was then added and the solution stirred for 18 hours. At this point the reaction mixture was heated at 80°C for 2 hours. The toluene was removed under reduced pressure to leave a yellow solid. This was washed with heptane and the product, isolated. 1H NMR showed the product contained some starting materials Synthesis 6 of CvclopentadienvltitaniumflV)(tri'-t-butylphosphinimine)dichloride tBu3P=N-TiCI3 (1.00 g, 2.70 mmol) and CpLi (0.194 g, 2.70 mmol) were combined as solids and toluene was added. The reaction mixture was stirred overnight, filtered through a sintered'glass frit and'then concentrated in vacuo. The resulting yellow solid was analyzed by NMR' and found to be pure product. Yield = 971 mg, 81%. Preparation of CvclopentadienvltitaniumflV)(tri-tert-butvlphosphinimine)f2-N.N-dimethvlamino)ben2vl Chloride. C.HgT;(NPtBu?)fCHgCfiH4NfCH^j)ei To a solution of cyclopentadienyltitanium(IV)(tri-t-butylphosphinimine) dichloride (1,904 g, 4.76 mmol) in anhydrous tetrahydrofuran (THF, 50 mL) at -78°C was added a solution of 2-N,N-dimethylaminobenzyl lithium (671 mg, 4.76 mmol) in THF (30 mL). A red color started to form immediately and the reaction was allowed to warm to room temperature. The solvent was removed in vacuo and the residue taken up in toluene and filtered. The toluene was then removed and the residues redissolved in hexane at 60°C. The solution was filtered and then placed in a -15°C freezer. The product formed as a pure orange crystalline solid on standing overnight and was isolated by filtration and pumping to dryness in vacuo. Yield = 1.45 g, 61%. 1H NMR (d8-toluene, 5 (298K)): 6.9-7.41 (m, Ph-H), 6.11 (s, Cp-H), 3.35 (d, J = 9.5 Hz, CHH). 3.03 (d, J = 9.5 Hz, CHH), 2.64 (s, N-CH3), 1.22 (d, J = 13.2 Hz, xBuH). 16 PART A2 A2.1 Preparation of CvclopentadienvltitaniumflV)(tri-tert-butylphosphinimine)(2-N,N-dimethvlamino)benzvl Chloride, CiH5Ti(NPtBu3)(CHgC5HgN(CH3)2)CI To a solution of cyclopentadieny!titanium(l V)(tri-t-butylphosphinimine) dichloride (1.904'g; 4.76 mmol) in anhydrous tetrahydrofuran (TMF, 50 mL) at -78°C was added a solution of 2-N.N-dimethylaminobenzyl fithium (671 mg, 4.76 mmol) in THF (30 mL). A red color started to form immediately and the reaction was allowed to warm to room temperature. The solvent was removed in vacuo and the residue taken up in toluene and filtered. The toluene was then removed and the residues redissolved in hexane at 60°C. The solution was filtered and then placed in a -15°C freezer. The product formed as a pure orange crystalline solid on standing overnight and was isolated by filtration and pumping to dryness'in vacuo. Yield =:1-.45 g,-61%. '1H NMR (da-toluene, 5 (298K)): 6.9 - 7.41 (m, Ph-H), 6.11 (s, Cp-H), 3.35 (d, J = 9.5 Hz, CHH), 3.03 (d, J = 9.5 Hz, CHH), 2.64 (s, N-CH3), 1.22 (d! J = 13.2 Hz, lBuH). A2.2 Preparation of Cvclopentadienvltitanium(lll)ftri-tert-butylphosphinimineK2-N.N-dimethvlamino)benzyl. C.H.TifNP'Bu^fCHgCfiKtNfCH^) To a flask containing cyclopentadienyltitanium(IV)(tri-tert-butylphosphinimine)(2-N,N-dimethylamino)benzyl chloride (600 mg, 1.23 mmol) and magnesium powder (1 g, 41 mmol) was added THF (30 mmol). The reaction was stirred for 5 days and then the THF was removed in vacuo. Hexane was added and the reaction flask warmed to 55°C. The solution was then filtered, concentrated in vacuo and cooled to -15°C. The product formed as a purple-red crystalline solid and was isolated by filtration and pumping to dryness in vacuo. Yield = 230 mg. Electron Paramagnetic Resonance (ESR) g = 1.9752. This g value confirms the presence of the Ti(lll) species. 17 A2.3 Preparation of Cvclopentadienvltitaniumftri-tert-butylphosphinimine)fbutadiene), CsHsTifNP'BtigMCdHg) Dry toluene (10 mL) was added to a flask containing cyclopentadienyltitanium(tri-tert-butylphosphinimine) dichloride (844 mg, 2.11 mmol) and magnesium butadiene complex, MgfG^He), (500 mg, 2.25 mmol) at room temperature. The reaction mixture immediately' became dark red and a slight exotherm was observed. After stirring for 1 hour the toluene was removed in vacuo and the product extracted with hexane. The solution was filtered and the hexane removed to leave the desired product as a pure dark red crystalline solid. Yield = 663 mg, 82%. 1H NMR (da-toluene, 5 (298K)): 5.66 (s; Cp-H), 4.75 (broad, butadiene), 1.09 (d, J = 12.5 Hz). A2.4 Preparation of CvclopentadienyltitaniurnnVUtri-te/t-butvlphosphinimine)-N,N'-dimethvlethvlenediamine, CgHgTi(NPtBUfl)fNfMe)CHpCH?N(Me)) To a solution of N.N'-dimethylethylenediamine (2.24 g, 2.70 mL, 25.4 mmol) in hexanes (15 mL) was slowly added a solution" of butyllithium (31.8 mL, 1.6 M in hexanes, 50.7 mmol). A white precipitate of the dilithio salt formed and this was isolated by filtration and dried in vacuo. A sample of the di-lithium salt of N,N'-dirnethylethylenediamine (0.100 g, 1.00 mmol) and cyclopentadienyltitanium(IV)(tri-f-butylphosphinimine)dichloride (0.400 mg, 1.00 mmol) were combined as solids and toluene (15 mL) was added. Upon addition of the solvent the reaction mixture rapidly changed from yellow to a brown, opaque solution. The reaction mixture was stirred for 1.5 hours and then filtered. The solvent was removed in vacuo yielding the product as a purple/brown solid. Yield = 317mg, 76%. 1H NMR (ds-toluene, 6 (298K)): 6.26 (s, Cp-H), 3.4 - 3.8 (broad multiplet, methylene protons), 2.91 (s, Me), 1.27(d, J = 12.4 Hz). 18 PART B Solution Polymerization PART B1 Solution Semi-Batch Reactor (SBR) Results All the polymerization experiments described below were conducted using a solution semi-batch reactor. All the chemicals (solvent, catalyst and cocatalyst) were fed into the reactor batchwise except ethylene which was fed on demand and no removalofproduct during the polymerization reaction. All the feed streams were purified prior to the reactor by contact with various absorption media to remove catalysts killing impurities such as water, oxygen, sulfur and polar materials as are known to those skilled in the art;'All components were stored and manipulated under an atmosphere of purified a'rgon or nitrogen. The SBR uses a programmable logical control (PLC) system with Wonderware 5.1 software for process control. Ethylene polymerizations were performed in a 500 mL Autoclave Engineers Zipperclave reactor equipped with an air driven stirrer.and an automatic temperaturercontrol system; The polymerization time was 10 minutes in each experiment. The reaction was terminated by adding 5 mL of methanol to the reactor and Two catalysts were used, namely C5H5T\(NPtBu3)(CH2C6^4N(CH3)2) (referred to as:."RS^676-89" in the following-table;'synthesis described in Part A, Section A2.2) and the comparative catalyst cyclopentadienyl titanium (IV) tri-t-butylphosphinimine dichloride ("JS304"; synthesis described in Part A, Section A1), were prepared as described in Part A. The catalysts were dissolved in toluene and the catalyst concentrations were between 0.7-5 mg/mL A commercially available methylalumoxane (PMAO-IP, purchased from Akzo-Nobel) was used in the experiments. The experiments were carried out as follows: 19 the polymer was recovered by evaporation of the cyclohexane. The polymerization activities were calculated based on the ethylene consumed during the reaction, not the weight of'the polymer produced. 1" The calculation of polymerization activity is based on the ethylene uptake. C: comparative Polymer molecular weights and molecular weight distributions were measured by GPC (Waters 150-C) at 140°C in r,2,4-frichlor6be'nzene calibrated using polyethylene standards. C: comparative The polyethylene produced by the inventive catalyst RS-676-89 has a low molecular weight tail, which contributes to a higher polydispersity of 5.4. The inventive experiment using RS-676-89 showed a different kinetic profile which may be a result of the Ti(lll) species. The "initial" activity of the inventive experiment was slower/lower, but the overall activity was high. This is very desirable for commercial-scale polymerizations having a residence time of more than 2 minutes. PART B2 The Continuous Solution Polymerization All the polymerization experiments described below were conducted on a continuous solution polymerization reactor. The process is continuous in all feed streams (solvent, monomers and catalyst) and in the removal of product. All feed streams were purified prior to the reactor by contact with various absorption media to remove catalyst killing 20 impurities such as water, oxygen and polar materials as is known to those skilled in the art. All components were stored and manipulated under an atmosphere of purified nitrogen. All the examples below were conducted in a reactor of 71.5 cc internal volume. In each experiment thevolumetric feed to trie reactor was kept constant and as a consequence so was the reactor residence time. The catalyst solutions were pumped to'the reactor independently and in some cases were mixed before entering the polymerization reactor (as indicated in the examples): Because of the low solubility of the catalysts, activators and MAO in cycl6hexahe, solutions were prepared in purified xylene. The catalyst was activated in-situ {in the polymerization reactor) at the reaction temperature in the presence of the monomers. The polymerizations were carried out in cyclohexane at a pressure of 1500' psi. Ethylene was supplied to the reactor-by-a calibrated:thermal mass' flow meter and was dissolved in the reaction solvent prior to the polymerization reactor, ifcomonomer (forex"ample'i-octerie) was used it was also premixed with the ethylene before entering the polymerization reactor. Under these conditions the ethylene conversion is a dependent variable controlled by the catalyst concentration, reaction temperature and catalyst activity, etc. The internal reactor temperature is monitored by a thermocouple in the polymerization medium and can be controlled at the required set point to +/- 0.5°C. Downstream of the reactor the pressure was reduced from the reaction pressure {1500 psi) to atmospheric. The solid polymer was then recovered as a slurry in the condensed solvent and was dried by evaporation before analysis. The ethylene conversion was determined by a dedicated on line gas chromatograph by reference to propane which was used as an internal standard. The average polymerization rate constant was calculated based on the reactor hold-up time, the catalyst concentration in the reactor and the ethylene conversion and is expressed in l/(mmormin). 21 Average polymerization rate (kp) = (Q/(100-Q)) x (1/[TM]) x (1/HUT) where : Q is the percent ethylene conversion. [TM] is the catalyst concentration in the reactorexpressed in mM. HUT is the reactor hold-up lime in minutes. Polymer Analysis, Melt index (Ml) measurements were conducted according to ASTM method D-1238-82. Polymer densities were measured on pressed plaques (AST-M D-1928-90) witha-densitometer. Example 1 CpTiNP^Bu^butadiene) (from Part A; Section A2.3) was added to the reactor at 9.3 x 10'6 mol/l along with Ph3C B(C6F5)4 (purchased from "Asahi Glass") at B/Ti = 1.00 (mol/mol). Both components were mixed-in the polymerization reactor. The reaction temperature was 1.60°C cTnd. 2.1 gram/min of ethylene was continuously added to the reactor. An ethylene conversion'of 98.8% was observed (see Table B2.1). Example 2 CpTiNP(tBu)3(butadiene) was added to the reactor at 9.3 x 10"6 mol/l along with B(C6F5)3 (purchased from "Boulder Scientific") at B/Ti = 2.5 (mol/mol). Both components were mixed before the polymerization reactor. The reaction temperature was 160°C and 2.1 gram/min of ethylene was continuously added to the reactor. An ethylene conversion of 70.7% was observed (see Table B2.1). Example 3 CpTiNP(lBu)3(butadiene) was added to the reactor at 2.3 x 10"6 mol/l along with Ph3C B(C6F5)4 (Asahi Glass) at B/Ti = 1.00 (mof/mol). Both components were mixed in the polymerization reactor. The reaction temperature was 160°C and 2.1 gram/min of ethylene was continuously added to the reactor. An ethylene conversion of 96.3% was observed (see Table B2.1). 22 Example 4 CpTiNP(fBu)3(butadiene) was added to the reactor at 5.3 x 10'6 mol/l along with MMAO-7 (purchased from "Akzo-Nobel") at Al/Ti = 40.0 (mol/mol). Both components were mixed in the polymerization reactor. The reaction temperature was 160°C and 2.1 gram/min of ethylene was continuously added to the reactor." An ethylene conversion of 89.4% was observed (see-Table B2.1). Example 5 CpTiNP(lBu)3(butadiene) was added to the reactor at 5.8 x 10'6 mol/l along with MMAO-7 (Akzo-Nobel) at Al/Ti = 40.0 (mol/mol). Both components were mixed in the polymerization reactor. The reaction temperature was 160°C and 2.1 gram/min of ethylene was continuously added to the reactor as was 1.0 ml/min of 1-octene. An ethylene conversion of 89.4% was observed (see Table B2.1). Example 6 CpTiNP^Bu^butadiene) was added to the reactor at 8.1 x 10"6 mol/l along witfrMMAO-7 (Akzo-Nobel) -at Al/Ti = 40.0 (mol/mol). Both components were mixed in the polymerization reactor. The reaction temperature was 160°C and 2.1 gram/min of ethylene was continuously added to the reactor as was 3.0 ml/min of 1-octene. An ethylene conversion of 90.2% was observed (see Table B2.1). Example 7 CpTiNP('Bu)3(butadiene) was added to the reactor at 8.1 x 10'6 mol/l along with MMAO-7 (Akzo-Nobel) at Al/Ti = 40.0 (mol/mol). Both components were mixed in the polymerization reactor. The reaction temperature was 160°C and 2.1 gram/min of ethylene was continuously added to the reactor as was 5.0 ml/min of 1-octene. An ethylene conversion of 90.4% was observed (see Table B2.1). Example 8 CpTiNP(lBu)3(butadiene) was added to the reactor at 1.9 x 10'6 mol/l along with MMAO-7 (Akzo-Nobel) at Al/Ti = 40.0 (mol/mol) and Ph3C 23 B(C6F5)4 (Asahi Glass) at B/Ti = 1.00 (mol/mol). CpTiNP(tBu)3(butadiene) and Ph3C B(C6F5)4 were mixed before the reactor and were subsequently mixed with the MMAO-7 in the reactor. The reaction temperature was 160°C and 2.1 gram/min of ethylene was continuously added to.the reactor as was 3.0 ml/min of 1-octene. An ethylene" conversion of'91-.3% was observed.(see Table B2.1); Example 9 CpTiNP([Bu)3(butadiene) was added to the reactor at 1.9 x 10'6 mol/l along with MMAO-7 (Akzo-Nobel) at Af/Ti = 40.0 (mol/mol) and Ph3C B(C6F5)4 (Asahi Glass) at B/Ti =±1.00 (mol/mol). CpTiNP(lBu)3(butadiene) and Ph3CB(C6F5)4 were mixed before the reactor and were subsequently mixed with the MMAO-7 in the reactor. The reaction temperature was 160°C and 2.1 gram/min of ethylene was continuously added to the reactor as was 5.0 ml/min of 1-octene: An ethylene conversion of 90.5% was observed (see Table B2;1).-Example 10 CpTiNP('Bu)3(butadiene) wasadded to the reactor at 1.9 x 10"6 mol/l along with MMAO-7 (Akzo-Nobel) at Al/Ti = 40.0 (mol/mol) and Ph3C B(C6F5)4 (Asahi Glass) at B/Ti = 1.00 (mol/mol). CpTiNP(lBu)3(butadiene) and Ph3C B(CeF5)4 were mixed before the reactor and were subsequently mixed with the MMAO-7 in the reactor. The reaction temperature was 160°C and 2.1 gram/min of ethylene was continuously added to the reactor as was 1.0 ml/min of 1-octene. An ethylene conversion of 91.3% was observed (see Table B2.1). Example 11 CpTiNP(!Bu)3(butadiene) was added to the reactor at 1.9 x 10"6 mol/l along with MMAO-7 (Akzo-Nobel) at Al/Ti = 40.0 (mol/mol) and Ph3C B(C6F5)4 (Asahi Glass) at B/Ti = 1.00 (mol/mol). CpTiNP((Bu)3(butadiene) and Ph3C B(C6F5)4 were mixed before the reactor and were subsequently mixed with the MMAO-7 in the reactor. The reaction temperature was 24 160°C and 2.1 gram/min of ethylene was continuouslyadded to the reactor. An ethylene conversion of 90.7% was observed (see Table B2.1). Example 12 CpTiNP(tBu)3(CH2C6H4-2-NMe2) (from Part A; Section A2.2) was added to the reactor at 9.3 x 10"6 mol/I along, with Ph3C B(C6F5)4 (Asahi Glass) at B/Ti =± 1.00 (mol/mol). Both components were1 mixed in the polymerization reactor. The reaction temperature was 160°C and 2.1 gram/min of ethylene was continuously added to the reactor. An ethylene conversion of 93.5% was observed (see Table B2.1). Example 13 CpTiNP(tBu)3(CH2C6H4-2-NMe2) was added to the reactor at 4.6 x 10"6 mol/I along with HNMe2Ph B(C6F5)4 (Akzo-Nobel) at B/Ti = 1.00 (mol/mol). Both components were mixed in the polymerization reactor. The reaction temperature was 160°C and 2.1 gram/min of "ethylene was continuously added to the reactor. An ethylene conversion of 91.5% was observed (see Table B2.1). Example 14 CpTiNP(tBu)3(CH2C6H4-2-NMe2) was added to the reactor at 13.0 x 10"6 mol/I along with MMAO-7 (Akzo-Nobel) at Al/Ti = 50.0 (mol/mol). Both components were mixed in the polymerization reactor. The reaction temperature was 160°C and 2.1 gram/min of ethylene was continuously added to the reactor as was 3.0 ml/min of 1-octene. An ethylene conversion of 89.1% was observed (see Table B2.1). Example 15 CpTiNP{tBu)3(CH2C6H4-2-NMe2) was added to the reactor at 9.3 x 10'6 mol/I along with MMAO-7 (Akzo-Nobel) at Al/Ti = 40.0 (mol/mol) and Ph3C B(C6F5)4 (Asahi Glass) at B/Ti = 1.00 (mol/mol). All components were mixed in the reactor. The reaction temperature was 160°C and 2.1 gram/min of ethylene was continuously added to the reactor. An ethylene conversion of 92.8% was observed (see Table B2.1). 25 Example 16 CpTiNP(tBu)3(CH2C6H4-2-NMe2) was added to the reactor at 9.3 x 10'6 mol/l along with MMAO-7 (Akzo-Nobel) at Al/Ti = 40.0 (moi/mol) and Ph3C B(C6F5)4 (Asahi Glass) at B/Ti = 1,00 (mol/mol). Ail components -were mixed in the reactor. The reaction temperature was 160°Oand 2.1 gram/min of ethylene was continuously added to'the reactor as was 3.0 ml/min of 1-octene. An ethylene conversionof 93.6% was observed (see Table B2.1). Comparative Example 17C (C5Me5)2ZrCl2 (purchased from "Strem") was added to'the reactor at 37 x 10"6 mol/l along with MMAO-3 (Akzo-Nobel, Al/Ti = 400 mol/mol). The reaction temperature was 140°C and 1.0 gram/min of ethylene was continuously added to the reactor. An ethylene conversion of 55.5% was observed (see Table B2.1). Comparative Example 18C (C5Me5)2ZrCl2 (Strem) was added to the reactor at 37 x 10"6 mol/l along with MMAO-3 (Akzo-Nobel, Al/Ti = 400 mol/mol). The reaction temperature was 160°C and 1.0 gram/min of ethylene was continuously added to the reactor. An ethylene conversion of 35.6% was observed (see Table B2.1). Comparative Example 19C (C5Me5)2ZrCI2 (Strem) was added to the reactor at 37 x 10'6 mol/l along with MMAO-3 (Akzo-Nobel, Al/Ti = 400 mol/mol). The reaction temperature was 160°C and 2.1 gram/min of ethylene was continuously added to the reactor. An ethylene conversion of 37.4% was observed (see Table B2.1). Comparative Example 20C rac-Et(ind)2ZrCI2 (purchased from "Witco") was added to the reactor at 37 x 10"6 mol/l along with MMAO-3 (Akzo-Nobel, Al/Ti = 400 mol/mol). The reaction temperature was 160°C and 2.1 gram/min of ethylene was 26 continuously added to the reactor. An ethylene conversion of 94.6% was observed (see Table B2.1). Comparative Example 21C rac-Et(ind)2ZrCI2 (Witco) was added to the reactor at 37 x 10'6 mol/l along with MMAO-3 (Akzo-Nobel, Al/Ti = 400 mol/mol). The reaction-temperature was 160°C and 2.1 gram/min of ethylene and 3.25 ml/min of 1-octene was continuously added to the reactor. An ethylene conversion of 94.8% was observed (see Table B2.1). 27 28 PART C Gas Phase Polymerization Catalyst Preparation and Polymerization Testing Using a Semi-Batch, Gas Phase Reactor The catalyst preparation methods described below employ typical, techniques for the syntheses and handling of air-sensitive,rnaterials.' Where appropriate, elemental compositions of the supported catalysts were measured by Neutron Activation analysis and a.reported accuracy of + 1% (weight basis). The supported catalysts were prepared by initially supporting MAO on a silica support, followed by deposition of the catalyst .component.- All the polymerization experiments described below were conducted using a semi-batch, gas phase polymerization reactor of total internal volume of 2.2 L. Reaction gas mixtures, including ethylene/butene mixtures (96 mole % ethylene, 4 mole % butene) were measured to the reactor on a continuous basis using a calibrated "thermal mass flow meter, following passage through purificatidn:media as-described above. A predetermined mass of the catalyst sample as added to the reactor under the flow of the inlet gas with no pre-contact of the catalyst with any reagent, such as a catalyst activator. The catalyst was activated in-situ (in the polymerization reactor) at the reaction temperature in the presence of the monomers, using a metal alkyl complex which has been previously added to the reactor to remove adventitious impurities. Purified and rigorously anhydrous sodium chloride was used as a catalyst dispersing agent. The internal reactor temperature is monitored by a thermocouple in the polymerization medium and can be controlled at the required set point to +/-1.0°C. The duration of the polymerization experiment was one hour. Following the completion of the polymerization experiment, the polymer was separated from the sodium chloride and the yield determined. 29 Table C1 illustrates data concerning the Al/transition metal ratios of the supported catalyst and polymer yield. Polymer properties are shown in Table C2. INDUSTRIAL APPLICABILITY The inventive complexes are well-suited for. use as a component in a catalyst system for the polymerization-of olefins- especially ethylene; Polyethylene produced with the inventive complexes is useful, for example, in the production of film, extruded parts and profiles and molded plastic goods. 30 31 WE CLAIM 1. A process for the polymerization or ethylene characterized in that said pocess Is conducted In the presence of: (a) an organometallic complex defined by the formula: wherein Cp is a cyclopentadienyMype ligand; L is an actrvatable Ligand; M is a metal selected from Ti and Zr; and PI is a phosphinimine ligand defined by the formula: wherein each R1 is independently selected from the group consisting of a hydrogen atom, a halogen atom, C1.20 hydrocarbyl radicals which are unsubstituted by or further substituted by a halogen atom, a C1-8 alkoxy radical, an amido radical, a C6-10 aryl or aryloxy radical, a silyl radical of the formula: wherein each R2 Is independently selected from the group consisting of hydrogen, a C1-8 alkyl or alkoxy radical, C8-10 aryl or aryloxy radicals, and a germanyl radical of the formula: Ge-(R2)3 wherein R2 is as defined above; and (b) an activator at a temperature of from 75°C to 320°C and a pressure of from 100 psi to 35 mega Pascals. 2. The process as claimed in claim 1 wherein said ethylene is copolymerized with a minor amount of an alpha olefin having from 3 to 10 carbon atoms. 3. The process as claimed in claim 1 wherein said activator Is an Ionic activator. 32 4. The process as claimed in claim 1, wherein each R1 fs tertiary butyl and M is titanium (III). A process for the polymerization of ethylene characterized in that said pocess is conducted in the presence of: an organometallic complex defined by the formula: wherein Cp is a cyclopentadienyl-type ligand; L is an activatable Ligand; M is a metal selected from Ti and Zr; and PI is a phosphinimine ligand defined by the formula: wherein each R1 is independently selected from the group consisting of a hydrogen atom, a halogen atom, C1-20 hydrocarbyl radicals which are unsubstituted by or further substituted by a halogen atom, a C1-8 alkoxy radical, an amido radical, a C6-10 aryl or aryloxy radical, a silyl radical of the formula: wherein each R2 is independently selected from the group consisting of hydrogen, a C1-6 alkyl or alkoxy radical, C6-10 aryl or aryloxy radicals, and a germanyl radical of the formula: Ge-(R2)3 wherein R2 is as defined above; and an activator at a temperature of from 75°C to 320°C and a pressure of from 100 psi to 35 mega Pascals.

Full Text

CYCLOPENTADIENYL/PHOSPHINIMINE CATALYST WITH ONE AND ONLY ONE ACTIVATABLE LIGANP
TECHNICAL FIELD
This invention relates to an olefin polymerization catalyst component which is an organometaHic complex having three ligands, namely a cyclopentadienyl ligand, a phosphinimine ligand and only one activatable ligand.
BACKGROUND ART
Certain "metallocenes". (especially bis-cyclopentadienyl complexes of group 4 metals) are highly productive catalysts for olefin polymerization when used in combination with an appropriate activator (see, for example, United States Patent CUSP") 4,542,199 (Sinn et at) and USP 5,198,401 (Hlatky and Turner).
Olefin polymerization catalysts which contain a group 4 metal and one cyclopentadienyl ligand, one phosphinimine ligand and two monoanionic activatable ligands are-disclosed in a commonly assigned patent application (Stephan et al). Thus, the catalysts of Stephan et a/are group 4 metals in the 4+ oxidation state.
We have now discovered a new family of olefin polymerization catalysts which contain a group 4 metal, a cyclopentadienyl ligand or phosphinimine ligand and only one activatable ligand. A preferred family of these catalysts contains Ti(lll) and offers an excellent kinetic profile when used in olefin polymerization.
DISCLOSURE OF INVENTION
The present invention provides a catalyst component for olefin polymerization which is an organometaHic complex defined by the formula:

2
wherein Cp is a cyclopentadienyl-type ligand; L is an activatable ligand; M is a metal selected from Ti and Zr; and PI is a phosphinimine ligand defined by the formula:

wherein each R1 is independently selected from the group consisting of a hydrogen atom, a halogen atom, C1-20 hydrocarbyl radicals which are unsubstituted by or further substituted by a halogen atom, a C1-8 alkoxy radical, an amido radical, a C6-10 aryl or aryloxy radical, a silyl radical of the formula:
-Si-(R2)3
wherein each R2 is independently selected from the group consisting of hydrogen, a C1-8 alkyl or alkoxy radical, C6-10 aryl or aryloxy radicals, and a germanyl radical of the formula:
Ge-(R2)3 wherein R2 is as defined above.
BEST MODE FOR CARRYING OUT THE INVENTION 1. Description of Catalyst Component
1.1 Metals
The catalyst component of this invention is a group 4 metal selected from titanium and zirconium.
1.2 Phosphinimine Ligand
The catalyst component of this invention must contain a phosphinimine ligand which is covalently bonded to the metal. This ligand is defined by the formula:

3
wherein each Ft1 is independently selected from the group consisting of a hydrogen atom, a halogen atom, C1-20 hydrocarbyl radicals which are unsubstituted by or further substituted by a halogen atom, a C1-8 alkoxy radical, a C6-10 aryl or aryloxy radical, an amido radical, a silyl radical of the formula:
-Si-(R2)3
wherein each R2 is independently selected from the group consisting of hydrogen, a C1-8 alkyl or alkoxy radical, C6-10 aryl or aryloxy radicals; and a germanyl radical of the formula:
Ge-(R2)3 wherein R2 isas defined above.
The preferred phosphinimines are those in which each R1 is a hydrocarbyl radical. A particularly preferred phosphinimine is tri-(tertiary butyl) phosphinimine (i.e. where each R1 is a tertiary butyl group). 1.3 Cvclopentadienvl-Type Liqand
The term cyclopentadienyl-type ligand (or "Cp ligand") refers to a ligand which is cyclic and forms a delocalized pi-borid with the group 4 transition metal. An exemplary (i.e. illustrative but non-limiting) list of "Cp ligands" includes substituted (or unsubstituted) cyclopentadienyl ligands, substituted (or unsubstituted) indenyf ligands, and substituted (or unsubstituted) fluorenyl ligands.
The use of "substituents" on such cyclic ligands is well known and is described, for example, in USP 5,324,800 (Welborn). An exemplary list of substituents for such Cp ligands includes C1-20 hydrocarbyl groups; substituted C1-20 hydrocarbyl groups wherein one or more hydrogen atoms is replaced by a halogen; an amido group, a phosphido group, or an alkoxy group. The substituent may form a bridge with the phosphinimine ligand.
For reasons of cost and simplicity, it is especially preferred that the Cp ligand is a cyclopentadienyl or indenyl ligand.

4
1.4 Activatable Liqand
The term "activatable ligand" refers to a ligand which may be activated by a cocatalyst (also known as an "activator" to facilitate olefin polymerization. Exemplary activatable ligands are independently selected from the group consisting of a hydrogen atom, a halogen atom, a C1-10 hydrocarbyl radical, a C1-10 alkoxy radicalra C5-10 aryl oxide radical; each of which said hydrocarbyl, alkoxy, and aryl oxide radicals may be unsubstituted by or further substituted by a halogen atom, a C1-8 alkyl radical, a C1-8 alkoxy radical, a C6-10 aryl or aryl oxy radical, an amido radical which is unsubstituted or substituted by up to two C1-8 alkyl radicals; a phosphido radical which is unsubstituted or substituted by up to two C1-8 alkyl radicals. 2. Description of Activators (or "Cocatalvsts")
The catalyst components described in part 1 above are used in combination with an "activator" (which may also be referred to by a person skilled in the art as a "cocatalyst") to form an active catalyst system for olefinpolymerization. Simple aluminum alkyls and alkoxides may provide comparatively weak cocatalytic activity under certain mild polymerization conditions. However, the preferred activators are alumoxanes and so-called ionic activators, as described below. 2.1 Alumoxanes
The alumoxane activator may be of the formula:
(R4)2AIO(R4A!O)mA!(R4)2
wherein each R4 is independently selected from the group consisting of C1-20 hydrocarbyl radicals and m is from 0 to 50, preferably R4 is a C1-4 alkyl radical and m is from 5 to 30. Methylalumoxane (or "MAO") is the preferred alumoxane.
Alumoxanes are well known as activators for metallocene-type catalysts.
Activation with alumoxane generally requires a molar ratio of aluminum in the activator to (group 4) metal in the catalyst from 20:1 to 1000:1. Preferred ratios are from 50:1 to 250:1.

5
2.2 Ionic Activators
Ionic activators are also well known for metallocene catalysts. See, for example, USP 5,198,401 (Hlatky and Turner). These compounds may be selected from the group consisting of:
(i) compounds of the formula [R5]+ [B(R7)4]' wherein B is a boron atom, R5 is a cyclic C5-7 aromatic cation or a triphenylmethyl cation and each R7 is independently selected from the group consisting of phenyl radicals which are unsubstituted or substituted with from 3 to 5 substituents selected from the group consisting of a fluorine atom, a C1-4 alkyl or alkoxy radical which is unsubstituted or substituted by a fluorine atom; and a silyl radical of the formula -Si-(R9)3; wherein each R9 is independently selected from the group consisting of a hydrogen atom and a C1-4 alkyl radical; and
(ii) compounds of the formula [(R8)tZH]+[B(R7)4]' wherein B is a boron atonv-Ris a hydrogen atom, Z is a nitrogen atom or.phosphorus atom, t is 2 or 3 and R8 is selected from the group consisting of C1-8 alkyl radicals, a phenyl radical which is unsubstituted or substituted by up to three C1-4 alkyl radicals, or one R8 taken together with the nitrogen atom may form an anilinium radical and R7 is as defined above; and (iii) compounds of the formula B(R7)3 wherein R7 is as defined above.
In the above compounds preferably R7 is a pentafluorophenyl radical, and R5 is a triphenylmethyl cation, Z is a nitrogen atom and R8 is a C1-4 alkyl radical or R8 taken together with the nitrogen atom forms an anilinium radical which is substituted by two C1-4 alkyl radicals.
The "ionic activator" may abstract the activatable ligand so as to ionize the catalyst center into a cation but not to covalently bond with the catalyst and to provide sufficient distance between the catalyst and the ionizing activator to permit a polymerizable olefin to enter the resulting active site.
Examples of ionic activators include: triethylammonium tetra(phenyl)boron,

6
tripropylammonium tetra(phenyl)boron, tri(n-butyl)ammonium tetra(phenyl)boron, trimethylammonium tetra(p-tolyl)boron, trimethylammonium tetra(o-tolyl)boron, tributylammonium tetra(pentafluorophenyl)boron, tripropylammonium tetra{o,p-dimethylphenyl)boron, tributylammonium tetra(m,m-dimethylphenyl)boron, tributyiammonium tetra(p-trifluoromethylphenyl)boron; tributylammonium tetra(pentafluorophenyl)boron, tri(n-butyl)ammonium tetra(o-tolyl)boron N.N-dimetriylaniliniuni tetra(phenyl)boron, N,N-diethylanilinium tetra(phenyl)boron, N,N-diethylanilinium tetra(phenyl)n-butylboron, N,N-2,4,6-pentamethyianilinium tetra(pheny!)boron di-(isopropyl)ammonium tetra(pentafluorophenyl)borpn, dicyclohexylammonium tetra(phenyl)boron triphenylphosphonium tetra(prienyl)boron tri(methylphenyl)phosphonium tetra(phenyl)boron, tri(dimethylphenyl)phosphonium tetra(phenyl)boron, tropillium tetrakispentafluorophenyl borate, triphenylmethylium tetrakispentafluorophenyl borate, benzene (diazonium) tetrakispentafluorophenyl borate, tropillium phenyltrispentafluorophenyl borate, triphenylmethylium phenyltrispentafluorophenyl borate, benzene (diazonium) phenyltrispentafluorophenyl borate, tropillium tetrakis (2,3,5,6-tetrafluorophenyl) borate, triphenylmethylium tetrakis (2,3,5,6-tetrafluorophenyl) borate, benzene (diazonium) tetrakis (3,4,5-trifluorophenyl) borate, tropillium tetrakis (3,4,5-trifluorophenyl) borate, benzene (diazonium) tetrakis {3,4,5-trifluorophenyl) borate, tropillium tetrakis (1,2,2-trifluoroetheny!) borate, triphenylmethylium tetrakis (1,2,2-trifluoroethenyl) borate,

7
benzene (diazonium) tetrakis (1,2,2-trifluoroethenyl) borate, tropillium tetrakis (2,3,4,5-tetrafluorophenyl) borate, triphenylmethylium tetrakis (2,3,4,5-tetrafluorophenyl) borate, and benzene (diazonium) tetrakis (2,3,4,5-tetrafluorophenyl) borate
Readily commercially available ionic activators include: N,N- dimethylaniliurntetrakispentafluorophenylborate; triphenylmethylium tetrakispentafluorophenylborate; and trispentafluorophenyl borane. 3. Homogeneous or Heterogeneous Catalyst
The catalyst system of this invention may be used in a homogeneous form in solution polymerization (where the term "homogeneous" means that the catalyst and cocatalyst/activator are soluble in, or miscible with, the polymerization solvent). However, when the catalyst is employed in a slurry or gas phase polymerization, it is highly preferred to use the catalyst in a heterogeneous or "supported form". It is also highly preferred that the catalyst does not cause reactor fouling. The art of preparing heterogeneous catalysts which do not lead to reactor fouling is not adequately understood, though it is generally accepted that the catalytic material should be very well anchored to the support so as to reduce the incidence of foufing resulting from the deposition of catalyst or cocatalyst which has dissociated from the support.
In general, heterogeneous catalysts may be grouped into three main categories: 3.1. Unsupported Alumoxane/Catalvst Mixtures
These catalysts may be easily prepared by evaporating the solvent or diluent from a liquid mixture of an alumoxane and the catalyst component. The resulting product is a solid at room temperature due to the comparatively high molecular weight of the alumoxane. There are two disadvantages to this approach, namely cost (i.e. alumoxanes are comparatively expensive - and the alumoxane is used as an expensive "support" material) and "reaction continuity/fouling" (i.e. the alumoxane may partially melt under polymerization conditions, leading to reactor

8
instability/fouling). United States Patent (USP) 4,752,597 (Turner, to Exxon) illustrates this approach for the preparation of a heterogeneous catalyst.
3.2. Metal Oxide Supported Catalysts
These catalysts are prepared by depositing the catalyst component and a cocatalyst on a very porous metal-oxide support. The catalyst and cocatalyst are substantially contained within the porestructure of the metal oxide particle. This means that a comparatively large metal oxide particle is used (typically particle size of from 40 to 80 microns). The preparation of this type of supported catalyst is described in USP 4,808,561 (Welborn, to Exxon).
3.3. Filled/Spray Dried Catalysts
This method of catalyst preparation is also well known. For example, USPs 5,648,310; 5,674,795 and 5,672,669 (all to Union Carbide) teach the preparation of a heterogeneous catalyst by spray drying a mixture which contains a metallocene catalyst, an alumoxane cocatalyst anda "filler" which is characterized by having a very small particle size (less than one micron) and by being unreactive with the catalyst and cocatalyst. The examples illustrate the use of very fine particle size "fumed" silica which has been treated to reduce the concentration of surface hydroxyls. The resulting catalysts exhibit good productivity. Moreover, they offer the potential to provide a catalyst which is not prone to "hot spots" (as the catalyst may be evenly distributed, at low concentration, throughout the heterogeneous matrix). However, these catalysts suffer from the potential disadvantage of being very friable because they are prepared with a fine, "inert" filler material which does not react with/anchor to the catalyst or cocatalyst.
Friable catalyst particles lead to the formation of "fines" in the polyethylene product, and may also aggravate reactor fouling problems.
An alternative approach is the preparation of spray dried catalysts using a hydrotalcite as a "reactive" filler (as opposed to the unreactive filler described in the above-mentioned USP to Union Carbide). This method of

9
catalyst preparation is described in more detail in a commonly assigned patent application. Either approach is suitable for use with the catalysts of this invention. 4. Polymerization Processes
The catalysts of this invention are suitable for use-in-any. conventional olefin polymerization process/such as the so-called "gas phase", "slurry", "high pressure" or "solution" polymerization processes.
The use of a heterogeneous catalyst is preferred for gas phase and slurry processes whereas a homogeneous catalyst is preferred for the solution process.
The polymerizationprocess according to this invention uses ethylene and may include other monomers which are copolymerizable therewith such as other alpha olefins (having from three to ten carbon atoms, preferably butene, hexene-or octene) and, under certain conditions, dienes such as hexadiene isomers, vinyl aromatic monomers such as styrene or cyclic olefin monomers such as norbornene.
The present invention may also be used to prepare elastomeric co-and terpolymers of ethylene, propylene and optionally one or more diene monomers. Generally, such elastomeric polymers will contain about 50 to abut 75 weight % ethylene, preferably about 50 to 60 weight % ethylene and correspondingly from 50 to 25% of propylene. A portion of the monomers, typically the propylene monomer, may be replaced by a conjugated diolefin. The diolefin may be present in amounts up to 10 weight % of the polymer although typically is present in amounts from about 3 to 5 weight %. The resulting polymer may have a composition comprising from 40 to 75 weight % of ethylene, from 50 to 15 weight % of propylene and up to 10 weight % of a diene monomer to provide 100 weight % of the polymer. Preferred but not limiting examples of the dienes are dicyclopentadiene, 1,4-hexadiene, 5-methylene-2-norbornene, 5-ethylidene-2-norbornene and 5-vinyl-2-norbornene. Particularly preferred dienes are 5-ethylidene-2-norbornene and 1,4-hexadiene.

10
The polyethylene polymers which may be prepared in accordance with the present invention typically comprise not less than 60, preferably not less than 70 weight % of ethylene and the balance one or more C1-10 alpha olefins, preferably selected from the group consisting of 1-butene, 1-hexene and 1 octene. The polyethylene; prepared in accordance with the present invention may be linear low density polyethylene having density from about 0.910 to 0.935 g/cc The present invention might also be useful to prepare polyethylene having a density below 0.910 g/cc - the so-called very low and ultra low density polyethylenes.
The most preferred polymerization process of this invention encompasses the use of the novel catalysts(together with a cocatalyst) in a medium pressure solution process. As used herein, the term "medium pressure solution process" refers to a polymerization carried out in a solvent for the polymer at an operating temperature from 100 to 320°C (especially-from.120 to 220oC)-and a total pressure of from 3 to 35 mega Pascals. Hydrogen may be used in this process to control (reduce) molecular weight. Optimal catalyst and cocatalyst concentrations are affected by such variables as temperature and monomer concentration but may be quickly optimized by non-inventive tests.
Further details concerning the medium pressure polymerization process are well known to those skilled in the art and widely described in the open and patent literature.
The catalyst of this invention may also be used in a slurry polymerization process or a gas phase polymerization process.
The typical slurry polymerization process uses total reactor pressures of up to about 50 bars and reactor temperature of up to about 200°C. The process employs a liquid medium (e.g. an aromatic such as toluene or an alkane such as hexane, propane or isobutane) in which the polymerization takes place. This results in a suspension of solid polymer particles in the medium. Loop reactors are widely used in slurry processes. Detailed descriptions of slurry polymerization processes are widely reported in the open and patent literature.

11
In general, a fluidized bed gas phase polymerization reactor employs a "bed" of polymer and catalyst which is fluidized by a flow of monomer which is at least partially gaseous. Heat is generated by the enthalpy of polymerization of the monomer flowing through the bed. Unreacted monomer exits the fluidized bed and is contacted with a cooling system to remove this heat. The cooled monomer is then re-circulated through the polymerization zone together with "make-up" monomer to replace that which was polymerized on the previous pass. As will be appreciated by those skilled in the art, the "fluidized" nature of the polymerization bed helps to evenly distribute/mix the heat of reaction and thereby minimize the formation of localized temperature gradients (or "hot" spots"). Nonetheless, it is essential that the heat of reaction be properly removed so as to avoid softening or melting of the polymer (and the resultant-and highly undesirable - "reactor chunks"). The obvious way to-maintain good mixing and cooling is to have a very high monomer flow
through the bed. However, extremely high monomer flow causes undesirable polymer entrainment.
An alternative (and preferable) approach to high monomer flow is the use of an inert condensable fluid which will boil in the fluidized bed (when exposed to the enthalpy of polymerization), then exit the fluidized bed as a gas, then come into contact with a cooling element which condenses the inert fluid. The condensed, cooled fluid is then returned to the polymerization zone and the boiling/condensing cycle is repeated.
The above-described use of a condensable fluid additive in a gas phase polymerization is often referred to by those skilled in the art as "condensed mode operation" and is described in additional detail in USP 4,543,399 and USP 5,352,749. As noted in the '399 reference, it is permissible to use alkanes such as butane, pentanes or hexanes as the condensable fluid and the amount of such condensed fluid preferably does not exceed about 20 weight per cent of the gas phase.
Other reaction conditions for the polymerization of ethylene which are reported in the "399 reference are:

12
Preferred Polymerization Temperatures: about 75°C to about 115°C (with the lower temperatures being preferred for lower melting copolymers - especially those having densities of less than 0.915 g/cc -and the higher temperatures being preferred for higher density copolymers and homopolymers); and
Pressure: up to about 1000 psi (with a preferred range of from about 100 to 350 psi for olefin polymerization)'.
The '399 reference teaches that the fluidized bed process is well adapted for the preparation of polyethylene but further notes that other monomers may be employed - as is the case in the process of this invention. EXAMPLES
The invention will now be illustrated in further detail by way of the following non-limiting examples. For clarity, the Examples have been divided into three parts, namely Part A (Catalyst Component Synthesis), Part B (Solution Polymerization) and Part C (Gas Phase Polymerization). Polymer Analysis
Gel permeation chromatography ("GPC") analysis was carried out using a commercially available chromatograph (sold under the name Waters 150 GPC) using 1,2,4-trichlorobenzene as the mobile phase at 140°C. The samples were prepared by dissolving the polymer in the mobile phase solvent in an external oven at 0.1% (weight/volume) and were run without filtration. Molecular weights are expressed as polyethylene equivalents with a relative standard deviation of 2.9% and 5.0% for the number average molecular weight (Mn) and weight average molecular weight (Mw), respectively. Melt index (Ml) measurements were conducted according to ASTM method D-1238-82.
Polymer densities were measured using pressed plaques (ASTM method D-1928-90), with a densitometer.
The following abbreviations are used in the Examples:
"Bu = tertiary butyl (e.g. tBu3 = tri-tertiary butyl)

13
Me = methyl
Et = ethyl tH NMR = proton nuclear magnetic resonance
'Pr = isopropyl
Ph = phenyl
Mw = weight average molecular weight
Mn = number average molecular weight
PD = polydisperstty (or Mw/Mn)
PE = polyethylene
Cat = catalyst
Hr. = hour
M = molar
MAO = methyl alumoxane PART A Catalyst Component Synthesis PART A1 (Prior Art)
Synthesis 1 of Cyclopentadienyltitanium(IV)(tri-t-butylphosphinimine)dichloride
Cyclopentadienyltitanium trichloride (4.025 g, 18.3 mmol) and N-trimethylsily!-tri-tert-buty!phosphinimine (5.47 g, 18.34 mmol) were combined as solids and dry toluene was added. The reaction was heated to 100°C for 1 hour and then allowed to cool to room temperature. The volatiles were removed in vacuo and the resulting yellow solid was isolated. Yield = 7.4 g. 1H NMR (da-toluene, 5 (298K)): 6.39 (singfet, 5H), 1,16 (doublet, J = 13.6 Hz, 27H). Synthesis 2 of Cvclopentadienvltitanium(IV)ftri-t-butylphosphinimineldichloride
To a solution of lBu3P=N-H (0.200 g, 0.921 mmol) in dry toluene at room temperature was added a hexane solution of n-BuLi (0.57 mL, 1.6 M, 0.92 mmol). The addition was dropwise and resulted in a slightly turbid solution after 15 minutes of stirring. The lithium salt of the phosphinimine was then added dropwise to a slurry of cyclopentadienyltitanium(IV)trichloride (0.202 g, 0.921 mmol) in toluene.

14
After 4 hours the reaction mixture was filtered through a sintered glass frit and the solvent removed in vacuo to leave the product as a bright green solid. The solid was found to be - 98% pure. Yield = 247 mg, 67.1%. Synthesis 3 of Cvclopentadienyltitanium(IV)ftri-t-butylphosphinimine)dichloride
fBu3P=N-H (0.200 g, 0.921 mmol) and
cyclopentadienyltitanium(IV)trichloride'(0.202 g,0.921 mmol) were combined as solids and toluene was added. The reaction was allowed to stir for 30 minutes and then triethylamine (1.30 mL, 9.21 mmol, 10 equiv.) was added dropwise. During the addition, the-solution changed from orange to yellow as the sparingly soluble titanium reagent dissolved. The reaction was stirred for an additional 30 minutes and then filtered to remove the precipitated ammonium salt. Removal of the solvent in vacuo gave the product as a yellow crystalline solid. Yield = 336 mg,' 91.3%. Synthesis 4 of Cyclopentadienyltitanium(IV)(tri-t-butvlphosphinimine)dichloride
To a solution of lBu3P=N-H (0.347-g, 1.60 mmbl) in toluene was added a hexane solution of n-BuLi (1.0 mL, 1.6 M, 1.6 mmol). The addition was dropwise and resulted in a slightly turbid solution after 15 minutes of stirring. The resulting lithium salt of the phosphinimine was then added dropwise to a stirred slurry of titanocene(IV)dichloride (0.398 g, 1.60 mmol) in toluene. After stirring at room temperature for 48 hours the solvent was removed in vacuo. The resulting brown solid was redissolved in the minimum amount of hot toluene and the solution filtered. Heptane was added to the solution and on standing overnight brown crystals of the product grew. These were isolated by decanting off the mother liquor and washing with heptane. Yield = 135 mg, 21 % (purity = 98%).
Synthesis 5 of CvclopentadienvltitaniumflVUtri-t-butvlphosphinimine)dichloride
To a solution of 'Bu3P=N-TiCb (0.370 g, 1.00 mmol) in toluene was added cyclopentadiene (0.660 g, 1.32 mL, 10.0 mmol). Triethylamine

15
(1.10 g, 1.39 mL, 10.0 mmol) was then added and the solution stirred for 18 hours. At this point the reaction mixture was heated at 80°C for 2 hours. The toluene was removed under reduced pressure to leave a yellow solid. This was washed with heptane and the product, isolated. 1H NMR showed the product contained some starting materials Synthesis 6 of CvclopentadienvltitaniumflV)(tri'-t-butylphosphinimine)dichloride
tBu3P=N-TiCI3 (1.00 g, 2.70 mmol) and CpLi (0.194 g, 2.70 mmol) were combined as solids and toluene was added. The reaction mixture was stirred overnight, filtered through a sintered'glass frit and'then concentrated in vacuo. The resulting yellow solid was analyzed by NMR' and found to be pure product. Yield = 971 mg, 81%. Preparation of CvclopentadienvltitaniumflV)(tri-tert-butvlphosphinimine)f2-N.N-dimethvlamino)ben2vl Chloride. C.HgT;(NPtBu?)fCHgCfiH4NfCH^j)ei
To a solution of cyclopentadienyltitanium(IV)(tri-t-butylphosphinimine) dichloride (1,904 g, 4.76 mmol) in anhydrous tetrahydrofuran (THF, 50 mL) at -78°C was added a solution of 2-N,N-dimethylaminobenzyl lithium (671 mg, 4.76 mmol) in THF (30 mL). A red color started to form immediately and the reaction was allowed to warm to room temperature. The solvent was removed in vacuo and the residue taken up in toluene and filtered. The toluene was then removed and the residues redissolved in hexane at 60°C. The solution was filtered and then placed in a -15°C freezer. The product formed as a pure orange crystalline solid on standing overnight and was isolated by filtration and pumping to dryness in vacuo. Yield = 1.45 g, 61%. 1H NMR (d8-toluene, 5 (298K)): 6.9-7.41 (m, Ph-H), 6.11 (s, Cp-H), 3.35 (d, J = 9.5 Hz, CHH). 3.03 (d, J = 9.5 Hz, CHH), 2.64 (s, N-CH3), 1.22 (d, J = 13.2 Hz, xBuH).

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PART A2
A2.1 Preparation of CvclopentadienvltitaniumflV)(tri-tert-butylphosphinimine)(2-N,N-dimethvlamino)benzvl Chloride, CiH5Ti(NPtBu3)(CHgC5HgN(CH3)2)CI
To a solution of cyclopentadieny!titanium(l V)(tri-t-butylphosphinimine) dichloride (1.904'g; 4.76 mmol) in anhydrous tetrahydrofuran (TMF, 50 mL) at -78°C was added a solution of 2-N.N-dimethylaminobenzyl fithium (671 mg, 4.76 mmol) in THF (30 mL). A red color started to form immediately and the reaction was allowed to warm to room temperature. The solvent was removed in vacuo and the residue taken up in toluene and filtered. The toluene was then removed and the residues redissolved in hexane at 60°C. The solution was filtered and then placed in a -15°C freezer. The product formed as a pure orange crystalline solid on standing overnight and was isolated by filtration and pumping to dryness'in vacuo. Yield =:1-.45 g,-61%. '1H NMR (da-toluene, 5 (298K)): 6.9 - 7.41 (m, Ph-H), 6.11 (s, Cp-H), 3.35 (d, J = 9.5 Hz, CHH), 3.03 (d, J = 9.5 Hz, CHH), 2.64 (s, N-CH3), 1.22 (d! J = 13.2 Hz, lBuH). A2.2 Preparation of Cvclopentadienvltitanium(lll)ftri-tert-butylphosphinimineK2-N.N-dimethvlamino)benzyl. C.H.TifNP'Bu^fCHgCfiKtNfCH^)
To a flask containing cyclopentadienyltitanium(IV)(tri-tert-butylphosphinimine)(2-N,N-dimethylamino)benzyl chloride (600 mg, 1.23 mmol) and magnesium powder (1 g, 41 mmol) was added THF (30 mmol). The reaction was stirred for 5 days and then the THF was removed in vacuo. Hexane was added and the reaction flask warmed to 55°C. The solution was then filtered, concentrated in vacuo and cooled to -15°C. The product formed as a purple-red crystalline solid and was isolated by filtration and pumping to dryness in vacuo. Yield = 230 mg. Electron Paramagnetic Resonance (ESR) g = 1.9752. This g value confirms the presence of the Ti(lll) species.

17
A2.3 Preparation of Cvclopentadienvltitaniumftri-tert-butylphosphinimine)fbutadiene), CsHsTifNP'BtigMCdHg)
Dry toluene (10 mL) was added to a flask containing cyclopentadienyltitanium(tri-tert-butylphosphinimine) dichloride (844 mg, 2.11 mmol) and magnesium butadiene complex, MgfG^He), (500 mg, 2.25 mmol) at room temperature. The reaction mixture immediately' became dark red and a slight exotherm was observed. After stirring for 1 hour the toluene was removed in vacuo and the product extracted with hexane. The solution was filtered and the hexane removed to leave the desired product as a pure dark red crystalline solid. Yield = 663 mg, 82%. 1H NMR (da-toluene, 5 (298K)): 5.66 (s; Cp-H), 4.75 (broad, butadiene), 1.09 (d, J = 12.5 Hz).
A2.4 Preparation of CvclopentadienyltitaniurnnVUtri-te/t-butvlphosphinimine)-N,N'-dimethvlethvlenediamine, CgHgTi(NPtBUfl)fNfMe)CHpCH?N(Me))
To a solution of N.N'-dimethylethylenediamine (2.24 g, 2.70 mL, 25.4 mmol) in hexanes (15 mL) was slowly added a solution" of butyllithium (31.8 mL, 1.6 M in hexanes, 50.7 mmol). A white precipitate of the dilithio salt formed and this was isolated by filtration and dried in vacuo.
A sample of the di-lithium salt of N,N'-dirnethylethylenediamine (0.100 g, 1.00 mmol) and cyclopentadienyltitanium(IV)(tri-f-butylphosphinimine)dichloride (0.400 mg, 1.00 mmol) were combined as solids and toluene (15 mL) was added. Upon addition of the solvent the reaction mixture rapidly changed from yellow to a brown, opaque solution. The reaction mixture was stirred for 1.5 hours and then filtered. The solvent was removed in vacuo yielding the product as a purple/brown solid. Yield = 317mg, 76%. 1H NMR (ds-toluene, 6 (298K)): 6.26 (s, Cp-H), 3.4 - 3.8 (broad multiplet, methylene protons), 2.91 (s, Me), 1.27(d, J = 12.4 Hz).

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PART B Solution Polymerization
PART B1 Solution Semi-Batch Reactor (SBR) Results
All the polymerization experiments described below were conducted using a solution semi-batch reactor. All the chemicals (solvent, catalyst and cocatalyst) were fed into the reactor batchwise except ethylene which was fed on demand and no removalofproduct during the polymerization reaction. All the feed streams were purified prior to the reactor by contact with various absorption media to remove catalysts killing impurities such as water, oxygen, sulfur and polar materials as are known to those skilled in the art;'All components were stored and manipulated under an atmosphere of purified a'rgon or nitrogen. The SBR uses a programmable logical control (PLC) system with Wonderware 5.1 software for process control. Ethylene polymerizations were performed in a 500 mL Autoclave Engineers Zipperclave reactor equipped with an air driven stirrer.and an automatic temperaturercontrol system;

The polymerization time was 10 minutes in each experiment. The reaction was terminated by adding 5 mL of methanol to the reactor and
Two catalysts were used, namely C5H5T\(NPtBu3)(CH2C6^4N(CH3)2) (referred to as:."RS^676-89" in the following-table;'synthesis described in Part A, Section A2.2) and the comparative catalyst cyclopentadienyl titanium (IV) tri-t-butylphosphinimine dichloride ("JS304"; synthesis described in Part A, Section A1), were prepared as described in Part A. The catalysts were dissolved in toluene and the catalyst concentrations were between 0.7-5 mg/mL A commercially available methylalumoxane (PMAO-IP, purchased from Akzo-Nobel) was used in the experiments. The experiments were carried out as follows:

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the polymer was recovered by evaporation of the cyclohexane. The polymerization activities were calculated based on the ethylene consumed during the reaction, not the weight of'the polymer produced.
1" The calculation of polymerization activity is based on the ethylene uptake.
C: comparative

Polymer molecular weights and molecular weight distributions were measured by GPC (Waters 150-C) at 140°C in r,2,4-frichlor6be'nzene calibrated using polyethylene standards.

C: comparative
The polyethylene produced by the inventive catalyst RS-676-89 has a low molecular weight tail, which contributes to a higher polydispersity of 5.4. The inventive experiment using RS-676-89 showed a different kinetic profile which may be a result of the Ti(lll) species. The "initial" activity of the inventive experiment was slower/lower, but the overall activity was high. This is very desirable for commercial-scale polymerizations having a residence time of more than 2 minutes. PART B2 The Continuous Solution Polymerization
All the polymerization experiments described below were conducted on a continuous solution polymerization reactor. The process is continuous in all feed streams (solvent, monomers and catalyst) and in the removal of product. All feed streams were purified prior to the reactor by contact with various absorption media to remove catalyst killing

20
impurities such as water, oxygen and polar materials as is known to those skilled in the art. All components were stored and manipulated under an atmosphere of purified nitrogen.
All the examples below were conducted in a reactor of 71.5 cc internal volume. In each experiment thevolumetric feed to trie reactor was kept constant and as a consequence so was the reactor residence time.
The catalyst solutions were pumped to'the reactor independently and in some cases were mixed before entering the polymerization reactor (as indicated in the examples): Because of the low solubility of the catalysts, activators and MAO in cycl6hexahe, solutions were prepared in purified xylene. The catalyst was activated in-situ {in the polymerization reactor) at the reaction temperature in the presence of the monomers. The polymerizations were carried out in cyclohexane at a pressure of 1500' psi. Ethylene was supplied to the reactor-by-a calibrated:thermal mass' flow meter and was dissolved in the reaction solvent prior to the polymerization reactor, ifcomonomer (forex"ample'i-octerie) was used it was also premixed with the ethylene before entering the polymerization reactor. Under these conditions the ethylene conversion is a dependent variable controlled by the catalyst concentration, reaction temperature and catalyst activity, etc.
The internal reactor temperature is monitored by a thermocouple in the polymerization medium and can be controlled at the required set point to +/- 0.5°C. Downstream of the reactor the pressure was reduced from the reaction pressure {1500 psi) to atmospheric. The solid polymer was then recovered as a slurry in the condensed solvent and was dried by evaporation before analysis.
The ethylene conversion was determined by a dedicated on line gas chromatograph by reference to propane which was used as an internal standard. The average polymerization rate constant was calculated based on the reactor hold-up time, the catalyst concentration in the reactor and the ethylene conversion and is expressed in l/(mmormin).

21
Average polymerization rate (kp) = (Q/(100-Q)) x (1/[TM]) x (1/HUT)
where : Q is the percent ethylene conversion.
[TM] is the catalyst concentration in the reactorexpressed in mM.
HUT is the reactor hold-up lime in minutes. Polymer Analysis,
Melt index (Ml) measurements were conducted according to ASTM method D-1238-82.
Polymer densities were measured on pressed plaques (AST-M D-1928-90) witha-densitometer. Example 1
CpTiNP^Bu^butadiene) (from Part A; Section A2.3) was added to the reactor at 9.3 x 10'6 mol/l along with Ph3C B(C6F5)4 (purchased from "Asahi Glass") at B/Ti = 1.00 (mol/mol). Both components were mixed-in the polymerization reactor. The reaction temperature was 1.60°C cTnd. 2.1 gram/min of ethylene was continuously added to the reactor. An ethylene conversion'of 98.8% was observed (see Table B2.1). Example 2
CpTiNP(tBu)3(butadiene) was added to the reactor at 9.3 x 10"6 mol/l along with B(C6F5)3 (purchased from "Boulder Scientific") at B/Ti = 2.5 (mol/mol). Both components were mixed before the polymerization reactor. The reaction temperature was 160°C and 2.1 gram/min of ethylene was continuously added to the reactor. An ethylene conversion of 70.7% was observed (see Table B2.1). Example 3
CpTiNP(lBu)3(butadiene) was added to the reactor at 2.3 x 10"6 mol/l along with Ph3C B(C6F5)4 (Asahi Glass) at B/Ti = 1.00 (mof/mol). Both components were mixed in the polymerization reactor. The reaction temperature was 160°C and 2.1 gram/min of ethylene was continuously added to the reactor. An ethylene conversion of 96.3% was observed (see Table B2.1).

22
Example 4
CpTiNP(fBu)3(butadiene) was added to the reactor at 5.3 x 10'6 mol/l along with MMAO-7 (purchased from "Akzo-Nobel") at Al/Ti = 40.0 (mol/mol). Both components were mixed in the polymerization reactor. The reaction temperature was 160°C and 2.1 gram/min of ethylene was continuously added to the reactor." An ethylene conversion of 89.4% was observed (see-Table B2.1). Example 5
CpTiNP(lBu)3(butadiene) was added to the reactor at 5.8 x 10'6 mol/l along with MMAO-7 (Akzo-Nobel) at Al/Ti = 40.0 (mol/mol). Both components were mixed in the polymerization reactor. The reaction temperature was 160°C and 2.1 gram/min of ethylene was continuously added to the reactor as was 1.0 ml/min of 1-octene. An ethylene conversion of 89.4% was observed (see Table B2.1). Example 6
CpTiNP^Bu^butadiene) was added to the reactor at 8.1 x 10"6 mol/l along witfrMMAO-7 (Akzo-Nobel) -at Al/Ti = 40.0 (mol/mol). Both components were mixed in the polymerization reactor. The reaction temperature was 160°C and 2.1 gram/min of ethylene was continuously added to the reactor as was 3.0 ml/min of 1-octene. An ethylene conversion of 90.2% was observed (see Table B2.1). Example 7
CpTiNP('Bu)3(butadiene) was added to the reactor at 8.1 x 10'6 mol/l along with MMAO-7 (Akzo-Nobel) at Al/Ti = 40.0 (mol/mol). Both components were mixed in the polymerization reactor. The reaction temperature was 160°C and 2.1 gram/min of ethylene was continuously added to the reactor as was 5.0 ml/min of 1-octene. An ethylene conversion of 90.4% was observed (see Table B2.1). Example 8
CpTiNP(lBu)3(butadiene) was added to the reactor at 1.9 x 10'6 mol/l along with MMAO-7 (Akzo-Nobel) at Al/Ti = 40.0 (mol/mol) and Ph3C

23
B(C6F5)4 (Asahi Glass) at B/Ti = 1.00 (mol/mol). CpTiNP(tBu)3(butadiene) and Ph3C B(C6F5)4 were mixed before the reactor and were subsequently mixed with the MMAO-7 in the reactor. The reaction temperature was 160°C and 2.1 gram/min of ethylene was continuously added to.the reactor as was 3.0 ml/min of 1-octene. An ethylene" conversion of'91-.3% was observed.(see Table B2.1); Example 9
CpTiNP([Bu)3(butadiene) was added to the reactor at 1.9 x 10'6 mol/l along with MMAO-7 (Akzo-Nobel) at Af/Ti = 40.0 (mol/mol) and Ph3C B(C6F5)4 (Asahi Glass) at B/Ti =±1.00 (mol/mol). CpTiNP(lBu)3(butadiene) and Ph3CB(C6F5)4 were mixed before the reactor and were subsequently mixed with the MMAO-7 in the reactor. The reaction temperature was 160°C and 2.1 gram/min of ethylene was continuously added to the reactor as was 5.0 ml/min of 1-octene: An ethylene conversion of 90.5% was observed (see Table B2;1).-Example 10
CpTiNP('Bu)3(butadiene) was*added to the reactor at 1.9 x 10"6 mol/l along with MMAO-7 (Akzo-Nobel) at Al/Ti = 40.0 (mol/mol) and Ph3C B(C6F5)4 (Asahi Glass) at B/Ti = 1.00 (mol/mol). CpTiNP(lBu)3(butadiene) and Ph3C B(CeF5)4 were mixed before the reactor and were subsequently mixed with the MMAO-7 in the reactor. The reaction temperature was 160°C and 2.1 gram/min of ethylene was continuously added to the reactor as was 1.0 ml/min of 1-octene. An ethylene conversion of 91.3% was observed (see Table B2.1). Example 11
CpTiNP(!Bu)3(butadiene) was added to the reactor at 1.9 x 10"6 mol/l along with MMAO-7 (Akzo-Nobel) at Al/Ti = 40.0 (mol/mol) and Ph3C B(C6F5)4 (Asahi Glass) at B/Ti = 1.00 (mol/mol). CpTiNP((Bu)3(butadiene) and Ph3C B(C6F5)4 were mixed before the reactor and were subsequently mixed with the MMAO-7 in the reactor. The reaction temperature was

24
160°C and 2.1 gram/min of ethylene was continuouslyadded to the reactor. An ethylene conversion of 90.7% was observed (see Table B2.1). Example 12
CpTiNP(tBu)3(CH2C6H4-2-NMe2) (from Part A; Section A2.2) was added to the reactor at 9.3 x 10"6 mol/I along, with* Ph3C B(C6F5)4 (Asahi Glass) at B/Ti =± 1.00 (mol/mol). Both components were1 mixed in the polymerization reactor. The reaction temperature was 160°C and 2.1 gram/min of ethylene was continuously added to the reactor. An ethylene conversion of 93.5% was observed (see Table B2.1). Example 13
CpTiNP(tBu)3(CH2C6H4-2-NMe2) was added to the reactor at 4.6 x 10"6 mol/I along with HNMe2Ph B(C6F5)4 (Akzo-Nobel) at B/Ti = 1.00 (mol/mol). Both components were mixed in the polymerization reactor. The reaction temperature was 160°C and 2.1 gram/min of "ethylene was continuously added to the reactor. An ethylene conversion of 91.5% was observed (see Table B2.1). Example 14
CpTiNP(tBu)3(CH2C6H4-2-NMe2) was added to the reactor at 13.0 x 10"6 mol/I along with MMAO-7 (Akzo-Nobel) at Al/Ti = 50.0 (mol/mol). Both components were mixed in the polymerization reactor. The reaction temperature was 160°C and 2.1 gram/min of ethylene was continuously added to the reactor as was 3.0 ml/min of 1-octene. An ethylene conversion of 89.1% was observed (see Table B2.1). Example 15
CpTiNP{tBu)3(CH2C6H4-2-NMe2) was added to the reactor at 9.3 x 10'6 mol/I along with MMAO-7 (Akzo-Nobel) at Al/Ti = 40.0 (mol/mol) and Ph3C B(C6F5)4 (Asahi Glass) at B/Ti = 1.00 (mol/mol). All components were mixed in the reactor. The reaction temperature was 160°C and 2.1 gram/min of ethylene was continuously added to the reactor. An ethylene conversion of 92.8% was observed (see Table B2.1).

25
Example 16
CpTiNP(tBu)3(CH2C6H4-2-NMe2) was added to the reactor at 9.3 x 10'6 mol/l along with MMAO-7 (Akzo-Nobel) at Al/Ti = 40.0 (moi/mol) and Ph3C B(C6F5)4 (Asahi Glass) at B/Ti = 1,00 (mol/mol). Ail components -were mixed in the reactor. The reaction temperature was 160°Oand 2.1 gram/min of ethylene was continuously added to'the reactor as was 3.0 ml/min of 1-octene. An ethylene conversionof 93.6% was observed (see Table B2.1). Comparative Example 17C
(C5Me5)2ZrCl2 (purchased from "Strem") was added to'the reactor at 37 x 10"6 mol/l along with MMAO-3 (Akzo-Nobel, Al/Ti = 400 mol/mol). The reaction temperature was 140°C and 1.0 gram/min of ethylene was continuously added to the reactor. An ethylene conversion of 55.5% was observed (see Table B2.1). Comparative Example 18C
(C5Me5)2ZrCl2 (Strem) was added to the reactor at 37 x 10"6 mol/l along with MMAO-3 (Akzo-Nobel, Al/Ti = 400 mol/mol). The reaction temperature was 160°C and 1.0 gram/min of ethylene was continuously added to the reactor. An ethylene conversion of 35.6% was observed (see Table B2.1). Comparative Example 19C
(C5Me5)2ZrCI2 (Strem) was added to the reactor at 37 x 10'6 mol/l along with MMAO-3 (Akzo-Nobel, Al/Ti = 400 mol/mol). The reaction temperature was 160°C and 2.1 gram/min of ethylene was continuously added to the reactor. An ethylene conversion of 37.4% was observed (see Table B2.1). Comparative Example 20C
rac-Et(ind)2ZrCI2 (purchased from "Witco") was added to the reactor at 37 x 10"6 mol/l along with MMAO-3 (Akzo-Nobel, Al/Ti = 400 mol/mol). The reaction temperature was 160°C and 2.1 gram/min of ethylene was

26
continuously added to the reactor. An ethylene conversion of 94.6% was observed (see Table B2.1). Comparative Example 21C
rac-Et(ind)2ZrCI2 (Witco) was added to the reactor at 37 x 10'6 mol/l along with MMAO-3 (Akzo-Nobel, Al/Ti = 400 mol/mol). The reaction-temperature was 160°C and 2.1 gram/min of ethylene and 3.25 ml/min of 1-octene was continuously added to the reactor. An ethylene conversion of 94.8% was observed (see Table B2.1).

27

28
PART C Gas Phase Polymerization
Catalyst Preparation and Polymerization Testing Using a Semi-Batch,
Gas Phase Reactor
The catalyst preparation methods described below employ typical, techniques for the syntheses and handling of air-sensitive,rnaterials.' Where appropriate, elemental compositions of the supported catalysts were measured by Neutron Activation analysis and a.reported accuracy of + 1% (weight basis).
The supported catalysts were prepared by initially supporting MAO on a silica support, followed by deposition of the catalyst .component.-
All the polymerization experiments described below were conducted using a semi-batch, gas phase polymerization reactor of total internal volume of 2.2 L. Reaction gas mixtures, including ethylene/butene mixtures (96 mole % ethylene, 4 mole % butene) were measured to the reactor on a continuous basis using a calibrated "thermal mass flow meter, following passage through purificatidn:media as-described above. A predetermined mass of the catalyst sample as added to the reactor under the flow of the inlet gas with no pre-contact of the catalyst with any reagent, such as a catalyst activator. The catalyst was activated in-situ (in the polymerization reactor) at the reaction temperature in the presence of the monomers, using a metal alkyl complex which has been previously added to the reactor to remove adventitious impurities. Purified and rigorously anhydrous sodium chloride was used as a catalyst dispersing agent.
The internal reactor temperature is monitored by a thermocouple in the polymerization medium and can be controlled at the required set point to +/-1.0°C. The duration of the polymerization experiment was one hour. Following the completion of the polymerization experiment, the polymer was separated from the sodium chloride and the yield determined.

29
Table C1 illustrates data concerning the Al/transition metal ratios of the supported catalyst and polymer yield. Polymer properties are shown in Table C2.
INDUSTRIAL APPLICABILITY
The inventive complexes are well-suited for. use as a component in a catalyst system for the polymerization-of olefins- especially ethylene; Polyethylene produced with the inventive complexes is useful, for example, in the production of film, extruded parts and profiles and molded plastic goods.

30

31 WE CLAIM
1. A process for the polymerization or ethylene characterized in that said pocess Is conducted In the presence of: (a) an organometallic complex defined by the formula:

wherein Cp is a cyclopentadienyMype ligand; L is an actrvatable Ligand; M is a metal selected from Ti and Zr; and PI is a phosphinimine ligand defined by the formula:

wherein each R1 is independently selected from the group consisting of a hydrogen atom, a halogen atom, C1.20 hydrocarbyl radicals which are unsubstituted by or further substituted by a halogen atom, a C1-8 alkoxy radical, an amido radical, a C6-10 aryl or aryloxy radical, a silyl radical of the formula:
wherein each R2 Is independently selected from the group consisting of hydrogen, a C1-8 alkyl or alkoxy radical, C8-10 aryl or aryloxy radicals, and a germanyl radical of the formula:
Ge-(R2)3
wherein R2 is as defined above; and
(b) an activator at a temperature of from 75°C to 320°C and a pressure of from 100 psi to 35 mega Pascals.
2. The process as claimed in claim 1 wherein said ethylene is copolymerized
with a minor amount of an alpha olefin having from 3 to 10 carbon atoms.
3. The process as claimed in claim 1 wherein said activator Is an Ionic
activator.

32
4. The process as claimed in claim 1, wherein each R1 fs tertiary butyl and M is titanium (III).
A process for the polymerization of ethylene characterized in that said pocess is conducted in the presence of: an organometallic complex defined by the formula:

wherein Cp is a cyclopentadienyl-type ligand; L is an activatable Ligand; M is a metal selected from Ti and Zr; and PI is a phosphinimine ligand defined by the formula:

wherein each R1 is independently selected from the group consisting of a hydrogen atom, a halogen atom, C1-20 hydrocarbyl radicals which are unsubstituted by or further substituted by a halogen atom, a C1-8 alkoxy radical, an amido radical, a C6-10 aryl or aryloxy radical, a silyl radical of the formula:
wherein each R2 is independently selected from the group consisting of hydrogen, a C1-6 alkyl or alkoxy radical, C6-10 aryl or aryloxy radicals, and a germanyl radical of the formula:
Ge-(R2)3
wherein R2 is as defined above; and an activator at a temperature of from 75°C to 320°C and a pressure of from 100 psi to 35 mega Pascals.

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Patent Number

207988

Indian Patent Application Number

IN/PCT/2001/00088/KOL

PG Journal Number

27/2007

Publication Date

06-Jul-2007

Grant Date

04-Jul-2007

Date of Filing

19-Jan-2001

Name of Patentee

NOVA CHEMICALS (INTERNATIONAL)S.A

Applicant Address

ROUTE DE LA GLANE 107, P.O.BOX 76, CH-1752 VILLARS-SUR-GLANE 1,

Inventors:

#	Inventor's Name	Inventor's Address
1	STEPHAN DOUGLAS W	1835 ARGUS STREET,LASALLE, ONTARIO N9J 3G5 CANADA
2	BROWN STEPHEN JOHN	157 MOUNT SPARROWHAWK PLACE S.E. CALGARY,ALLBERTA T2Z 2G7 CANADA;
3	JEREMIC DUSAN	240 SANDSTONE DRIVE N.W.CALGARY ALBERTA T3K 3$6 CANADA
4	WANG QINYAN	89 HARVEST GLEN WAY N.E. CALGARY.ALBERTA T3K 4J3,
5	VON HAKEN SPENCE RUPE T, EDWARD	401-11, STREET N.W.CALGARY, ALBERT T2N 1X5

PCT International Classification Number

C07F17/00

PCT International Application Number

PCT/CA99/00526

PCT International Filing date

1999-06-08

PCT Conventions:

#	PCT Application Number	Date of Convention	Priority Country
1	2.243,726	1998-07-21	Canada