MXPA99011789A - Polymerisation catalysts - Google Patents

Abstract

Los complejos de metal de transición adecuados para utilizarse en la polimerización de olefinas comprenden grupos insaturados que tienen un grupo funcional de base de Lewis. Los grupos preferidos son dienos que tienen funcionalidad dialquilamino. Los complejos pueden estar adecuadamente soportados por el uso de dienos funcionalizados para proporcionar los complejos de metal de transición que, en presencia, de activadores, son particularmente adecuados para los procesos en fase gaseosa.

Description

POLYMERIZATION CATALYSTS FIELD OF THE INVENTION The present invention relates to catalysts suitable for the polymerization of olefins, in particular to catalysts comprising supported transition metal complexes suitable for use in the polymerization of ethylene or the copolymerization of ethylene with alpha olefins.

BACKGROUND OF THE INVENTION The use of transition metal complexes as components of the catalyst compositions suitable for the polymerization of olefins is well known. For example, olefin polymerization catalysts based on metallocene complexes are known. These catalysts typically comprise bis (cyclopentadienyl) zirconium complexes together with activators such as aluminoxanes and are set forth in detail in EP 129368 and EP 206794. When used for polymerization in the gas phase, these complexes are typically supported by, for example. use, silica. However, attempts have been made to fix or tie these metallocene complexes in order to allow them to be used as catalysts P1759 / 99MX heterogeneous for the polymerization of olefins, in particular for use in a paste or gas phase. The document, EP 586 167-A1 discloses the functionalization of metal complexes with polymerizable groups, which allow the formation of metallocene-containing polymers, usually low-yield polyolefins, providing a method for fixing the metal complexes to the supports, for example to silica . US 5 498 581 discloses the production of metallocene-containing catalyst systems, in the solid state, incorporating an olefinic group attached to a metallocene (e.g. (cyclopentadienyl) (fluorenyl) ZrCl2) bridged to (methyl-1-butenyl) methylene) in a solid prepolymer. US 5 492 973, US 5 492 974, US 5 492 975, US 5 492 978, and US 5 492 985, disclose the formation of ligands bound to polymers by the reaction of a metallated polymer (for example polystyrene) with a chlorinated cyclopentadienyl-containing portion (Cp), followed by reaction with a metal compound (e.g. CpMCl) to provide a catalyst precursor attached to the polymer. However, this method presents the possible disadvantage that the modification of the ligand necessary to effect the binding of the polymer can interfere with the chemistry of the active site.

P1759 / 99MX US 5 466 766 discloses a process for preparing supported metallocene complexes using a ligand that has an active halogen and reacting it with a hydroxylated support to give an immobilized complex (eg silica-0-Cp-fluorenylmethylsilane ZrCl2) . This method also presents the possible disadvantage that the modification of the ligand necessary to effect the binding of the polymer can interfere with the chemistry of the active site and the release of the polar compounds as a by-product on the interaction of the active halogen with the supporting hydroxyl function ( for example HCl) that could act as a poison for the olefin polymerization catalyst systems. EP 670 336-A1 discloses bridged bis-Cp complexes, for example bis-indenyl zirconium chlorides with silyl bridge, which possess alkylamino substituents bound to the ligand, for example to the indenyl entity. These are then reacted with a support of hydroxylated oxide (for example silica) treated with halogenated silanes (RO) 3 Si (4-CH 2 Cl-Ph) and Me 3 SiCl) in a solvent (for example toluene) to effect the quaternization by N quaternization. of the amine (for example [indenyl-N + (Me) 2-CH2-Ph-Si-support] [Cl] "). WO 96/04319 discloses the immobilization of a borate activator to the P1759 / 99MX surface of a support to form a supported borate (for example [support-O-B (C6F5) 3] "[Hl +) with subsequent treatment with dialkylmetallocene (for example Cp2M (Me) 2) to give an immobilized catalyst (eg [OB-support (CßFs) 31"[Cp2M (Me)] +) JP 1-259005 and 1-259004 disclose complex preparation with ligands containing the silane functionality (eg (MeO) 3Si-CH2-CH2-indenyl) ZrCl3) and their use in supported catalyst formulations using hydroxyl oxide supports A possible problem with the approach may be the release of the compounds polarized by-products as the silane interacts with the supporting hydroxyl functional group (eg MeOH) and its role as poisons for the olefin polymerization catalyst systems Other complexes with similar functional groups have been discussed but their specific use is not shown for attaching or joining the metallocene complex on a support, for example EP 670 325-A2, exhibits bridged bis-Cp complexes, for example bis-indenylzirconium chlorides linked with silyl bridge, which possess alkylamino substituents bound to the ligand, for example to the indenyl entity. There is no indication of use P1759 / 99MX of alkylamino substituents for binding purposes, which have been set forth herein. US 5 486 585 discloses the preparation of metal complexes having ligands containing silyl bridges having amido groups (for example (((Me2N) 2Si) (2-Me indenyl) ZrCl. The complexes can be used with an activator to make A catalyst system that can be supported by a few details of the preferred supported support method, therefore, it would be very desirable to have a method of immobilization for these metallocene complexes that is not based on the chemical modification of the ligand system that remains attached to the site of the active metal during use as a polymerization catalyst It would also be desirable to have a method of immobilization of metal complexes that does not involve the release or formation of reactive materials during the immobilization process. that could be used for a wide range of metal complexes. There have been a large number of patents that describe polymerization catalyst systems based on transition metal complexes that also comprise an unsaturated moiety, for example a ligand.

P1759 / 99MX conjugated diene neutral or unconjugated, which complex with the complex metal. These catalyst systems are disclosed in WO 95/00526 and WO 96/04290, which are incorporated herein by reference.

DETAILED DESCRIPTION OF THE INVENTION We have now discovered that these complexes can be adequately supported with the use of an unsaturated entity when contacted with a Lewis base functional group. Therefore, according to this invention, a transition metal complex suitable for use in the polymerization of olefins comprising a transition metal complex of the formula is provided: LxQyM - D wherein: M is titanium, zirconium or hafnium in the oxidation state +2 or +4, L is a group that contains a delocalized and cyclic anionic p system through which it is attached to the MQ group is an entity bound to M by a bond s, which comprises boron or a member of Group 14 of the Periodic Table and also comprises nitrogen, phosphorus, sulfur or oxygen, the entity has up to P1759 / 99 X 60 atoms that are not hydrogen atoms. x = 1 or 2 y = 0 or 1 so that when x = 1, y = 1 and when x = 2, y = 0, and D is a fixed, conjugated or unconjugated, neutral entity, optionally substituted with one or more hydrocarbyl groups, D has up to 40 carbon atoms and forms a p complex with M, when M is the oxidation state +2 and a complex s with M, when M is in the oxidation state +4 and has minus one Lewis base group B. The group L is preferably a CsH group attached to Q and linked in a 5? binding mode with M or in a 5 substitution group substituted with one more substituents independently selected from hydrocarbyl, silyl, germyl, halo, cyano and combinations thereof, the substituent has up to 20 non-hydrogen atoms and, optionally, two of these substituents (except cyano or halo) together cause L to have a fused ring structure. The group L is preferably cyclopentadienyl or substituted cyclopentadienyl, for example indenyl. When group Q is present (when y = 1) it can be adequately represented as Z-Y where P1759 / 99MX Y is -O-, -NR '-PR and Z is SiR2, CR * 2, SiR2SiR * 2, CR * 2CR * 2, CR * = CR *, CR2SiR * 2, or GeR * 2; wherein: R * in each occurrence is independently hydrogen or a selected member of hydrocarbyl, silyl, halogenated alkyl, halogenated aryl and combinations thereof, R * has up to 10 non-hydrogen atoms and optionally two R * groups of Z (when R * is not hydrogen) or a group R * of Z and a group R * of Y form a ring system. The most preferred complexes are amidosilane or amidoalkanediyl complexes, wherein the metal is titanium. When there are two L groups present (ie when x = 2) these can be joined together by an appropriate bridge group represented by (R2Z) P-L where Z is silicon, germanium or carbon. p is an integer from 1 to 8, R is hydrogen a group selected from hydrocarbyl or combinations thereof and L is as defined above. The most preferred complexes of this type P1759 / 99MX are those wherein M is zirconium, L is indenyl and (R2Z) P is CH2CH2, ie Z = carbon, R = H and p = 2. Typical examples of transition metal complexes suitable for use in this invention they are represented below. When x = 1.

Alternatively when x = 2, suitable complexes are represented by the following formula: Examples of suitable unsaturated entities include olefinic, acetylenic or imido ligands that include cyclic derivatives. A particularly preferred entity is a diene.

P1759 / 99MX Examples of suitable diene groups which may contain the B group of the Lewis Base include s-trans-? 4 l, 4-diphenyl-1,3-butadiene; s-trans-? 4-3 -methyl-1,3-pentadiene, s-trans-? -l, 4-dibenzyl-1,3-butadiene; s- trans-? 4-2, 4-hexadiene; s-trans-? 4-1, 3 -pentadiene; s- trans -? -l, 4-ditolyl-l, 3-butadiene; s- trans -? -l, 4-bis (trimethylsilyl) -1,3-butadiene; s-cis-? -l, 4-diphenyl-1,3-butadiene; s-cis-? 4-3-methyl-1,3-pentadiene; s-cis-? 4-2, 4-hexadiene; s-cis-? 2,4-hexadiene; s-cis-? 4l, 3-pentadiene; s-cis-? 4-l, 4-ditolyl-1,3-butadiene; and s-cis-? 4- 1, 4-bis (trimethylsilyl) -1,3-butadiene, the s-cis-diene group forms a p complex as defined herein, with the metal. Particularly suitable are butadienes substituted with 1,4-diphenyl. The Lewis Base Group B present in the unsaturated entity can be selected from the following groups: -NR2, -PR2, AsR2, -OR, -SR wherein R can be hydrogen, halogen, C 1 -C 20 aryl, C 7 -C 0 alkylaryl, C 7 -C a arylalkyl, C 1 -C 6 arylalkyl or y can be the same or different or can be joined to form cyclic species containing from 2 to 20 atoms of carbon. The appropriate examples of Base groups of P1759 / 99MX Lewis include the following A particularly preferred diene to be used as the unsaturated portion in the present invention is 1-phenyl-4- (N, N '-dimethylaminophenyl) -1,3-butadiene represented by the formula: Illustrative and non-limiting examples of the preferred complexes are: (Ethylenebis-indenyl) zirconium (Me2N-dpbd) (EBIZr (Me2N-dpbd)) (Tert-butylamido) (? 5-tetramethyl leiclopentadieni) dimethylsilanetitanium (Me2N-dpbd) where (Me2N-dpbd) represents l-Phenyl-4- (4-N, N '-dimethylaminophenyl) -1,3-butadiene P1759 / 99MX Another suitable complex that is used in the present invention may be represented by formula 1: Y ARm wherein L is as described above M is a metal atom of group IIIB, IVB, VB or VIB of the Periodic Table X is a heteroatom or a hydrocarbyl group having from 1 to 40 carbon atoms and is a hydrocarbyl group that has from 1 to 40 carbon atoms and wherein X and / or Y contain at least one Lewis Base Group B as previously defined. A is a metal atom of Group IB, IIB, IIIA, IIIB, IVA, VA, VB, VIB, VIIB or VIIIB of the Periodic Table. R is identical or may be different and each is a perhalogenated C1-C40 hydrocarbon radical, and m = 1-5. The complexes according to the present P1759 / 99MX invention can be adequately supported. Therefore, a supported catalyst system suitable for use in the polymerization of olefins is provided, comprising: (A) transition metal complex of the formula: LxQyM - D wherein M is titanium, zirconium or hafnium in the oxidation state +2 or +4, L is a group containing a delocalized, cyclic anionic p system, through which the group is attached to M, Q is a bound entity to M and L by a bond s comprising boron or a member of Group 14 of the Periodic Table and also comprising nitrogen, phosphorus, sulfur or u. oxygen, the portion has up to 60 atoms that are not hydrogen; x = 1 or 2 y = 0 or 1 so that when x = 1, y = 1 and when x = 2, y = 0 and D is an unsaturated, unconjugated, neutral conjugate, optionally substituted with one or more hydrocarbyl groups, D has up to 40 carbon atoms and forms a p complex with M, P1759 / 99MX when M is in the oxidation state +2 and a complex s with M when M is in the oxidation state +4, and has at least one group B of Lewis Base, and (B) a support. Typically, the support can be any inert organic or inorganic solid, particularly porous supports such as talc, inorganic oxides and resinous support materials such as polyolefins. Suitable inorganic oxide materials that can be used include Group 2, 13, 14 or 15 of the metal oxides such as silica, alumina, silica, alumina, silica-alumina and mixtures thereof. Other inorganic oxides that can be used either alone or in combination with silica, alumina or silica-alumina are magnesia, titanium or zirconium. Other suitable support materials can be used, for example finely divided polyolefins such as polyethylene. The most preferred support materials that are used with the supported catalysts according to the process of this invention are silica. Suitable silicas include Crosfield ES70 and Grace Davison 948. It is preferred that the silica is made each before used and this is typically carried out by heating at elevated temperatures, for example between 200 and 850 degrees C.

P1759 / 99MX The support can preferably be treated to modify its surface properties. Suitable reagents are reactive, metallic and non-metallic alkyl compounds, and non-metallic and reactive metal hydrides, and reactive compounds containing alkyl and / or hydride functional groups. Examples include magnesium alkyls, boron alkyls, aluminum alkyls, gallium alkyls, titanium alkyls, zirconium alkyls, hafnium alkyls, zinc alkyls and the corresponding hydrides and mixed alkylhydride compounds. An example of suitable mixed alkylhydride compounds is d-isobutylaluminum hydride. When used as a component for a catalyst system in the polymerization of olefins, the supported complexes of the present invention are used in the presence of an activating technique or a suitable activator. Therefore, in accordance with another aspect of the present invention, a catalyst system suitable for the polymerization of olefins is provided, comprising: (a) a supported catalyst as defined above, and (b) an activation technique or a activator. The complexes can be made catalytically active by the combination with the appropriate activating cocatalyst and by the use of a P1759 / 99MX activation, which are effective for the supported transition metal complexes of the present invention. Suitable activating cocatalysts used herein include polymeric or oligomeric alumoxanes, especially methylalumoxane, methyloalumoxane modified with triisobutyl aluminum or diisobutyl alumoxane; strong Lewis acids, such as for example Group 13 compounds substituted with C1-30 hydrocarbyls, in special klO compounds of tri (hydrocarbyl) aluminum- or tri (hydrocarbyl) boron and halogenated derivatives thereof having 10 carbon atoms in each hydrocarbyl group or halogenated hydrocarbyl group, more especially perfluorinated compounds of Tri (aryl) boron and more preferably tris (pentafluorophenyl) borane; ion-forming, uncoordinated, compatible, inert, non-polymeric compounds (including the use of these compounds under oxidation conditions); bulk electrolysis and combination of techniques and activating cocatalysts that are mentioned in the foregoing. The activating cocatalysts and the above activating techniques have already been taught previously with respect to these metal complexes in the document mentioned WO 95/00526 which is incorporated herein by reference. A particularly preferred activator is tris (pentafluorophenyl) boron.

P1759 / 99MX Suitable ion forming compounds useful as cocatalysts comprise a cation which is a Bronsted acid capable of donating a proton, and an anion, uncoordinated, compatible, inert, A. "Preferred anions are those that contain a single coordination complex comprising a metalloid or metal core that carries a charge, the anion is able to balance the charge of the species active catalyst (the metal cation) that is formed when the two components are combined Also, the anion must be sufficiently labile to be displaced by the olefinic, diolefinic and acetylenically unsaturated compounds or by other neutral Lewis bases such as for example ethers or nitriles Suitable metals include, without limitation, aluminum, gold and platinum, Suitable metalloids include, without limitation, boron, phosphorus and silicon Compounds containing anions comprising coordination complexes containing a single metal or metalloid atom are available particularly in commercial form as compounds containing a single boron atom in the anion portion. - __ Preferred boron compounds are salts such as: tris tetrakis (pentafluorophenyl) borate tetrakis (pentafluorophenyl) borate triethylammonium P1759 / 99MX N, N-dimethylarylin tetrakis (pentafluorophenyl) borate of N, N-diethylolium tetrakis (pentafluorophenyl) borate. The most preferred activators of this type are trialkylmonium tetrakis (pentafluorophenyl) borates. The molar ratio of the complex to the activator that is employed in the process of the present invention may be in the range of 1: 10000 to 100: 1. A preferred range is from 1: 5000 to 10: 1 and most preferred is from 1:10 to 1: 1 .. In a preferred protocol the supported catalyst can be prepared by the addition of a solution of the activator in a suitable solvent towards a silica paste activated and treated with a trialkylammonium compound, followed by the addition of a metallocene complex solution in the same solvent. Alternatively, the complex can be added to the trialkylammonium treated with silica before the addition of the activator. Therefore, according to another aspect of the present invention, there is provided a method for preparing a supported catalyst comprising the steps of: (a) adding an activator in a suitable solvent to a support; P1759 / 99MX (b) the addition of a transition metal complex as described above, to the solution obtained in step (a); and (c) the withdrawal of the solvent. Suitable solvents for the preparation of the supported complexes are alkanes and aromatic solvents such as pentanes, hexanes, heptanes, octanes, Isopar * ™ ', toluene, xylenes, benzenes and mixtures thereof. A solvent particularly suitable for the preparation of the catalyst is toluene. Suitable trialkylaluminum compounds are trialkylaluminum (TMA), triethylaluminum (TEA) or triisobutylaluminum (TIBAL). The supported catalyst of the present invention has the advantage of allowing the catalyst to be fixed to the support and also allows a greater flexibility of preparation, in particular with greater preparation options. In addition, the morphology of the product can be improved, the clogging during the process can be reduced and both activity and productivity can be improved. The supported catalyst system according to the present invention is suitable for use in the polymerization of olefins, in particular in the homopolymerization of ethylene or the copolymerization of ethylene with other alpha olefins, in particular those having from 3 to 10 carbon atoms. With P1759 / 99MX higher preference, alpha olefins are 1-butene, 1-hexene and 4-methyl-1-pentene. ? According to another aspect of the present invention a process for the Polymerization of ethylene or the copolymerization of ethylene and alpha olefins having from 3 to 10 carbon atoms, which comprises carrying out the process in the presence of a catalyst system comprising a supported transition metal complex and an activating klO as the one that has just been described. The catalyst system according to the present invention is more suitable for use in the gas phase or in the paste phase, but it is most suitable for it to be used in the gas phase. A particularly preferred process is to operate using a fluidized bed and in particular a process as described in EP 699213. The use of the supported catalyst system according to the polymers of the present invention can be prepared with densities in the range of 0.905 to 0.960 g / cc and a melt index in the range of 0.1 to 20, according to ASTM D1238, condition E (2.16 Kg at 190 degrees C). The present invention will be illustrated below with reference to the following Examples.

P1759 / 99MX Example 1 Preparation of 1-pheny1-4- (4-N, N '-? Dimethylaminophenyl) -1,3-butadiene (Me2N-dpbd) Triphenylbenzylphosphonium chloride (Aldrich, 4.044g, 10.4 mmol) and para-N, N'-dimethylaminocinnamaldehyde (Aldrich, 1682g, 9.6 mmol) was dissolved in ethanol (Aldrich, dry denatured, 200 ml) under nitrogen. To the stirring solution was added lithium ethoxide (Aldrich 20.8ml) 10 of IM solution in ethanol; 20.8 mmol) dropwise, over a period of 15 minutes at 20 ° C. The formation of precipitate was observed before the addition was complete. The flask was wrapped in aluminum foil and left to stir for 17 hours. The mixture of The reaction was filtered in air, the solid was washed on the filter frit with aqueous ethanol (60% ethanol v / v, 50ml) and air-dried for 5 minutes to give 1. 408g of the objective compound as a yellow solid (59% yield). Traces of ethanol and water are Were removed by heating the yellow solid under vacuum for 2 hours at 50 ° C. 1H nmr (in CDC13) showed that the product was a mixture of 80:20 of the trans: cis isomers.

Example 2_ Preparation of (and ilenbis-indenyl) zirconium (ea? -dpbd) (EBIZr (Me2? -dpbd)) (Ethylenebis-indenyl) zirconium dichloride P1759 / 99MX (Witco, 0.419g, 1 mmol) and (Me2N-dpbd) (prepared as in the Example, 0.249g, 1 mmol) were weighed into a flask in a glove box (< lppm 02 / H20). Toluene (freshly distilled over Na, 28 ml) was added and the pulp was stirred with a magnetic stirring bar for 2 hours. N-butyl lithium was added (Aldrich, 1.25 ml of 1.6M solution in hexane, 2mmol) in a term of 1 minute at 20 ° C. The mixture was stirred for 9 hours at 20 ° C and filtered in the glove box (25- | 10 50 μm deep). 5 milliliters of solvent was removed from the solution in vacuo. The solution was left in a freezer (-35 ° C) for 36 hours, and yellow crystals of unreacted diene were removed by filtration. The solution was concentrated to about half the volume in vacuo and put back in the freezer for 16 hours to give a mixture of brown / black solid and yellow crystals, isolated by filtration and the 1H nmr showed to be a mixture of white and diene product without react (molar ratio 85:15).

Example 3 Preparation of the Supported Catalyst TEA-treated silica was prepared in the following manner: 20 kg of Crosfield ES70 (activated at 500 ° C) formed a paste in 110 liters of hexane. 31.91 liters of 0.940M TEA in hexane were added (1.5 P1759 / 99 X mmol / Al / g silica) and the pulp was stirred (illegible) hours at 30 ° C. The silica was allowed to settle and the hexane supernatant was recovered. The silica (illegible) was washed with hexane, until the concentration of Al in the wash reached > lmmol Al / liter. Then the silica was dried in vacuo at 60 ° C. A portion of TEA-silica (lg) was used to form a paste with hexane (Aldrich, dry, 5 ml) in a glove box (< lppm 02 / H20). The solid prepared in Example 2 (8.1 mg) was dissolved in hexane (Aldrich, dry, 5 ml) to give a very intense red / brown solution, TEA / yes / hexane was added to the paste and stirred. The solid settled was colored red / brown and the supernatant was completely colorless. An additional example of the solid (3.0 mg) was dissolved in hexane (Aldrich, dry, 5 ml) and added to the paste in the same way. The settled solid apparently did not change color, but the supernatant was once again completely colorless. The supernatant was decanted from the solid and used to dissolve tris (pentafluorophenyl) boron (Witco, 8.9 mg, 17.3 μmol) which was added to the treated silica with stirring. The solvent was removed in vacuo to give a pink solid of free flow.

Example 4_ Preparation of the Supported Catalyst A portion of TEA-silica (1.094g) prepared P1759 / 99MX as above was used to form a paste with hexane (Aldrich, dry, 5 ml) in a glove box (< lppm 02 / H20). The solid prepared in Example 2 (405 mg) was dissolved in hexane (Aldrich, dry, 20 ml) to give a very intense red / brown solution. Aliquots of this solution (3 ml) were added to the TEA / silica paste, which was stirred and allowed to settle. The addition was continued until the supernatant remained slightly colored. Approximately 10 ml of the supernatant was decanted from the solid and used to dissolve tris (pentafluorophenyl) boron (Witco, 25.3 mg, 49.4 μmol), which was added to the treated silica with stirring. After 30 minutes, the solvent was removed under vacuum to give a free flowing pink solid.

EXAMPLE 5 Preparation of (tert-butylamido) (5-tetramethylethylcycloadiene) dimethylsilane titanium (Me2N-dpbd) To a solution of 185 mg (0.502 mmol) of dimethylsilyl (tetramethylcyclopentadienyl) (tert-butylamido) titanium dichloride and 125 mg (0.502 mmol) of l- (4-dimethylaminophenyl) -4-phenyl butadiene in 20 ml of toluene, 0.628 ml of n-BuLi (1.6 M hexane) was added at 0 ° C. The dark purple mixture was stirred for 12 hours at room temperature. The 1H-NMR showed P1759 / 99MX only 50% conversion, so that another 0.650 ml of n-BuLi was added and the reaction was stirred for another 12 hours. 5 ml of hexane were added. Filtration of the solution after cooling to 20 ° C and evaporating the solvent from the filtrate led to the isolation of a purple powder containing 25_% molar of free diene (Me2N-dpbd) and 75% molar of the (CH3) 2Si complex ( C5 (CH3) i) (NC (CH3) 3) Ti (Me2N-dpbd).

EXAMPLE 6 Preparation of Supported Catalyst The solid of example 5 (20.0 mg) was partially dissolved in hexane (Aldrich, dry, 15 ml) and the deep red / brown color solution was added to the silica treated with TEA (example 3, lg) which formed a paste in hexane (Aldrich, dry, 10 ml) with stirring. The settled solids were red / brown and the supernatant was completely colorless. The supernatant was decanted and to the solid was added the residual solid which was dissolved in toluene (Aldrich, dry, 5 ml). The supernatant completely decolorized after stirring and the solid was allowed to settle. The paste was filtered, washed with toluene (Aldrich, dry, 5 ml) on the filter frit and dried with nitrogen to give a pink / purple solid. The tris (pentaf luorophenyl) boron (Witco, 19mg, 37μmol) was dissolved in hexane (Aldrich, dry, 10ml) and the solid was added to the solution with P1759 / 99MX agitation. The solvent was removed under vacuum to give a pink / purple solid, free flowing.

EXAMPLE 1 Copolymerization of Ethylene / l-Hexene Using Supported Catalysts [0103] Tests were carried out in a stirred steel 2.51 autoclave, which was first purged with nitrogen (95 ° C, 1.5h). To the reactor was added dry sodium chloride (300g) and potassium hydride (0.54g) and heating continued (95 ° C, lh) before cooling to 73 ° C. Ethylene was added to obtain a pressure of 0.8 Mpa and the required amount of 1-hexene was added by an HPLC pump. The catalyst was injected under nitrogen pressure into the stirred reactor and the temperature was raised to 75 ° C. The reactor was maintained at 75 ° C and ethylene and 1-hexene were supplied to maintain the constant pressure and the ethylene / 1-hexene ratio throughout the duration of the reaction. Subsequently, the reactor was cooled to 20 ° C and the pressure was vented. The polymer product was removed, washed with methanolic hydrochloric acid followed by aqueous ethanol, dried (vacuum, 50 ° C) and weighed to obtain a yield. The results of the supported catalysts prepared in examples 3, 4 and 6 are given in the table.

P1759 / 99MX Example Preparation of Supported Catalyst The silica treated with TEA (prepared according to example 3, 3g) was mixed in toluene (dry, 15 ml) to form a paste. To this was added a solution of toluene with tris (pentafluorophenyl) boron (Boulder Scientific, concentration 7.85% w / w, 45 μmol borane) followed by a toluene solution of the EBIZr complex (Me2N-dpbd) (example 2, 15ml, 45μmol). Zr). The pulp was stirred and then the solvent was removed in vacuo to give a brick-red free-flowing solid.

Example Preparation of Supported Catalyst The method of Example 8 was used except that the order of addition of tris (pentafluorophenyl) boron and EBIZr (Me2N-dpbd) was reversed. A brick solid red color of free flow was obtained.

P1759 / 99MX E p e 10 Emplo y Comparati o ^. Preparation of Catalyst Supported The method of Example 8 was used except that a toluene solution of (ethylenebis-indenyl) zirconium trans- (1,4-diphenylbutadiene) (Boulder Scientific, concentration 1.32% w / w) was used in place of the toluene solution of the analog with dimethylamino function EBIZr (Me2N-dpbd). A free-flowing solid red brick color was obtained.

Examples 11 to 15 Copolymerization of Ethylene / l -Hexenne Tests were carried out in a stirred steel 2.51 autoclave, which was first purged with nitrogen (95 ° C, 1.5h). Dry sodium chloride (300g) and silica treated with triisobutylaluminum (TIBA-Si02) were added to the reactor., 0.6g) prepared in the following manner: silica (Grace Davison, 948, 50g) which was fluidized in a flow of dry nitrogen. The temperature was raised to 200 ° C for 2 hours and maintained for 5 hours before cooling to 100 ° C for 1 hour. A solution of triisobutylaluminum hexane (IM, 75ml) was added to the fluidized silica and the fluidization was continued for an additional hour, after which the treated silica was cooled to room temperature and anaerobically transferred to a glove box with an inert atmosphere. . The reactor was adjusted P1759 / 99MX at 70 ° C. Ethylene was added to obtain a pressure of 0.65Mpa, and the required amount of 1-hexene was added by a mass flow controller. The catalyst was injected under nitrogen pressure to the stirred reactor together with an additional amount of TIBA-Si02 (0.4g). The reactor was maintained at 70 ° C and ethylene and 1-hexene were supplied to maintain a constant pressure and the ratio of ethylene / 1-hexene over the duration of the reaction. The reactor was then cooled to 30 ° C and the pressure vented. The polymer product was removed, washed with water and with methanolic hydrochloric acid followed by aqueous ethanol, dried (vacuum, 50 ° C) and weighed to obtain a yield. The results of the supported catalyst prepared in Examples 8 to 10 are given in the following table.

Example 16 Preparation of (tert-butylamido) (? 5-tetramethylethylpentadienyl) dimethylsilanetitanium (Me2N-dpbd) (tert-butylamido) dichloride was mixed (? 5- tetramethylcyclopentadienyl) dimethyilathytitanium (0.368g, lmmol) and Me2N-dpbd (according to example 1, 0. 249g, lmmol) in toluene (dry, 30ml). N-Butyl lithium (Aldrich, 2 mmol, 1.25 ml of 1.6M hexane solution) was added at 40 ° C and stirred for 16 hours. The P1759 / 99 X solution was filtered and the solvent was removed in vacuo. The solid was washed with hexane (Aldrich, dry, 15 ml), filtered and residual hexane was removed in vacuo to leave a dark solid. The 1 H NMR analysis showed that this ratio was 1.4: 1 molar of the title compound and the free starting diene.

Example 17 Preparation of the Supported Catalyst The solid of Example 16 (72.5mg) was dissolved in toluene (dry, 5ml) and a toluene paste (dry, 20ml) of TEA-SiO2 (according to Example 2, 5g) was added. ) at 20 ° C with shaking. Upon settlement, the supernatant turned out to be clear and the solid had a very dark color. The solvent was removed in vacuo to give a free flowing purple solid. This solid (2g) was mixed in toluene (dry, 6ml) and added with toluene solution (4ml) of tris (pentafluorophenyl) boron (Boulder Scientific, 20.5mg), with stirring. There was no obvious color change or color change of the supernatant. The solvent was removed in vacuo leaving a free-flowing dark purple solid.

Example 18 Copolymerization of Ethylene / l-Hexene The polymerization was carried out using the supported catalyst of Example 17 according to P1759 / 99MX method described in example 7. The result is also given below in the following Table.

P1759 / 99 X

Claims (21)

1. NOVELTY OF THE INVENTION Having described the present invention, it is considered as a novelty and, therefore, the content of the following CLAIMS is claimed as property: 1. A transition metal complex suitable for use in the polymerization of olefins comprising a complex of the formula: LxQyM - D wherein: M is titanium, zirconium or hafnium in the oxidation state +2 or +4; L is a group that contains a p anionic, cyclic, delocalised system through which it is linked to the M group; Q is a portion linked to M by a bond s, comprising boron or a member of Group 14 of the Periodic Table and also comprising nitrogen, phosphorus, sulfur or oxygen, the portion having up to 60 non-hydrogen atoms; x = 1 or 2 y = 0 or 1 so that when x = 1, y = 1 and when x = 2, y = 0, and D is an unsaturated, conjugated or unconjugated, neutral portion, optionally substituted with one or more hydrocarbyl groups, D has up to 40 atoms
2. P1759 / 99MX carbon and forms a p complex with M, when M is in the oxidation state +2 and a complex s with M, when M is in the oxidation state +4 and that it has at least one B group of Base of Lewis. 2. A complex according to claim 1, wherein M is titanium, y = 1, x ***** 1 and Q is represented by ZY, where: Y is -O-, -S-, -NR * - , -PR * -, and Z is SiR2, CR * 2, SiR2SiR * 2, CR * 2CR * 2, CR * = CR *, CR2SiR * 2, or GeR * 2; wherein: R * at each occurrence is independently hydrogen, or a selected member of hydrocarbyl, silyl, halogenated alkyl, halogenated aryl, and combinations thereof; R * has up to 10 non-hydrogen atoms and, optionally, two R * groups of Z _ (when R * is not hydrogen) or a R * group of Z and a R * group of Y form a ring system. 3. A complex according to claim 2, having the formula:
3. D. P1759 / 99MX
4. 4. A complex according to claim 1, wherein M is zirconium, y = 0 and x = 2.
5. 5. A complex according to claim 4, having the formula:
6. 6. A transition metal complex suitable for use in the polymerization of defines, comprising a complex having the formula: wherein L is a group containing a p anionic, delocalized, cyclic system through which the group is attached to M, M is a metal atom of group IIIB, IVB, VB or VIB of the Periodic Table, P1759 / 99MX X is a heteroatom or a hydrocarbyl group having 1 to 40 carbon atoms, Y is a hydrocarbyl group having 1 to 40 carbon atoms and wherein X and / or Y contain at least one Base B Group of Lewis and A is a metal atom of Group IB, IIB, IIIA, IIIB, IVA, VA, VB, VIB, VIIB or VIIIB of the Periodic Table; R is identical or different and each is a C-C40 perhalogenated hydrocarbon radical, and m = 1-5. A complex according to any of the preceding claims, wherein group D is a diene. A complex according to any one of the preceding claims, wherein the Lewis Base group B is selected from -NR2, -PR2 / AsR2, -OR, -SR wherein R can be hydrogen, halogen, C1-C20 aryl / C -C4 alkylaryl, C -C arylalkyl, C8-C40 arylalkenyl and can be the same or different or can be joined to form cyclic species containing between 2 and 20 carbon atoms. 9. A complex according to any of the preceding claims, wherein the group D is 1-phenyl-4 (N, N1-dimethylaminophenyl) 1,3-butadiene. 10. The complex (ethylene bis- P1759 / 99MX indenyl) zirconium (1-pheny1-4- (N, N '-dimethylaminophenyl) -1, 3-butadiene 11. The complex (tert-butylamido) (n5-tetramethylcyclopentadienyl) dimethylsilanetitanium (1-phenyl-4-) (N, N'-dimethylaminophenyl) 1,3-butadiene 12. A supported catalyst system suitable for use in the polymerization of olefins, comprising: (A) a transition metal complex of the formula: LxQyM-D wherein M is titanium, zirconium or hafnium in the oxidation state +2 or +4, L is a group containing an anionic, cyclic, delocalized p-system, through which the group is attached to M, Q is a portion bound to M and L by a bond s, comprising boron or a member of Group 14 of the Periodic Table and also comprising nitrogen, phosphorus, sulfur or oxygen, the portion has up to 60 non-hydrogen atoms; x = 1 or 2 y = 0 or 1 so that when x = 1, y = 1 and when x = 2, y = 0 and D is an unsaturated portion, conjugated or not P1759 / 99MX conjugated, neutral, optionally substituted with one or more hydrocarbyl groups, D has up to 40 carbon atoms and forms a p complex with M, when M is in the oxidation state +2 and a complex s with M, when M is in the +4 oxidation state, and has at least one Lewis Base B group, and (B) a support. 13. A supported catalyst system according to claim 12, wherein the support is silica. 14. A catalyst system suitable for use in the polymerization of olefins comprising: (a) a supported catalyst according to claim 12, and (b) an activator or an activation technique. 15. A catalyst system according to claim 14, wherein the activator is tris (pentafluorophenyl) borane. 16. A catalyst system according to claim 14, wherein the activator is a trialkylammonium tetrakis (pentafluorophenyl) borate. 1
7. 7. A catalyst system according to claims 14 to 16, wherein the molar ratio between the complex and the activator is in the range of 1: 10000 to 100: 1. 1
8. 8. A catalyst system according to P1759 / 99MX claim 17, wherein the molar ratio between the complex and the activator is in the range of 1: 10 to 1: 1. 1
9. 9. A method for preparing a supported catalyst system comprising the steps of: (a) adding an activator in a suitable solvent to a support; (b) adding a transition metal complex according to claims 1 to 11, to the solution obtained from step (a) and (c) removing the solvent. 20. A process for the polymerization of ethylene or the copolymerization of ethylene and alpha olefins having from 3 to 10 carbon atoms, comprising carrying out the process in the presence of a catalyst system according to claims 14 to 18. 21. A process according to claim 20, which is carried out in the gas phase. P1759 / 99MX