MXPA01010596A - Delayed activity supported olefin polymerization catalystcompositions and method for making and using the same - Google Patents

Abstract

The invention provides supported catalyst and methods for making and using the same, which are characterized as employing organometallic Group 4-10 catalysts with specially selected dienes, which, when combined with a cocatalyst, result in a supported catast which has improved kinetic profiles in the gas polymerization process.

Description

i CATALYTIC COMPOSITIONS WITH SUPPORT WITH DELAYED ACTIVITY TO POLYMERIZE OLEFINS AND METHOD TO MAKE THEM AND USE THEM BACKGROUND OF THE INVENTION Catalysts for polymerization of olefins used in gas-phase processes are usually supported on a carrier in order to obtain a polymer with acceptable morphology. In desired form, the polymer particles will have a low content of fine particles (defined as particles that have a particle size < 125 μm) and a low content of agglomerates (defined as particles having a particle size> 1500 μm) and will be of an acceptable bulk density (> 0. 3 g / ml). Although the elevated activity characteristic of the metallocenes and catalysts With restricted geometry is advantageous from a productivity perspective, problems of polymer morphology could result because the supported catalyst is at maximum activity when injected into the reactor. This could give as The result is a very fast polymerization and a fracturing of the catalyst particles which leads to the formation of unacceptable amounts of fines, or to a combination of fines and high exotherms, which leads to the formation of agglomerates. In addition, fouling of the catalyst injector can occur which leads to the premature need to stop the polymerization and clean the injector. In contrast, traditional Ziegler-Natta catalysts do not achieve maximum activity until after the catalyst has been injected into the reactor. This difference is attributed in part to the fact that the addition of a cocatalyst, such as triethylaluminum, to the reactor can result in delayed activation of the catalyst. See, for example, Boor, John Jr. , Ziegler-Natta Catalysts and Polymeri zations, 1979, Academic Press, NY, Chapter 18: Kinetics. To control the polymerization of at least one α-olefin by means of a restricted geometry or metallocene catalyst in a gas phase polymerization process, a method within the reactor to activate the metal complex would be advantageous. However, this is problematic due to the fact that typical metal complexes and co-catalysts used for the polymerization of olefins easily form extremely active polymerization catalysts. US Patent 5,693,727 describes the addition of catalyst components as a liquid spray to the reactor. This patent provides that the entire co-catalyst or a portion thereof can be fed separately from the metal compounds to the reactor. This patent does not exemplify supported catalysts. US patent 5,763,349 describes the mixing of a metallocene halide and a cocatalyst on a support. The subsequent addition of a metal alkyl was then used to generate the active catalyst. Similarly, US Patent 5,763,349, teaches the introduction of a metal alkyl to the reactor to achieve the actuation. WO 95/10542 discloses the addition of supported catalyst and co-catalyst separately on two different carriers. Prior to introduction to the reactor, the supported metallocene halide / co-catalyst has minimal catalytic activity if any, indicating that all activation occurs within the reactor. This technology is based on the migration, inside the reactor, of either the metal complex or the co-catalyst from one particle to the other to achieve activation, which can lead to problems of product morphology. It is known that the complexes of Ti (II) and Zr (II) -diene such as those described in the patent E.U.A. No. 5,470,993 (incorporated in its entirety in the present invention for reference) can be activated by trispentafluorophenylborane or borate co-catalysts. These catalyst compositions often exhibit extremely high initial polymerization rates, elevated exotherms and decreasing reaction kinetics profiles in a batch reactor Those working in the industry will find a great advantage in the fully formulated catalyst composition for the gaseous polymerization of α-olefins that has presented a delayed initiation of the polymerization, a profile of improved reaction kinetics, and a high productivity with an increased catalyst lifetime, and at the same time generate a polymeric product characterized by fines and reduced agglomerates. All references in the present invention to elements belonging to certain groups refer to the Periodic Table of the Elements published and protected by CRC Press, Inc., 1995. In addition, any reference to Group or Groups must be to the Group or Groups as such. as reflected in this Periodic Table of the Elements using the IUPAC group numbering system. The complete teaching of any patent, patent application, provisional application or publication referred to in the present invention is incorporated herein by reference. The present invention provides a supported catalyst composition for use in the gas phase polymerization of one or more α-olefins and methods of making and using it, said catalyst composition comprising: A) an inert support, B) an Metal complex of Group 4-10 corresponding to the formula in which M is a metal of one of Groups 4 to 10 of the Periodic Table of the Elements, which is in the formal oxidation state +2 or +4, Cp is an anionic ligand group with p bonds, Z is a divalent moiety attached to Cp and linked to M through any of a covalent or covalent / covalent bond, comprising boron or a member of group 14 of the Periodic Table of the Elements, and further comprising nitrogen, phosphorus, sulfur or oxygen; X is a neutral conjugated diene-type ligand group having up to 60 atoms, or a dianionic derivative thereof; and C) an ionic co-catalyst that can convert the metal complex into an active catalyst for polymerization, wherein said catalyst composition is characterized by having an improved kinetic profile in a gas phase polymerization process. In one embodiment, the invention provides a supported catalyst composition as previously identified having a kinetic profile in the gas phase polymerization of one or more α-olefins in a batch reactor, which obeys the following relationship: Kr = A30 / A90 < 1.6 in which Kr is the ratio of the cumulative net activity of the catalyst 30 minutes after the start of the polymerization (A30) divided by the net cumulative activity of the catalyst 90 minutes after the start of the polymerization (A90). A30 and 9o are determined by calculating the grams of polymer / grams of catalyst composition with x time support (hours) x total monomer pressure (100 kPa). In another embodiment, the invention provides supported catalyst compositions and methods for making and using the same, in which the supported catalyst composition, when injected into a gas phase polymerization reactor, and in contact with one or more α-olefin monomers, has a Kr which is at least 10% less than K * r, where K * r is the net cumulative catalyst activity ratio for a comparative catalyst composition with support prepared using the metal complex (t-butyl and lido) dimet i 1 - (tetramethylcyclopentadienyl) silanetitanium (II) 1,3-pentadiene and a co-catalyst comprising (diet i 1 alumino-oxi phenyl) tris (pentaf luorophenyl) -borate of Armenian. The present invention provides a fully formulated supported catalyst composition with restricted geometry that exhibits high productivity with increased catalyst life. In particular, it has been found that, through the selection of a metal complex with an appropriate diene-type ligand in combination with an appropriate co-catalyst, in contrast to the known compositions which are characterized as having an initial catalytic activity elevated followed by a period of decreasing catalytic activity, the compositions of the present invention exhibit an improved kinetic profile through at least the first 90 minutes of polymerization. More specifically, the catalyst compositions could present in an initial catalyst activity that is less exothermic than for the comparative catalyst compositions. Additionally, the activity of the catalyst could also be increased over a longer period than that of the comparative catalyst compositions. Finally, the catalyst activity can finally decrease under reactor conditions at a rate that is lower than those for the comparative catalyst compositions. Suitable metal complexes could be derived from any transition metal, preferably group 4 metals that are in the formal oxidation state +2, or +4. Preferred compounds include metal complexes with restricted geometry containing an anionic ligand group with p-bonds, which may be cyclic or non-cyclic anionic ligand groups with delocalized p-bonds. Examples of such anionic ligand groups with p-bonds are the conjugated or non-conjugated dienyl groups, cyclic or non-cyclic, allyl groups, borate benzene groups and arene groups. By the term "linked with p-bonds" it is meant that the ligand group is linked to the transition metal by means of the delocalised electrons present on a p-bond. Each atom in the group linked with delocalized p-bonds can be substituted independently with a radical selected from the group consisting of hydrogen, halogen, hydrocarbyl, halogenhydrocarbyl, radicals containing heteroatoms of groups 15 or 16, metalloid radicals substituted with hydrocarbyl in which the metalloid is selected from group 14 of the Periodic Table of the Elements, and such hydrocarbyl or substituted hydrocarbyl metalloid radicals are also substituted with a heteroatom containing portion of Group 15 or 16. Within the term "hydrocarbyl" are including straight, branched and cyclic C 1 -C 2 alkyl radicals, C 6 -C 20 aromatic radicals, C 7 -C 20 alkyl substituted aromatic radicals and C 7 -C 20 aryl substituted alkyl radicals. In addition, two or more of said radicals can together form a fused ring system, including partially or completely hydrogenated ring fused systems, or these can form a metallocylate with the metal. Suitable hydrocarbyl substituted organometalloid radicals include monosubstituted, bisubstituted and tri-substituted radicals of Group 14 elements in which each of the hydrocarbyl groups contains from 1 to 20 carbon atoms. Examples of suitable hydrocarbyl substituted organometalloid radicals include trimethylsilyl, t-butyl-1-yl, ethyldimethylsilyl, methyldiethylsilyl, triphenylgermyl, and trimethylglyceryl groups. Examples of heteroatom containing portions of Group 15 or 16 include amine, phosphine, ether or thioether portions or divalent derivatives thereof, for example amide, phosphide, ether or thioether groups attached to the transition metal or metal of the series of lanthanides, and attached to the hydrocarbyl group or to the group containing the hydrocarbyl substituted metalloid. Examples of anionic groups, with delocalized p-links include but are not 1 mimic cyclopentadienyl, indenyl, fluorenyl, tetrahydroindenyl, tetrahydrofluorenyl, octahydrofluorenyl, pentadienyl, dimethyl-cyclohexadienyl, dimethyldihydroanthracenyl, dimethylhexahydro-anthracenyl, dimethylhydroanthracene, and boratabenzene groups, as well as the Ci-Cio or substituted hydrocarbyl substituted derivatives. with silyl substituted with C1-C10 hydrocarbyl thereof. Anionic groups with preferred delocalized p-links are cyclopentadienyl, tet ramet ilciclopent adieni lo, indenyl, 2,3-dimet il indenyl, fluorenyl, 2-met i 1 indenyl, 2-met il-4-phenyl indeni lo, tetrahydrofluorenyl, octahydrofluorenyl , tetrahydroindenyl, 2-methyl-s-indacenyl, 3- (N-pyrrolidinyl) indenyl, and cyclopenta (1) phenanthrenyl. Boratabenzenes are anionic ligands which are benzene analogs containing boron. These are known in the prior art and have been described by G. Herberich, et al., In Organometallics, 1995, 14, 1, 471-480. The preferred boratabenzenes correspond to the formula: wherein each R "is independently selected from the group consisting of hydrocarbyl, silyl or germyl radicals, each of said R" having up to twenty atoms other than hydrogen, and being optionally substituted with a group containing an element of Group 15 or 16. In complexes involving divalent derivatives of such groups with delocalized p-bonds, one atom thereof is bound by a covalent bond or a divalent group covalently linked to another atom of the complex, thereby which forms a system with a bridge portion. A preferred class of such Group 4 metal coordination complexes used in accordance with the present invention corresponds to the formula: wherein Cp is an anionic group, with delocalized p bonds that is attached to M, which contains up to 50 non-hydrogen atoms; is a metal of group 4 of the Periodic Table of the Elements in the formal oxidation state +2 or +4; X is a conjugated diene of C4_30 represented by the formula: CR- CR3 / 4 CHRl CHR4 in the dual R1, R2, R3 and R4 are each independently hydrogen, aromatic, substituted aromatic, fused aromatic, substituted fused, aliphatic, substituted aliphatic, aromatics containing heteroatoms, fused aromatics containing heteroatoms, or silyl; And it is -O-, -S-, -NR-, or -PR-; and Z is SiR2, CR2, SiR2SIR2, CR2CR2, CR = CR, CR2SiR2 or GeR2, BR2, B (NR2) 2, BR2BR2, B (NR2) 2B (NR2) 2, in which R in each occurrence is selected in the form independently of the group consisting of hydrogen, hydrocarbyl, silyl, germyl, cyano, halogen and combinations thereof, said R having up to twenty non-hydrogen atoms, or the adjacent R groups together forming a divalent derivative (i.e. a hydrocarbyl group) ilo, siladiilo or germadiilo) with which a system of fused rings is formed. A more preferred class of such metal coordination complexes of group 4 used in accordance with the present invention corresponds to the formula: in the cijial: M is titanium or zirconium in the formal oxidation state +2 or +4; X is a conjugated diene of C5_30 represented by the formula: wherein R1, R2, R3 and R4 are each independently hydrogen, aromatic radicals, substituted aromatics, fused aromatics, substituted fused aromatibs, aliphatics, substituted aliphatypes, aromatic containing heteroaryl, fused aromatic heteroary containing | atoms, or silyl; And it is -O-, -S-, -NR * -, or -PR * -; and Z is SiR * 2, CR * 2, SiR * 2SiR * 2, CR * 2CR * 2, CR * = CF7, CR * 2SiR * 2 or GeR * 2, R and R * each time they appear they are selected in independent of the group consisting of hydrogen? hydrocarbyl, silyl, germyl, cyano halogen and combinations thereof, said R having up to 20 non-hydrogen atoms, or the adjacent R groups together form a divalent derivative: e (ie, a hydrocarbaryl, siladiyl or germadiyl group) whereby a fused ring system is formed. Illustrative group 4 metal complexes that could be used in the practice of the present invention include: (tert-butylamido) (tetramethyl-5-cyclopentadienyl) dimethylsilanetitanium (II) 1,4-diphenyl-1, 3-butadiene, (tert-butylamido) (2-met il indeni 1) -dimet i 13 Ilanotitanium (II) l, 4-diphenyl-l, 3-butadiene, (tert-butylamido) (2-met i 1 indenyl) dimethylpilanetitanium (IV) 1,3-butadiene, (tert-butylamido) (2,3-dimethyl indenyl) -dimet il. silanot itanium (11) 1,4-diphenyl-1,3-butadiene, tert-butylamido) (2,3-dimethyl-indenyl) -dimethyl-silanetitanium (IV) 1,3-butadiene, (tert-butylamido) (2) , 3-dimethylindenyl) -dimethyl-silanetitanium (II) 1,3-pentadiene, include ion-forming compounds (including the use of such compounds under oxidizing conditions), especially the use of ammonium salts of phosphonium, oxonium, carbonium, silylium, sulfonium or ferrocenium of non-coordinating compatible anions, Lewis acids, such as the compounds of group 13 substituted with hydrocarbyl of C? _30, especially compounds of tri (hydroxy) aluminum or tri (hydrocarbyl) -boron and the halogenated (including perhalogenated) derivatives thereof, having from 1 to 20 carbon atoms in each of the hydrocarbyl or halogenated hydrocarbyl groups, more especially perfluorinated t-ri (aryl) boron compounds, and in even more special form tri s (pent af luorofenil) borane, and c Oombinations of the previous activating co-catalysts. The above activating co-catalysts have been previously described with respect to different metal complexes in the following references: US patent 5,132,380, 5,153,157, 5,064,802, 5,321, lp6, 5,721,185 and 5,350,723 Lewis acid combinations can also be used, especially the combination of a trialkylaluminum compound having from 1 to 4 carbon atoms in each alkyl group and a halogenated tri (hydrocarbyl boron) compound having 1 and 20 carbon atoms in each hydrocarbyl group, especially tris (pent af luorofeni) 1) -borane, further combinations of such mixtures of acid DS of Lewis with a polymeric or oligomeric alumoxane, and combinations of a single acid of Neutral Lewis, especially tris (peAtaf luorofenil) borane with a polymeric or oligomeric alumoxane. Suitable ionic compounds useful as cb-catalysts in one embodiment of the present invention comprise a cation which is a Bronsted acid that can donate a proton, and a compatible non-coordinating anion, A ". present invention, the term "non-coordinating" means an anion or a substance that is not coordinated with the precursor complex containing metal of group 4 or the catalytic derivative thereof, or that coordinates only weakly with such complexes, thereby remaining labile enough to be displaced by a Lewis base such as an olefin monomer.

A non-coordinating amon refers specifically to an anion which, when functioning as an anion that balances the charge in a cationic metal complex, does not transfer an anionic substituent or a fragment thereof to said cation thereby forming complexes neutral "Compatible anions" are anions that do not degrade to neutral: when the initially formed complex decomposes and does not interfere with the desired subsequent polymerization or with other uses of the complex. Preferred anions are those that contain a coordination complex comprising one or more charged metal or metalloid atoms whose anion is capable of balancing the charge of the active catalyst species (of the metal cation) which could be formed when the two components. Furthermore, said anion must be sufficiently labile to be displaced by olefinic, diolefinic, and more saturated compounds with acetylene or with other Lewis bases such as ethers or nitriles. Suitable metals include, but are not limited to, aluminum D, gold and platinum. Suitable metalloids include, but are not limited to, boron, phosphorus and silicon Compounds containing anions, which comprise coordination complexes that hydrocarbyloxide, hydrocarbyl substituted with hydrocarbyloxide, hydrocarbyl substituted with organometal, hydrocarbyl substituted with organometalloid, hydrocarbon loxy substituted with organometal, halogenohydrocarbyloxy, hydrocarbyl substituted with halogenohydrocarbyloxy, hydrocarbyl substituted with halocarbyl, and silylhydrocarbyl substituted with halogen (including perhalogenated hydrocarbyl radicals, perhalogenated hydrocarbyloxy and perhalogenated silylhydrocarbyl), said Q having up to 20 carbon atoms with the proviso that Q appears in no more once as halide. Examples of suitable Q groups are described in the patent E.U.A. 5,296,433 and in WO 98/27119, as well as elsewhere. In a more preferred embodiment, d is 1, that is, the counter ion has a single negative charge and is A "The activating co-catalysts comprising boron, which are particularly useful in the preparation of catalysts of this invention, are can represent by the following general formula: (L * -H) + (BQ4) "; in which: L * is as previously defined; B is boron in a formal oxidation state of 3; and Q is a hydrocarbyl group, hydrocarbyloxy, hydroxy lobi substituted with organometal, fluorinated hydrocarbyl, fluorinated hydrocarbyloxy or fluorinated silylhydrocarbyl with up to 20 non-hydrogen atoms, provided that in no more than one occasion Q is hydrocarbyl. More preferred, Q is each time a fluorinated aryl group, or a dialkylaluminum-oxy phenyl group, especially a pentafluorophenyl group or a diethylaluminum-oxyphenyl group appears. Illustrative, but not limiting, examples that can be used as an activating cocatalyst in the preparation of the improved catalysts of this invention are substituted ammonium salts such as: trimethylammonium tetraphenyl borate, methyldioctadecyl ammonium tetraphenyl borate, tetraphenylborate of triet ilamonio, tripropylammonium tetraphenyl borate, tri (n-butyl) ammonium tetraphenyl borate, and methenyltetradethyl octadecyl 1-ammonium rafenylborate, N, N-dimethylolium tetraphenylborate, N, N-diethylamyl tetraphenylborate, tetraphenylborate N, N-dimet i 1 (2, 4, 6 -trimet ilani 1 inio), tetraki s (pentafluoropheni 1) trimetholammonium borate, tet rakis (pentaf luorophenyl) borate methyl-ditetradecylammonium, tet raki s (pent af luorofeni 1) methyl-dioctadecylammonium borate, triethyl ammonium tetrakis (pentafluorophenyl) borate, tripropium lamonium tetrakis (pentafluorophenyl) borate, tetrakis (pentaf luorofeni 1) tri (n-butyl) ammonium borate, tetrakis (pentaf luorophenyl) ) borate of tri (sec-butyl) ammonium, tetrakis (pentaf luorophenyl) borate of N, N-dimethylanilinium, tetrakis (pentafluorophenyl) borate of N, N-diethylanilinium, tetrakis (pentafluorophenyl) borate of N, N-dimethyl (2, 4, 6-trimethylanilinium, tetrakis (2, 3, 4, 6-tetrafluorophen il) trimethylammonium borate, tetrakis (2, 3, 4, 6-tetrafluorophenyl) borate triethyl ammonium, tetrakis (2, 3, 4, 6-tetraf luorophenyl) borate tripropyl ammonium, tetrakis (2,3,4, 6 - tet raf luorofeni 1) tri (n-butyl) ammonium borate, tetrakis (2, 3, 4, 6-tetraf luorophenyl) borate of dimet i 1 (t-but i 1) ammonium, tetrakis (2, 3, 4, 6-tetraf luorophenyl) borate of N, N-dimethylanilinium, N, -diethylanilinium tetrakis (2, 3, 4, 6-tetraf luorophenyl) borate, tetrakis (2, 3, 4, 6-tetraf luorofenil) borate N, N-dimet i 1 - (2,4,6-trimethylanilinium). Dialkyl ammonium salts such as: tetrakis (pentafluorophenyl) borate of dioctyl monoclonal acid, tet rakis (pentaf luorofenyl) borate of di tet radecylammonium, and tetrakis (pentafluorophenyl) borate of dicyclohexylammonium. Phosphonium trisust salts such as tetrakis (pentafluorophenyl) borate of tri phenyl phosphonium, tetrakis (pent af luorophenyl) borate of meth i ldioct adecyl phosphonium, and tet raki s (pentaf luorophenyl) borate of t ri (2, 6-dimethyl phenyl) phosphonium. Those co-catalysts referred to in this application are preferred as Armenian salts of boron-containing anions, more particularly, triammonium salts, containing one or two C ?4-C2o alkyl groups on the cation of ammonium and anions that are tet raki spentaf luorofenilborato. Preferred Armenian salt cocatalysts are tet rakis (pent af luorophenyl) borate methyldi (octadecyl) ammonium and tetrakis (pentaf luorophenyl) borate methyldi (tet radecyl) ammonium, or mixtures including them. Such mixtures include protonated ammonium cations obtained from amines comprising two C? 4, C15 o or C? 8 alkyl groups and a methyl group. Such amines are referred to in the present invention as Armenians and the cationic derivatives thereof are referred to as Armenian cations. These can be obtained from Witco Corp., under the trade name KemamineTM T9701, and of Alzo-Nobel under the trade name Armeen ™ M2HT. Another suitable ammonium salt, to be used especially in the heterogeneous catalyst compositions is formed after the reaction of an organometal or organometalloid compound, especially a tri (alkyl (C6-6)) aluminum compound with an ammonium salt of a 1-tris (fluoroaryl) borate hydroxyaryl compound. The resulting compound is an organomethaloxaryl 1 tris (f luoroari 1) borate compound which is generally insoluble in aliphatic liquids. Typically, such compounds are conveniently precipitated on support materials, such as silica, alumina or silica attenuated with trialkylaluminum, to form a cocatalyst mixture on support. Examples of suitable compounds include the reaction product of a tri (alkyl (Ci-6)) aluminum compound with the ammonium salt of a hydroxyaryl tri (fluoroaryl) borate compound. Exemplary fluoroaryl groups include perfluorophenol, perfluoronaphthyl, and perfluorobiyl. Particularly preferred hydroxyaryl tris (f luoroaryl) borates include the ammonium salts, especially the above Armenian salts of: (-dimet i 1 alumino-oxy-1-phenyl) tris (pent a -fluorophenyl) borate, ( 4-dimet i 1 alumino-oxy-3, 5-di (trimethylsilyl) -1-phenyl) tris (penta-fluorophenyl) borate, (4-dimethyl-alum-3-yl-5-di (t-butyl) -1 phenyl) tris (pentaf luorophenyl) borate, (4-dimethyl-lalumino-oxy-1-benzyl) tris (pentafluorophenyl) borate, (4-dimethyl-1-alumino-oxy-3-met-1-phenyl) tris - (pentafluorophenyl) ) borate, (4-dimethyl ilalumino-oxi-tetraf luoro-1-phenyl) tris (pentafluorophenyl) borate, (5-dimet i 1 alumino-oxy-2-naphthyl) tris (pentafluorophenyl) borate, 4 - (4-dimet ilalumino-oxy-1-phenyl) phenyltris- (pentafluorophenyl) borate, 4- (2- (4-dimethyl-ilalumino-phenyl-1-propan-2-yl) -phenyloxy) tris (pentafluorophenyl) -borate, (4-dimethylaluminum - oxy-1-phenyl) tris (pentafluorophenyl) borate, (4-diethylalumino-oxy-3, 5- di (trimetyl-1-silyl) -1-phenyl) tris (pentafluorophenyl) borate, (4-dimethylalumino-oxy-3,5-di (t-butyl) -1-phenyl) tris (pentafluorophenyl) borate, -diet ilalumino-oxy-1-benzyl) tris (pentafluorophenyl) borate, (4-dimethylalumino-oxy-3-methyl-1-phenyl) tris (pentafluorophenyl) borate, (4 -diet ilalumino-oxy-tetrafluoro-1-phenyl) tris (pentaf luorophenyl) borate, (5-ethyl-ilalumino-oxy-2-naphthyl) tris (penta-fluoro-phenyl) -borate, 4- (4-diethyl ilalumino-oxy-1-phenyl) phenyltris- (pentafluorophenyl) borate, 4- (2- (4-dimethylalumino-oxy phenyl) propane-2-yl) phenyloxy) tris (pentafluorophenyl) borate, (4-diisopropylalumino-oxy-1-phenyl) tris- (pentaf luorophenyl) borate, (4-diisopropylalumino-oxy-3, 5-di (trimethylsilyl) -1-phenyl) tris (pentafluorophenyl) borate, (4) -dii sopropil alumino -oxy-3, 5-di (t-butyl) 1-phenyl) tris (pentafluorophenyl) borate, (4-diisopropyl 1 alumino-oxy-1-benzyl) tris- (pentafluorophenyl) borate, (4) -diisopropylalumino-oxy-3-methyl-1-phenyl) tris (pentafluorophenyl) borate, (4-diisopropyl-1alumino-oxy-tetrafluoro-1-phenyl) tris (pentafluorophenyl) borate, (5-diisopropyl-1-alumino-oxy-2) -naphthyl) tris- (pentaf luorophenyl) borate, 4- (4-diisopropylalumino-oxy-1-phenyl) phenyltris (pentaf luorophenyl) borate, and 4- (2- (4-diisopropylalumino-oxyphenyl) -propan-2 -yl) phenyloxy) tris (pentafluorophenyl) borate. An especially preferred ammonium compound is (4-diethylalumino-oxy-1-phenyl) tris (pentaf luorofeni 1) methyldi- (tetradecyl) ammonium borate, (4-diethylalumino-oxy-lf eni 1) tri s (pentaf luorophenyl) ) methyldi- (hexadecyl) ammonium borate, (4-diethylalumino-oxy-1-phenyl) tris (pent af luorofenyl) methyldi- (octadecyl) ammonium borate, and mixtures thereof. The above complexes are described in the document WO96 / 28480, which is equivalent to the document USSN 08 / 610,647, filed March 4, 1996, and USSN 08 / 768,518, filed December 18, 1996. Another suitable activating co-catalyst comprises a salt of a cationic oxidizing agent and a non-coordinating anion , compatible represented by the formula: (? xe +) d (A'd-) e, in which: Oxe + is a cationic oxidizing agent that has a charge of e +; e is an integer from 1 to 3; and A'd "and d are as previously defined Examples of cationic oxidizing agents include: ferrocenium, hydrocarbyl substituted ferrocenium, Ag + or Pb + 2. The preferred embodiments of A d ~ are those anions previously defined with respect to Bronsted acid. containing activating co-catalysts, especially tet raki s (penta fluorophenyl) borate Another suitable co-catalyst activator comprises a compound which is a salt of a carbenium ion and a compatible, non-coordinating anion, represented by the formula: + A '"in which: ® + is a carbenium ion of C? _20; and A "is a compatible, non-coordinating anion having a charge of 1. A preferred carbenium ion is the trityl cation, ie tri phenylmethyl io.An additional suitable activating co-terminator comprises a compound which is a salt of a silyl ion and a compatible, non-coordinating anion represented by the formula: R3SiX 'nA' in which: R is a hydrocarbyl of C? _? 0; X 'is a Lewis base; n is O, 1 or 2, and A "is as previously defined. Preferred silylium salt activating co-catalysts are tetrakispentaf luteinophenylborate trimethylsilyl io, tet rakispentaf luorophenylborate of triethyl ester and the ether-substituted adducts thereof. Silylium salts have previously been described in generic form in J. Chem Soc. Chem. Comm., 1993, 383-384, as well as Lambert, J.B., et al., Organometal lies, 1994, 13, 2430-2443. The use of the above silylium salts as activating co-catalysts for the addition polymerization catalysts is claimed in the patent E.U.A. 5,625,087. Certain complexes of alcohols, mercaptans, silanols and oximes with tris (pentafluorophenyl) borane as co-catalysts are also effective and can be used in accordance with the present invention. Such co-catalysts are described in the patent E.U.A. 5,296,433. In a preferred embodiment, the co-catalyst will comprise a compound corresponding to the formula: (A + a) b (EJJ) "cd, in which: A is a charge cation + a, E is an anion group having from 1 to atoms, not counting the hydrogen atoms, which also contains two or more Lewis base sites: J independently, each occasion that appears, is a Lewis acid coordinated with at least one Lewis base site of E , and optionally two or more such J groups can be joined together in a portion having multiple functional groups of the Lewis acid type, j is a number from 2 to 12 and a, b, c, and d are integers of 1 to 3, with the condition that axb equals acx d. Such compounds are described and claimed in the application USSN 09/251664, filed on February 17, 1999. Examples of the co-catalysts of this class that are most preferred are the substituted imidazole anions having the following structures: wherein: A + is as previously defined, and preferably is a trihydrocarbylammonium cation, which contains one or two C10-alkyl groups or / especially the methyldioct acrylammonium cation, R 'each time it appears is selected in the form independently of the group consisting of hydrogen, hydrocarbyl, silyl, germyl, cyano, halogen and combinations thereof, each of said R 'having up to 30 non-hydrogen atoms (especially a methyl group or a C10 hydrocarbyl group or top), and L is a t-aff luoroarilboro or trisf luoroarylaluminum compound containing three fluoroaryl groups of C6_20, especially pentafluorophenyl groups.

The molar ratio of cat to precursor / co-catalyst used preferably ranges from 1:10 to 10: 1, more preferred from 1: 5 to 5: 1, even more preferred from 1: 1.5 to 1.5: 1. Preferably, the catalyst and activator co-catalyst are present on the support in an amount of from 5 to 200, more preferably from 10 to 75 micromoles per gram of support. Preferred supports for use in the present invention include silicas, aluminas and aluminosilicates with high porosity and mixtures thereof. The most preferred support material is silica. The support material may be in granulated, agglomerated, compressed form, or in any other physical form. Appropriate materials include, but are not limited to, silicas available from Grace Davison (W.R. Grace Division. & CO.) Under the designations SD 3216.30, Davison Syloid 245, Davison 948 and Davison 952, and Crossfield under the designation ES70, and Degussa AG under the designation Aerosil 812; and the available aluminas from Akzo Chemicals Inc. under the designation Ketzen Grade B. Suitable carriers for the present invention preferably have a surface area as determined by nitrogen porosimetry using the method B.E.T. from 10 to 1,000 m2 / g, and more preferred from 100 to 600 m2 / g. The pore volume of the support, as determined by nitrogen adsorption, is conveniently from 0.1 to 3 cm3 / g, preferably from 0.2 to 2 cm3 / g. The average particle size depends on the method used, but is generally 0.5 to 500 μm, preferably 1 to 100 μm. It is known that both silica and alumina inherently possess small amounts of hydroxyl functional groups. When used as a support in the present invention, these materials are preferably subjected to a thermal treatment or a combination of chemical and thermal treatment to reduce the content of hydroxyl groups thereof. Typical thermal treatments are carried out at a temperature between 30 ° C and 1000 ° C (preferably between 250 ° C and 800 ° C for four or more) for a period of 10 minutes up to 50 hours in an inert atmosphere or air or under reduced pressure, that is, at a pressure less than 200 Torr. When calcination occurs under reduced pressure, the preferred temperatures are 100 to 800 ° C. The residual hydroxyl groups are then removed by chemical treatment. Typical chemical treatments include contacting with Lewis acid type alkylating agents such as trihydrocarbylaluminum compounds, t-hydrocarbylchlorosilane compounds, t-hydrocarbylalkoxysilane compounds or with similar agents. Functional groups can be added to the support with an agent that provides functional groups silane or chlorosilane to bind to them the pendant functional groups silane - (Si-R) =, or chlorosilane - (Si-Cl) =, in which R is a hydrocarbyl group of C? .10. Agents that provide appropriate functional groups are compounds that react with the hydroxyl groups on the surface of the support or that react with the silicon or aluminum of the matrix. Examples of suitable agents that provide functional groups include phenylsilane, hexamethyldisilazane, di-phenyl-tin, met-phenyl-1-silane, dimethyl-tin, diethylamine, dichlorosilane, and dichlorodimethansilane. Techniques for forming such silica or alumina compounds with functional groups were previously described in US Patents 3,687,920 and 3,879,368. Alternatively, the agent that provides functional groups can be an aluminum component that is selected from an alumoxane or an aluminum compound of the formula: AlRVR2y, wherein: R1 each time it occurs is independently hydride or R #, R2 is hydride, R # or OR #, R # each time it is presented is selected independently from the group consisting of hydrogen, hydrocarbyl, silyl, said R # having up to 20 atoms other than hydrogen, x ' is 2 or 3, and 'is 0 or 1 and the sum of x' + y 'is 3. Examples of suitable R1 and R2 groups include methyl, methoxy, ethyl, ethoxy, propyl (all isomers), propoxy (all isomers), butyl (all isomers), butoxy (all isomers), phenyl, phenoxy, benzyl and benzyloxy. Preferably, the aluminum component is selected from the group consisting of tri (hydrocarbyl (C? 4)) aluminum compounds. The most preferred aluminum components are trimethylaluminum, triethylaluminum, triisobutylaluminum, and mixtures of the same. Such treatment typically occurs by: (a) adding a sufficient amount of solvent to the calcined silica to obtain a suspension; (b) adding to the suspension the agent in an amount of 0.1 to 5 mmoles of agent per gram of calcined silica, preferably 1 to 2.5 mmoles of agent per gram of calcined silica to form a treated support; (c) washing the treated support to remove the unreacted agent to form a washed support, and (d) drying the washed support by heating it or a combination thereof by subjecting it to reduced pressure. Suitable support materials, also referred to as carriers or carrier materials, used in the present invention include those carrier materials that are typically used in supported catalyst techniques, and more particularly the catalyst technique with support for polymerization. of addition of olefin with support. Examples include porous resin materials, for example, polyolefins such as polyethylenes and polypropylenes or styrene-divinylbenzene copolymers, and solid inorganic oxides including oxides of metals of Groups 2, 3, 4, 13, or 14, such as such as silica, alumina, magnesium oxide, titanium oxide, thorium oxide, as well as mixed silica oxides. Suitable mixed silica oxides include those of silica and one or more metal oxides of group 2 or 13, such as the mixed oxides of yes 1 ice-magnesium dioxide and yes 1 ice-alumina. Silica, alumina and mixed oxides of silica and one or more metal oxides of group 2 or 13 are preferred as support materials. Preferred examples of such mixed oxides are silicas-aluminas. The most preferred support material is silica. The shape of the silica particles is not critical and the silica can be in a granular, spherical, agglomerated, vaporized or other form. Suitable support materials for the present invention preferably have a surface area as determined by nitrogen porosimetry using the B.E.T method. from 10 to 1,000 m2 / g, and more preferred from 100 to 600 m2 / g. The pore volume of the support, as determined by nitrogen adsorption, is typically up to 5 cm3 / g, conveniently between 0.1 and 3 cm3 / g, preferably from 0.2 to 2 cm3 / g_. The average particle size is not critical but is generally from 0.5 to 500 μm, preferably from 1 to 200 μm, most preferred up to 100 μm. Preferred supports for use in the present invention include silicas, aluminas and aluminosilicates with high porosity and mixtures thereof. The most preferred support material is silica. The support material may be in granulated, agglomerated, compressed or in any other physical form. Suitable materials include, but are not limited to, silicas available from Grace Davison (Division of WR Grace &Co.) under the designations SD 3216.30, Davison Syloid ™ 245, Davison 948 and Davison 952, and Crossfield under the designation ES70 , and De Degussa G under the designation Aerosil ™ 812: and the available aluminas from Akzo Chemicals Inc. under the designation Ketzen ™ Grade B. It is known that both silica and alumina inherently possess small amounts of hydroxyl functional groups. In the practice of the present invention, these materials are preferably heat treated with a combination of chemical and thermal treatment to reduce the content of hydroxyl groups thereof. Typical thermal treatments are carried out at a temperature between 30 ° C and 1000 ° C (preferably between 250 ° C and 800 ° C for 5 hours or more) for a period of 10 minutes up to 50 hours in an inert atmosphere or air or under reduced pressure, that is, at a pressure lower than 200 Torr. When calcination occurs under reduced pressure, the preferred temperatures are 100 to 800 ° C. The residual hydroxyl groups are then removed by chemical treatment. Typical chemical treatments include contacting with Lewis acid type alkylating agents such as trihydrocarbylaluminum compounds, trihydrocarbylchlorosilane compounds, hydrocarbon compounds, coxy tin or with similar agents.

Functional groups can be added to the support with an agent that provides functional groups silane or chlorosilane to bind to them the pendant functional groups silane - (Si-R) =, or chlorosilane - (Si-Cl) =, in which R is a hydrocarbyl group of C? _? 0. Agents that provide appropriate functional groups are compounds that react with the hydroxyl groups on the surface of the support or that react with the silicon or aluminum of the matrix. Examples of suitable agents that provide functional groups include phenylsilane, hexamethyldisilazane, di-phenyl-tin, methyl-phenylsilane, dimethylsilane, diethylsilane, dichlorosilane, and dichlorodimethylene. Techniques for forming such silica or alumina compounds with functional groups were previously described in US Patents 3,687,920 and 3,879,368, the teachings of which are found in the present invention. To prepare the catalyst compositions of the present invention in one embodiment, the metal complex, co-catalyst and catalyst support are suspended together in a compatible solvent, usually using an amount of solvent that is greater than the volume of support pore. The supported catalyst composition is subsequently dried while at the same time heat or a combination of heat and vacuum is applied to render the supported catalyst composition substantially free of solvent. In a preferred embodiment of the invention, a double sequence impregnation technique is used. In this preferred embodiment of the invention, the support is heated to remove water and reacted with an appropriate agent that provides functional groups to form a support precursor. The support precursor is contacted sequentially with a first solution of either a metal or co-catalyst complex, and thereafter it is contacted with a second solution of the other metal complex or co-catalyst. . In each of the two steps of contacting, the solution with which it is put in contact will be provided in an amount such that at no time will 100% of the pore volume be exceeded. Optionally, the support precursor can be dried to remove the compatible solvent after contacting the first solution. This feature, however, is not required, with the condition that the solid remains as a dry, free-flowing powder. In another preferred embodiment of the invention, the support is heated to remove water and reacted with an appropriate agent that provides functional groups to form a precursor of the support. The support precursor is suspended in a first solution of the metal complex or co-catalyst to form a supported catalyst. Sufficient compatible solvent is removed from the catalyst to obtain a recovered catalyst having free flow, ie, in which the amount of compatible solvent is less than 100% of the pore volume of the product. support precursor. After this, the propellant with the recovered carrier is contacted with a second solution of the other metal complex or cocatalyst, in which the second solution is provided in an amount less than 100% of the pore volume of the precursor. of the support, to form the supported catalyst composition. Because the amount of the second solution is insufficient to cause the supported catalyst composition to have free flow, an additional step of solvent removal is unnecessary. However, if desired, the compatible solvent can be removed in a more complete manner by applying heat, reduced pressure, or a combination thereof. In a particularly preferred embodiment, the metal complex is applied in the first solution, and the co-catalyst is applied in the second solution, in particular when the co-catalyst is easily degraded by the application of heat or by a combination of heat and vacuum during drying. In the case of each of these preferred modalities, and in particular in the case of the double impregnation technique, sufficient mixing must be carried out to ensure that the metal and co-catalyst complex are evenly distributed within the pores of the support precursor, and to ensure that the Support precursor will continue to have free flow. Some examples of mixing devices include batch rotary mixers, single cone mixers, double cone mixers, vertical conical dryers, etc. While not wishing to be bound by theory, it is believed that the catalyst compositions of the invention, prior to exposure to polymerization conditions, remain primarily in a non-altered chemical form, i.e., the metal complex and the compound. The catalysts remain in a relatively undisturbed and catalytically inactive form until they are exposed to the polymerization conditions. Once inside the reactor, at higher temperatures or a combination thereof in the presence of monomer, the catalyst composition becomes more active.

Therefore, catalysts can be prepared with lower initial reaction exotherms and with increasing polymerization rates (ascending kinetic profile), which could lead to improved performance in the polymerization reactor and improved polymer morphology. Catalysts can be used to polymerize unsaturated monomers with ethylene or a combination thereof unsaturated with acetylene having from 2 to 100,000 carbon atoms either alone or in combination. Preferred monomers include the C2-20 α-olefins in particular ethylene, propylene, isobutylene, 1-butene, 1-pentene, 1-hexene, 3-metyl-1 -pent ene, 4-methyl-1-pentene, 1-octene, 1-decene, long chain macromolecular α-olefins, and mixtures thereof. Other preferred monomers include styrene, styrene substituted with C? _4alkyl, tetrafluoroethylene, vinylbenzocyclobutane, and ilidene norbornene, 1,4-hexadiene, 1,7-octyl adieno, vinyl cyclohexane, 4-vinylcyclohexane, divinylbenzene, and mixtures thereof with ethylene. The long chain macromolecular α-olefins are vinyl-terminated polymeric remnants formed in-itself during the continuous solution polymerization reactions. Under appropriate processing conditions such long chain macromolecular units are easily polymerized in the polymeric product together with ethylene and other short chain olefins monomers to give small amounts of long chain branching in the resulting polymer. The most desired α-olefin polymers, prepared using the catalyst compositions of the present invention, have inverse molecular architecture, which means that a copolymer of two or more olefins contains an increased content of the highest molecular weight comonomer in the highest molecular weight fractions thereof. In general, polymerization can be achieved under conditions well known in the prior art for polymerization reactions of the Ziegler-Natta or Kaminsky-Sinn type, such as temperatures between 0-250 ° C and pressures ranging from atmospheric pressure to 1000 atmospheres (0.1 to 100 Mpa.). Typically the best practices will be used, that is, the feeding currents must be dry and deoxygenated in an appropriate way to eliminate impurities; the temperature controls should be in place to minimize the reaction exotherm and avoid the escape reactions; appropriate scrubbers will be used as needed, eg silica treated with aluminum 1 -aluminum, potassium hydride, etc. Appropriate gas phase reactions could use the condensation of the monomer or monomers used in the reaction, or of an inert diluent to remove heat from the reactor. The support is preferably used in an amount that provides a weight ratio of catalyst (based on the metal): support from 1: 100,000 to 1:10, more preferred from 1: 50,000 to 1:20, and more preferred still from 1: 10,000 to 1:30. In most polymerization reactions, the molar ratio of the catalyst to the polymerizable compounds used is 10"12: 1 to 10" 1: 1, more preferred from 10"12: 1 to 10 ~ 5: 1. The catalysts can also be used, in combination with at least one additional homogeneous or heterogeneous polymerization catalyst, in the same reactor or in separate reactors connected in series or in parallel, to prepare polymer combinations having the desired properties. of a procedure as such is described in WO 94/00500, equivalent to the EUA application Serial No. 07 / 904,770, as well as in the EUA application Serial No. 087/10958, filed on January 29, 1993, The teachings of which are incorporated in the present invention The following metal complexes, which have been found to be preferred in the practice of the claimed invention, correspond to the formula: wherein M is titanium or zirconium in the formal oxidation state +2 or +4; X is diphenylbutadiene, or 1,6-di-phenyl-2,4-hexadiene; And it's -NR-; and Z is SiR2, and R, each time it is presented is independently selected from the group consisting of hydrogen, hydrocarbyl, silyl, germyl, cyano, halogen and combinations thereof, said R having up to 20 non-hydrogen atoms , or the adjacent R groups together form a divalent derivative (i.e., a hydrocarbonyl group, siladiyl or germadiyl) whereby a fused ring composition is formed. Those of these preferred metal complexes in which M is titanium and Z is SiMe 2 and And it is N-t-butyl are especially useful in the practice of the claimed invention. In another aspect, it has been discovered that the following co-catalysts, formed as the reaction product of an organometal compound, especially tri (alkyl (C6-6)) aluminum with an ammonium salt of a hydroxyaryl ris compound (fluoroar 1) borate, are preferred to be used in the practice of the claimed invention. Such co-catalysts can be conveniently blocked at the ends to form organometaloxyaryl compounds (R) (fluoroari 1) borate which makes them insoluble in hexane, and facilitates their precipitation on the support, typically silica, alumina or silica attenuated with trialkylaluminium. These cocatalysts have previously been described in WO 98/27119. An especially preferred co-catalyst to be used in the practice of the claimed invention includes the reaction product of a tri (alkyl (Ci-6)) aluminum compound with the ammonium salt of diethylalumino-oxyaryltris (perfluoroaryl) borate.

EXAMPLES Unless indicated otherwise, all manipulations were performed in an inert atmosphere either in a glove chamber filled with argon or under nitrogen using Schlenk techniques.

Reactives (t-butyl) (tet ramethyl-5-cyclopentadienyl) dimethylsilanetitanium (II)? 4-1,3-pentadiene and (t-butyl-lime) (tet ramet il-5) cyclopentadienyl) dimethylsilanetitanium (II) 1,4-di-phenyl-1,3-but-adiene as described in the US patent No. 5,470,993 examples A2 and 17 respectively. The compound tris- (pentaf luorophenyl) (4-hydroxy phenyl) borate of bis (tallowalkyl hydrogenated) methylammonium was prepared as described in PCT98 / 27119. The ISOPAR®E hydrocarbon mixture was obtained from the company Exxon chemical. All other solvents were purchased from Aldrich Chemical Company as anhydrous reagents and further purified by a nitrogen purge and passed through a 30.5 cm column of alumina in pieces which was heat treated overnight at 250 ° C. . All other reagents were purchased from Aldrich Chemical Company and used without further purification.

Preparation of silica 948 treated with TEA A 200 g sample of Davison 948 silica (available from Grace -Davi son) was calcined for 4 hours at 250 ° C in air, then transferred to a glove chamber filled with nitrogen. A 15 g sample of the silica was suspended in 90 ml of hexane, and 30 ml of a 1.0 M solution of triethylaluminum in hexanes was added over the course of several minutes. The rate of addition was slow enough to avoid refluxing the solvent. The suspension was stirred on a mechanical shaker for 1 hour. At this time, the solids were collected on a fritted funnel, washed three times with 50 ml portions of hexanes, and dried in vacuo. 1. Preparation of 40/40 μmol / g of [C5Me4SiMe2NtBu] Ti (B1NB) / AM2HT over TEA / silica A Preparation of 1,4-bis (1-naphil) butadiene (B1NB) 3 - (1-naphthalene) -2-propenoyl chloride 3 - (1 -naphthalenyl) -2-propionic acid (7.5 g, 0.038 mole) was suspended in 15 ml of oxalyl chloride and heated at reflux for 2 hours.

The resulting solution was evaporated to obtain 8.0 g (99%) of a yellow solid. 3 - . 3 - (1 -na f tal eni l) -2-propenal To a stirred solution of 3- (l-naphthalenyl) -2-propenoyl chloride (2.5 g, 0.012 mol) and 6.03 g (0.023 mol) of triphenylphosphine in 50 ml of acetone were added 7.65 g (0.013 mol) of bis (tri-phenyl-1-phosphine) -tetrahydroborate-copper in one portion. After one hour, the solution was filtered and the filtrate was evaporated to dryness. The residue was dissolved in 20 ml of chloroform and treated with 6 g of cuprous chloride, and allowed to stir for one hour and filtered. The solvent was evaporated to dryness to obtain 1.66 g (79%) of solid 1, 4 -bi s (1 -naphyl) butadiene To a stirred solution of 1-naphthylmethane and 11-phenylphosphonium chloride (3.98 g, 0.009 mole) in 30 ml of benzene was added a phenyl lithium ether / cyclohexane (5 ml, 0.009 mole) and allowed to stir for 30 minutes. A solution of 3- (1 -nafti 1) propenal (1.61 g, 0.009 mole) of 10 ml of benzene was added and the mixture was stirred for 14 hours. The mixture was filtered and the precipitated material was digested with toluene and filtered. The filtrate was concentrated to obtain a yellow solid (1.2 g, 45%) which was a mixture of about 5: 1 of the trans, ci-ss trans isomers. The trans, trans isomer was recrystallized selectively with toluene (400 mg).

B. Preparation of [C5Me4SiMe2NtBu] Ti (B1NB) A 50 ml flask was charged with [C5Me4SiMe2NtBu] TiCl2 (238 mg, 0.646 mmol), 1,4-bis (1 -naft i 1) butadiene (198 mg, 0.646 mmol), and 35 mL of hexanes. To the yellow suspension was added n-BuLi by syringe at 25 ° C (0.53 ml, 2.5 M, 1.33 mmoles). The immediate formation of a brown mixture was observed. After stirring for 15 minutes, the mixture was heated to reflux for 2 hours. The red / brown mixture was cooled slightly and then filtered through the Celite ™ filter aid in a sintered funnel. The filter cake was washed once with 10 ml of hexanes. The volatile compounds were removed from the red colored filtrate and the solid was recrystallized from hexanes to give 163 mg (42% yield) of a brick red solid.

C. Preparation of 40/40 μmol / g of [C5Me4 S_iMe2NtBu] Ti (B1NB) / AM2HT on TEA / silica A suspension of silica treated with TEA (prepared as described above, 2.50 g) in 4 ml of toluene was treated with a mixture of Armenian (p-hydroxyphenyl) tris (pentafluorophenyl) borate (2.5 ml, 0.040 M, 100 mmol) and TEA (1.1 ml, 0.10 M, 110 mmol) (thereby forming in si tu (diethylalumino -oxi phenyl) ) tris- (pentaf luorophenyl) borate of Armenian (AM2HT)). The suspension was stirred vigorously for 20 seconds and then a solution of the compound [(tert-butylamido) (dimethyl) - (tetramethylcyclopentadienyl) silane] titanium bis (1-naphthyl) butadiene in toluene (5.0 ml, 0.020 M, 100 mmol) was added. ). The mixture was stirred vigorously for one minute and then the volatile compounds were removed under vacuum to obtain 2.58 g of a red / brown solid with free flow. 2. Preparation of 40/40 μmol / g of [C5Me4SiMe2NtBu] Ti (B1NB) / AM2HT on TEA / silica A Preparation of 1,4-dibenzybutyl adienum (DBB) Diisobutylaluminum (DIBAL-H) (82.5 ml, 1.0 M, 82.5 mmole) was added, under an argon atmosphere, through an addition funnel to a solution of 3-phenylpropino (9.55 g, 82.2 mmol) in 40 ml of hexanes at 25 ° C. The solution was stirred for 20 minutes and then heated at 56 ° C for four hours. After cooling, the volatiles were removed in vacuo and about 125 ml of cold THF were added slowly.

Solid CuCl (9.77 g, 98.7 mmol) was added to the solution over a period of five minutes. The resulting black mixture was stirred for one hour, and then poured into a mixture of hexanes and dilute HCl. The organic layer was separated and the aqueous layer was extracted 3x with 150 ml of hexanes. The combined organic layers were washed with saturated NaHCO 3 and dried with anhydrous Na 2 SO 4. Removal of the volatile compounds gave a yellow / green solid. Recrystallization with hot hexanes gave 4.4 g of pale yellow crystals (46% yield).

, B. Preparation of [C5Me4SiMe2NtBu] Ti (DBB) Under an inert atmosphere of argon, a 50 ml flask was charged with [C5Me4SiMe2NtBu] TiCl2 (238 mg, 0.646 mmole), 1,4-dibenzylbutadiene (198 mg, 0.646 mmole), and 35 ml of hexanes. To the yellow suspension was added n-BuLi by syringe at 25 ° C (0.53 ml, 2.5 M, 1.33 mmoles). The immediate formation of a brown mixture was observed. After stirring for 15 minutes, the mixture was heated to reflux for 2 hours. The red / brown mixture was cooled slightly and then filtered through the diatomaceous earth filter aid in a sintered funnel. The filter cake was washed once with 10 ml of hexanes. The Volatile compounds were removed from the red colored filtrate and the solid was recrystallized from hexanes to give 163 mg (42% yield) of a brick red solid.

C Preparation of 40/40 μmol / g of [C5Me4SiMe2NfcBu] Ti (DBB) / AM2HT on TEA / silica A suspension of silica treated with TEA (prepared as described above, 2.00 g) in 5 ml of toluene was treated with a mixture of (p-hydroxy phenyl) tris (pentaf) luorofenil) Armenian borate (2.0 ml, 0.040 M, 80 mmol) and TEA (0.88 ml, 0.10 M, 88 mmol). The suspension was stirred vigorously for 30 seconds and then a solution of the compound [(tert-butylamido) (dimet i 1) tetramet-ilcyclopentadienyl) was added if the no] titanium 1,4-dibenzybutadiene in toluene (4.0 ml, 0.020 M, 80 mmoles). The mixture was stirred vigorously for 1 minute and then the volatile compounds were removed under vacuum to obtain 2.08 g of a brick-red solid with free flow.

D. Preparation of 30/30 μmol / g of [C5Me4 SiMe2NtBu] Ti (DBB) / AM2HT on TEA / silica To 2.86 g of silica treated with TEA prepared as described above, a mixture of AM2HT (1.2 ml of a 9.95 solution was added % by weight diluted to 3 ml) and TEA (0.05 ml of a 1.9 M solution in toluene). The mixture was vigorously stirred until a free flowing powder was obtained and the solvent was removed in vacuo. Then (t-butyl amide) (dimethyl) (tetramethylcyclopentadienyl) silane titanium 1,4-dibenzylbutadiene (3.80 ml of a 0.023 M solution in toluene) was added. The mixture was vigorously stirred until a free-flowing powder was obtained and then the volatile compounds were removed in vacuo. 3. Preparation of the catalysts [C5Me4 S_iMe2NtBu] Ti (1,4-diphenyl-l, 3-butadiene) and _C_5Me4SiMe2NfcBu] Ti (1,3-pentadiene) with AM2HT on TEA / silica TO . Catalyst preparation 30/30 μmol / g of [C5Me4SiMe2NtBu] Ti (1,4-diphenyl-1,3-butadiene) / AM2HT To 4.0 ml of a 0.040 M solution of (p-hydroxyphenyl) tris- (pentafluorophenyl) borate of Armenian in toluene was added 0.1 ml of a 1.9 M solution of Et3Al in toluene. This solution was mixed for 1 minute, then added to a Davison 948 silica treated with 4.04 g of Et3Al, prepared as described above, in 10 ml of toluene. To this suspension was added 3.2 ml of a 0.05 M solution of (t-butyl-lido) (tet ramet il-5-cyclopenta-dienyl) dimethylsilanetitanium (II) 1,4-di-phenyl-1, 3-but adieno in toluene. The solvent was removed in vacuo to give a free-flowing red / brown solid.

B. Catalyst preparation 30/30 μmol / g of [CsMe4SiMe2NtBu] Ti (1,3-pentadiene) / AM2HT A 3.0 ml of a 0.040 M solution of p-hydroxy f eni 1 tri s (pent af luorofeni 1) Armenian borate in toluene was added 70 μl of a 1.9 M solution of Et3Al in toluene. This solution was mixed for 30 seconds, then added to a Davison 948 silica treated with 3.0 g of Et3Al, prepared as described above, in 12 ml of toluene. To this suspension was added 0.55 ml of a 0.22 M solution of (t-butyl-lmido) (tet ramet il-5-cyclopentadienyl) dimet ilsilanotitanium (II)? -l, 3-pentadiene in toluene. The combined mixture was briefly suspended (<1 minute), and the solvent was removed in vacuo to give a green / brown, free-flowing solid. 4. Polymerizations A fixed, shaken 2.5-liter autoclave was charged with 200 g of dry NaCl containing 0.67 g of TEA / silica, and stirring was started at 300 rpm. The reactor was pressurized to 7 bars of ethylene and heated to 70 ° C. 1-hexene was introduced to a level of 8000 ppm as measured by mass 84 in a mass spectrometer. In a separate vessel, 0.1 g of catalyst was mixed with 0.5 g of additional scavenger. The combined catalyst and scrubber were injected sequentially into the reactor. The ethylene pressure was maintained in a stream on demand, and hexene was supplied as a liquid to the reactor to maintain the ppm concentration. The temperature was regulated by a heating bath with a tap for cold water. After 90 minutes, the reactor was depressurized, and the salt and polymer were removed by a drain valve. The polymer was washed with distilled water in abundance to remove the salt, then dried at 50 ° C. Activity values were calculated based on ethylene consumption. The results for the catalyst prepared above are given in the following Table I: TABLE I Catalyzed Run: Complex of A30a A90a Kr Exotherm # metal (° C) 1 * 3BB CGC (PD) 1 94 53 1.77 30 2 3A CGC (DPB) 2 86 89 0.97 7 3 2D CGC (DBB) 3 133 96 1.39 6 4 2C CGC (DBB) 130 105 1.24 5.8 2C CGC (DBB) 179 121 1.48 6.8 6 IC CGC (BINB) 4 201 125 1.61 31.5 7 IC CGC (BINB) 203 124 1.64 32 8 IC CGC (BINB) 163 96 1.70 22.4 * Comparative, it is not an example of the invention. to the units are grams of polymer / gram of catalyst composition with support * t time (hours) • ethylene pressure (100 kPa) 1 (t-butylamido) (dimethyl) (tet ramet ilcyclopenta-dienyl) silanot i tanium 1,3-pentadiene. 2 (t-butylamido) (dimethyl) (tetramethylcyclopentadienyl) silanetitanium 1,4-diphenyl-1,3-butadiene. 3 (t-butylamido) (dimethyl) (tetramethylcyclopentadienyl) silanetitanium 1,4-dibenzyl-1,3-butadiene. 4 (t-butyl and lime) (dimethyl) (t et ramet ile iclopent a-dienyl) silanetitanium 1,4-dinaphthyl-l, 3-butadiene As indicated in Table 1, catalyst systems 3A, 2C and 2D each presented a Kr less than 1.6. In turn, each of these catalyst compositions presented a less declining profile than that of the comparative catalyst compositions 3B and IC.

Claims (17)

1. NOVELTY OF THE INVENTION Having described the present invention, it is considered as a novelty and therefore the content of the following is claimed as property: CLAIMS 1. - A method for preparing a catalyst for olefin polymerization comprising: (a) selecting a metal complex corresponding to the formula: Cp-Mx \ / Z wherein M is a metal of one of Groups 4 to 10 of the Periodic Table of the Elements, which is in the formal oxidation state +2 or +4; Cp is an anionic ligand group with p bonds; Z is a divalent moiety bound to Cp and linked to M through any one of a covalent or covalent / covalent bond, comprising boron or a member of group 14 of the Periodic Table of the Elements, and further comprising nitrogen, phosphorus, sulfur or oxygen; and X is a neutral conjugated diene-type ligand group having up to 60 atoms, or a dianionic derivative thereof; (b) selecting an ionic co-catalyst that can convert the metal complex into an active catalyst for polymerization; and (c) placing the metal complex and the co-catalyst on a support, wherein said catalyst composition is characterized as having an improved kinetic profile in a gas phase polymerization process.
2. 2. A method for preparing a catalyst for olefin polymerization comprising: (a) selecting a metal complex corresponding to the formula: wherein Cp is an anionic group, with delocalized p bonds that is attached to M, which contains up to 50 non-hydrogen atoms; M is a metal of group 4 of the Periodic Table of the Elements in the formal oxidation state +2 or +4; X is a conjugated diene of C4_30 represented by the formula: wherein R1, R2, R3 and R4 are each independently hydrogen, aromatic, substituted aromatic, fused aromatic, substituted fused, aliphatic, substituted aliphatic, aromatics containing heteroatoms, fused aromatics containing heteroatoms or silyl; And it is -O-, -S-, -NR-, or -PR-; and Z is SiR2, CR2, SiR2SiR2, CR2CR2, CR = CR, CR2SiR2 or GeR2, BR2, B (NR2) 2, BR2BR2, B (NR2) 2B (NR2) 2, in which R in each occurrence is selected in the independently of the group consisting of hydrogen, hydrocarbyl, silyl, germyl, cyano, halogen and combinations thereof, said R having up to 20 non-hydrogen atoms, or the adjacent R groups together forming a divalent derivative (i.e. a hydrocarbyl group) ilo, siladiilo or germadiilo) with which a system of fused rings is formed; (b) selecting a cocatalyst from the group consisting of polymeric or oligomeric alumoxanes; neutral Lewis acids; non-polymeric, compatible, non-coordinating compounds, ion formers; and combinations thereof; and (c) placing the metal complex and the co-catalyst on a support, characterized in that the catalyst composition, when injected into a batch gas phase polymerization reactor, and brought into contact with ethylene, has a profile of kinetics that obeys the following inequality: in which Kr refers to the cumulative net activity in polymer grams / grams of catalyst * hour "bars of ethylene at 30 minutes after the start of polymerization (A30) divided by the cumulative net activity in polymer grams / grams of aliquator cat. »hour« bars at 90 minutes after starting polymerization (A90) • 3.- A method for preparing a catalyst for olefin polymerization comprising: (a) select a metal complex that corresponds to the formula: wherein Cp is an anionic group, with delocalized p bonds that is attached to M, which contains up to 50 non-hydrogen atoms; M is a metal of group 4 of the Periodic Table of the Elements in the formal oxidation state +2 or +4; X is a conjugated diene of C4_30 represented by the formula: wherein R1, R2, R3 and R4 are each independently hydrogen, aromatic, substituted aromatic, fused aromatic, substituted fused, aliphatic, substituted aliphatic, aromatics containing heteroatoms, fused aromatics containing heteroatoms or silyl; And it is -O-, -S-, -NR-, or -PR-; and Z is SiR2, CR2, SiR2SiR2, CR2CR2, CR = CR, CR2SiR2 or GeR2, BR2, B (NR2) 2, BR2BR2, B (NR2) 2B (NR2) 2, in which R in each occurrence is selected in the independently of the group consisting of hydrogen, hydrocarbyl, silyl, germyl, cyano, halogen and combinations thereof, said R having up to 20 non-hydrogen atoms, or the adjacent R groups together forming a divalent derivative (i.e. a hydrocarbyl group) ilo, siladiilo or germadiilo) with which a system of fused rings is formed; (b) selecting a co-catalyst from the group consisting of polymeric or oligomeric alumoxanes; neutral Lewis acids; non-polymeric, compatible, non-coordinating, ion-forming compounds; and combinations thereof; and (c) placing the metal complex and the co-catalyst on a support, characterized in that the catalyst composition, when injected into a batch gas phase I polymerization reactor, and brought into contact with ethylene, presents a Kr the cujal is at least 10% less than the Kr for a comparative composition of the catalyst with support prepared using ii [(tetramethylcyclopentadienyl) ('dimet il si 1 il) (nt-? Butylamido)] t itanio (11) ) piperi l¡eno and a salt of tet raki s (pentaf luorofeni 1) borate of a monosubstituted ammonium complex and disubstituted with long chain alkyl in which Kr refers to the net cumulative activity in grams per polymer / grams of i! cat al i zador »hour» bars of ethyl 'ene at 30 minutes after the start of the polymerization (A30) divided by the cumulative net activity in grams of polymer / grams of at ikator »hour» bars at 90 minutes after initiating polymerization : A90) • 4. - The method according to any of claims 1, 2 or 3, further characterized in that the metal complex corresponds to the formula: wherein: M is titanium or zirconium in the formal oxidation state +2 or +4; R each time it appears is independently selected from the group consisting of hydrogen, hydrocarbyl, silyl, germyl, cyano, halogen, and combinations thereof, said R having up to 20 atoms other than hydrogen, or the adjacent R groups forming together a divalent derivative (i.e. a hydrocarbyl ilo, siladiyl or germadiyl group) whereby a fused ring system is formed; each X is a conjugated diene of C4_30 represented by the formula: wherein R1, R2, R3 and R4 are each independently hydrogen, aromatic, substituted aromatic, fused aromatic, substituted fused, aliphatic, substituted aliphatic, aromatic heteroatom containing, fused aromatic containing heteroatoms or silyl; And it is -O-, -S-, -NR * -, -PR * -; and Z is SiR * 2, CR * 2, SiR * 2SiR * 2, CR * 2CR * 2, CR * = CR *, CR * 2SiR * 2 or GeR * 2, in which R * each time hydrogen appears or a group selected from silyl, hydrocarbyl, hydrocarbyloxy and combinations thereof, said R * having up to 30 carbon or silicon atoms. 5. - The method according to any of claims 1, 2 or 3, further characterized in that each X is a conjugated diene C6-30 represented by the formula: wherein R1, R2, R3 and R4 are each independently aromatic, substituted aromatic, fused aromatic, substituted fused, aliphatic, substituted aliphatic, aromatics containing heteroatoms, fused aromatics containing heteroatoms or silyl. 6 - The method according to any of claims 1, 2 or 3, further characterized in that the co-catalyst is represented by the formula: (L * -H) d + (A ') d "in which: L * is a Lewis base neutral; (L + -H) + is a Bronsted acid; A d ~ is a non-coordinating, compatible anion that has a charge of d ~, and d is an integer from 1 to 3. More preferred A'd "corresponds to the formula [M * Q4]"; wherein M * is boron or aluminum in the formal +3 oxidation state; and Q each time it appears is independently selected from hydride, dialkyl lime, halide, hydrocarbyl, halogenhydrocarbon, halocarbyl, hydrocarbyl, hydrocarbyl substituted hydrocarbyl, hydrocarbyl substituted with organometal, hydrocarbyl substituted with organometalloid, halogenohydrocarbyloxy, hydrocarbyl substituted with halogenohydrocarbyloxy, hydrocarbyl substituted with halocarbyl, and silylhydrocarbyl substituted with halogen (including perhalogenated hydrocarbyl radicals, perhalogenated hydrocarbyloxy and perhalogenated silylhydrocarbyl), said Q having up to 20 atoms with the proviso that Q appears in no more than one ve as halide. 7. - The method according to any of claims 1, 2 or 3, further characterized in that the co-catalyst is represented by the formula: (L * -H) + (BQ4) ", in which L * is a base of Neutral Lewis, B is boron in a formal oxidation state of 3, and Q is a hydrocarbyl, hydrocarbon loxy, hydrocarbyloxy substituted with organometal, fluorinated hydrocarbyl, fluorinated hydrocarbyloxy or fluorinated silyl hydrocarbyl group with up to 20 non-hydrogen atoms, with the proviso that in no more than one occasion Q be hydrocarbyl 8. - The method according to any of claims 1, 2 or 3, further characterized in that the co-catalyst is represented by the formula: [L * -H] + [ (C6F5) 3BC6H4-0-MoRcx_? Xay] ", in which M ° is a metal or metalloid that is selected from groups 1-14 of the Periodic Table of the Elements; Rc each time it appears is independently hydrogen or a group having from 1 to 80 atoms other than hydrogen, which is hydrocarbyl, hydrocarbyl 1, or hydrocarbon 1 s i 1 i hydrocarbon; Xa is a non-interfering group having from 1 to 100 atoms which are not hydrogen, which is hydrocarbyl substituted by halogen, hydrocarbyl substituted by hydrocarbyl amino, hydrocarbyl substituted by hydrocarbyloxy, hydrocarbylamino, di (hydrocarbyl) amino, hydrocarbyloxy or halide; x is an integer other than zero which can vary from 1 to an integer equal to the valence of M °; and is zero or an integer other than zero which can vary from 1 to an integer equal to 1 less than the valence of M °; and x + y is equal to the valence of M °. 9. - The method according to any of claims 1, 2 or 3, further characterized in that R1 and R4 are each a benzyl radical or a substituted benzyl radical. 10. The method according to any of claims 1, 2 or 3, further characterized in that R1 and R4 are each a phenyl radical or a substituted phenyl radical. 11. A catalyst composition with support comprising: (a) a metal complex corresponding to the formula: wherein Cp is an anionic group, with delocalized p bonds that is attached to M, which contains up to 50 non-hydrogen atoms; M is a metal of group 4 of the Periodic Table of the Elements in the formal oxidation state +2 or +4; X is a conjugated diene of C4_30 represented by the formula: wherein R1, R2, R3 and R4 are each independently hydrogen, aromatic, substituted aromatic, fused aromatic, substituted fused, aliphatic, substituted aliphatic, aromatics containing heteroatoms, fused aromatics containing heteroatoms or silyl; And it is -0-, -S-, -NR-, or -PR-; and Z is SiR2, CR2, SiR2SiR2, CR2CR2, CR = CR, CR2SiR2 or GeR2, BR2, B (NR2) 2, BR2BR2, B (NR2) 2B (NR2) 2, in which R in each occurrence is selected in the independently of the group consisting of hydrogen, hydrocarbyl, silyl, germyl, cyano, halogen and combinations thereof, said R having up to 20 non-hydrogen atoms, or the adjacent R groups together forming a divalent derivative (i.e. a hydrocarbyl group) ilo, siladiilo or germadiilo) with which a system of fused rings is formed; (b) a co-catalyst that is selected from the group consisting of polymeric or oligomeric alumoxanes; neutral Lewis acids; non-polymeric, compatible, non-coordinating, ion-forming compounds; and combinations thereof; and (c) a support, characterized in that the catalyst composition, when injected into a reactor for gas phase polymerization in batches, and brought into contact with ethylene, has a kinetic profile that obeys the following inequality: Kr = A30 / A90 < 1.6 in which Kr refers to the cumulative net activity in grams of polymer / grams of catalyst "hour * bars of ethylene at 30 minutes after the start of polymerization (A30) divided by the cumulative net activity in grams of polymer / grams of catalyst * hour «bars at 90 minutes after starting polymerization (A90) - 12.- A supported catalyst composition comprising: (a) a metal complex corresponding to the formula: wherein Cp is an anionic group, with delocalized p bonds that is attached to M, which contains up to 50 non-hydrogen atoms; M is a metal of group 4 of the Periodic Table of the Elements in the formal oxidation state +2 or +4; X is a conjugated diene of C4-30 represented by the formula: wherein R, R, R and R4 are each independently hydrogen, aromatic, substituted aromatic, fused aromatic, substituted fused, aliphatic, substituted aliphatic, aromatics containing heteroatoms, fused aromatics containing heteroatoms or silyl; And it is -0-, -S-, -NR-, or -PR-; and Z is SiR2, CR2, SiR2SiR2, CR2CR2, CR = CR, CR2SiR2 or GeR2, BR2, B (NR2) 2, BR2BR2, B (NR2) 2B (NR2) _, in which R at each occurrence is selected in the independently of the group consisting of hydrogen, hydrocarbyl, silyl, germyl, cyano, halogen and combinations thereof, said R having up to 20 non-hydrogen atoms, or the adjacent R groups together forming a divalent derivative (i.e. a hydrocarbyl , siladiil or germadiil) with which a system of fused rings is formed; (b) a co-catalyst that is selected from the group consisting of polymeric or oligomeric alumoxanes; neutral Lewis acids; non-polymeric, compatible, non-coordinating, ion-forming compounds; and combinations thereof; and (c) a support, characterized in that the catalyst composition, when injected into a batch gas phase polymerization reactor, and contacted with ethylene, has a Kr which is at least 10% less than the Kr for a comparative catalyst composition with support prepared using [(tetramethylcyclopentadienyl) (dimethylsilyl 1) (nt-butylidene)] thienium (11) piperylene and a tetrakis (pentaf luorophenyl) borate salt of a monosurbed ammonium complex disubstituted with long-chain alkyl in which Kr refers to the cumulative net activity in grams of polymer / grams of catalyst »hour» bars of ethylene at 30 minutes after the start of polymerization (A30) divided by the net cumulative activity in polymer grams / grams of catalyst »hour» bars at 90 minutes after starting the polymerization (A90) • 13.- The supported catalyst composition according to any of claims 11 or 12, further characterized in that R1 and R4 are each a benzyl radical or a substituted benzyl radical. 14. The catalyst composition with support according to any of claims 11 or 12, further characterized in that R1 and R4 are each a phenyl radical or a substituted phenyl radical. 15. A catalyst composition comprising: A) an inert support; B) a metal complex of Group 4-10 that corresponds to the formula: Cp-Mx \ / Z wherein M is a metal of one of Groups 4 to 10 of the Periodic Table of the Elements, which is in the formal oxidation state +2 or +4; Cp is an anionic ligand group with p bonds; Z is a divalent moiety bound to Cp and linked to M through any one of a covalent or covalent / covalent bond, comprising boron or a member of group 14 of the Periodic Table of the Elements, and further comprising nitrogen, phosphorus, sulfur or oxygen; X is a neutral conjugated diene-type ligand group having up to 60 atoms, or a dianionic derivative thereof; and C) an ionic co-catalyst that can convert the metal complex into an active catalyst for polymerization, wherein said catalyst composition is characterized by having an improved kinetic profile in a gas phase polymerization process. 16. The catalyst composition according to claim 14, which has a kinetic profile in the gas phase polymerization of one or more α-olefins in a batch reactor, which obeys the following relationship: Kr = A30 / A90 <; 1.6 in which Kr is the ratio of the cumulative net activity of the catalyst 30 minutes after the start of polymerization (A30) divided by the net cumulative activity of the catalyst 90 minutes after polymerization initiation (A90). A30 and A90 are determined by calculating the grams of polymer / grams of catalyst composition with x time support (hours) x total monomer pressure (100 kPa). 17. The composition according to claim 15, further characterized in that the supported catalyst composition, when injected into a gas phase polymerization reactor, and comes in contact with one more α-olefin monomers, presents a which is at least 10% less than K * r, in which K * r is the net cumulative catalyst activity ratio for a comparative catalyst composition with support prepared using the metal complex (t-butyl and lime) dimethyI- (tetramethylcyclopentadienyl) silanethi anium (II) 1,3-pentadiene and a co-catalyst comprising (diet i 1 alumino -oxi phenyl) tris (pentafluorophenyl) -borate of Armenian.