MXPA00012756A - A catalyst composition and methods for its preparation and use in a polymerization process - Google Patents

Abstract

The present invention relates to a catalyst composition and a method for making the catalyst composition of a polymerization catalyst and a carboxylate metal salt. The invention is also directed to the use of the catalyst composition in the polymerization of olefin(s). In particular, the polymerization catalyst system is supported on a carrier. More particularly, the polymerization catalyst comprises a bulky ligand metallocene-type catalyst system.

Description

A CATALYZING COMPOSITION AND METHODS FOR ITS PREPARATION AND USE IN A POLYMERIZATION PROCESS Field of the Invention The present invention relates to a catalyst composition and methods for preparing the catalyst composition and to its use in a process for polymerizing olefins. In particular, the invention is directed to a method for preparing a catalyst composition of a metallocene catalyst system with bulky ligand and / or a conventional type transition metal catalyst system, and a carboxylate metal salt. Background of the Invention Advances in polymerization and catalysts have resulted in the ability to produce many new polymers that have improved physical and chemical properties useful in a wide variety of superior products and applications. With the development of new catalysts the choice of polymerization type (solution, slurry, high pressure or gas phase) to produce a particular polymer has been greatly extended. Also, advances in polymerization technology have provided efficient, highly productive and economically improved processes. Especially illustrative of these advances is the development of technology that uses metallocene type systems with bulky ligand. Regardless of the technological advances in the polyolefins industry, common problems as well as new challenges associated with the operability of the process still exist. For example, the tendency of a gas phase or mud phase process to form scale and / or sheet is a challenge. For example, in a continuous mud process the formation of scale on the walls of the reactor, which act as a heat transfer surface, must result in many operational problems. Bad heat transfer during polymerization can result in particles of the polymer adhering to the walls of the reactor. These polymer particles can continue to polymerize in the walls which can result in premature deterioration of the reactor. Also, depending on the conditions of the reactor, some of the polymers can be dissolved in the reactor diluent and redeposited on, for example, the surfaces of the metal heat exchanger. In typical continuous gas phase processes, a recycling system is employed for many reasons including the removal of the heat generated in the process by the polymerization. The generation of incrustations, lamination and / or static in a gas phase process can lead to the ineffective operation of several reactor systems. For example, the cooling mechanism for the recycling system, the temperature probes used to control the process and the distributor plate, if affected, can lead to early deterioration of the reactor. Evidence of, and solutions to, several operability problems of the process have been attacked by many in the art. For example, U.S. Patent Nos. 4,792,592, 4,803,251, 4,855,370 and 5,391,657 all discuss techniques for reducing static generation in a polymerization process by introducing to the process, for example, water, alcohols, ketones, and / or inorganic chemical additives; the international publication WO 97/14721 published on April 24, 1997 discusses the suppression of fines that can cause rolling by adding an inert hydrocarbon to the reactor; U.S. Patent No. 5,627,243 discusses a new type of distributor plate for use in gas phase reactors of the fluidized bed; the international publication WO 96/08520 discusses avoiding the introduction of a scrubber to the reactor; U.S. Patent No. 5,461,123 discusses using sound waves to reduce lamination; U.S. Patent No. 5,066,736 and European Patent EP-A1 0 549 252 discuss the introduction of an activity retarder into the reactor to reduce agglomerates; U.S. Patent No. 5,610,244 relates to feeding shaping monomer directly into the reactor above the bed to prevent fouling and improve the quality of the polymer; U.S. Patent No. 5,126,414 discusses including an oligomer removal system to reduce fouling of the distributor plate and provide polymers without gels; European patent EP-A1 0453 116 published on October 23, 1991 discusses the introduction of antistatic agents to the reactor to reduce the amount of laminations and agglomerates; U.S. Patent No. 4,012,574 discusses adding an active compound on the surface, a perfluorocarbon group, to the reactor to reduce fouling; U.S. Patent No. 5,026,795 discusses the addition of an antistatic agent with a liquid carrier in the polymerization zone in the reactor; U.S. Patent No. 5,410,002 discusses using a conventional titanium / magnesium supported catalyst system from Ziegler-Natta where a selection of antistatic agents is added directly to the reactor to reduce fouling; U.S. Patent Nos. 5,034,480 and 5,034,481 discuss a product of the reaction of a conventional Ziegler-Natta titanium catalyst with an antistatic to produce ultra high molecular weight ethylene polymers; U.S. Patent No. 3,082,198 discusses introducing a quantity of carboxylic acid dependent on the amount of water in a process for polymerizing ethylene using an organo titanium / aluminum catalyst in a liquid hydrocarbon medium; and U.S. Patent No. 3,919,185 discloses a slurry process using a non-polar hydrocarbon diluent using a conventional Ziegler-Natta type or Phillips-type catalyst and a polyvalent metal salt of an organic acid having a molecular weight of less 300. There are several other known methods for improving operability including coating the polymerization equipment, for example, by treating the walls of a reactor using chromium compounds as described in U.S. Patent Nos. 4,532,311 and 4,876,320; by injecting various agents into the process, for example, international publication WO 97/46599 published on December 11, 1997 discusses feeding a thin metal zone in the polymerization reactor a non-supported soluble metallocene catalyst system and injecting anti-scale or agents antistatic in the reactor; control the polymerization rate particularly at the beginning; and reconfigure the reactor design. Other persons in the art to improve the operability of the process have discussed modifying the catalyst system by preparing the catalyst system in different ways. For example, methods in the art include combining the compounds of the catalyst system in a particular order; manipulate the proportion of various compounds of the catalyst system; vary the contact time and / or the temperature when the components of a catalyst system are combined; or simply add several compounds to the catalyst system. These techniques or combinations thereof are discussed in the literature. Especially illustrative in the art is the methods and methods of preparation for producing bulky ligand metallocene type catalyst systems, more particularly bulky ligand metallocene type catalyst systems supported with reduced tendencies to form scale and better operability. Examples of these include: International Publication WO 96/11961 published April 26, 1996 discusses as an component of a supported catalyst system an antistatic agent for reducing scale and lamination in polymerization processes of gas, slurry or liquid reservoir; U.S. Patent No. 5,283,278 is directed toward the prepolymerization of a metallocene catalyst or a conventional Ziegler-Natta catalyst in the presence of an antistatic agent; U.S. Patent Nos. 5,332,706 and 5,473,028 have presented a particular technique for forming a catalyst by incipient impregnation; U.S. Patent Nos. 5,427,991 and 5,643,847 describe the chemical bonding of noncoordinating anionic activators to supports; U.S. Patent No. 5,492,975 discusses metallocene-type catalyst systems bonded with polymer; U.S. Patent No. 5,661,095 discusses supporting a metallocene-type catalyst on a copolymer of an olefin and an unsaturated silane; the international publication WO 97/06186 published on February 20, 1997 shows the removal of inorganic and organic impurities after the formation of a metallocene-type catalyst itself, the international publication WO 97/15602 published on May 1, 1997 discusses metal complexes easily bearable; International Publication WO 97/27224 published July 31, 1997 relates to forming a transition metal compound supported in the presence of an unsaturated organic compound having at least one terminal double bond; and European patent A2-811 638 discusses using a metallocene catalyst and an activation co-catalyst in a polymerization process in the presence of an antistatic agent containing nitrogen. Although all these possible solutions could reduce the level of scale or lamination to some extent, some are expensive to use and / or can not reduce scale and lamination to a level sufficient to operate a continuous process successfully, particularly a commercial process or big scale. Thus, it would be advantageous to have a polymerization process capable of operating continuously with improved reactor operability and at the same time producing new and improved polymers. It would also be very beneficial to have a continuous operation polymerization process that has more stable catalyst productivities, reduced incrustation / lamination tendencies and increased duration of operation. SUMMARY OF THE INVENTION This invention provides a method for making a new and improved catalyst composition and for its use in polymerization processes. The method comprises the step of combining, contacting, combining and / or mixing a catalyst system, preferably a supported catalyst system, with a carboxylate metal salt. In one embodiment the catalyst system comprises a conventional type transition metal catalyst compound. In the most preferred embodiment the catalyst system comprises a metallocene catalyst compound with bulky ligand. The combination of the catalyst system and the carboxylate metal salt is useful in any olefin polymerization process. The preferred polymerization processes are a gas phase process or a mud phase process, more preferably a gas phase process. In one embodiment, the invention provides a method for making a catalyst composition useful for the polymerization of olefins, the method includes combining, contacting, stirring and / or mixing a polymerization catalyst with at least one carboxylate metal salt. In one embodiment, the polymerization catalyst is a conventional type transition metal polymerization catalyst, more preferably a supported conventional type transition metal polymerization catalyst. In the most preferred embodiment, the polymerization catalyst is a bulky ligand metallocene-type catalyst, more preferably a bulky ligand-supported metallocene-type polymerization catalyst. In a preferred embodiment, the invention is directed to a catalyst composition comprising a catalyst compound, preferably a conventional type transition metal catalyst compound, more preferably a bulky ligand metallocene-type catalyst compound, an activator and / or co-catalyst. catalyst, a carrier, and a carboxylate metal salt. In the most preferred method of the invention, the carboxylate metal salt is stirred, preferably dry stirred, and more preferably is tumbled or fluidized, with a catalyst system or polymerization catalyst comprising a carrier. In this most preferred embodiment, the polymerization catalyst includes at least one bulky ligand metallocene-type catalyst compound, an activator and a carrier. In still another embodiment, the invention relates to a process for polymerizing olefins in the presence of a catalyst composition comprising a polymerization catalyst and a carboxylate metal salt, preferably the polymerization catalyst comprises a carrier, more preferably the polymerization catalyst. comprises one or more of a combination of conventional type catalyst compound and / or a metallocene-like catalyst compound with bulky ligand. In a preferred method for making the catalyst composition of the invention, the method comprises the steps of combining a bulky ligand metallocene-type catalyst compound, an activator and a carrier to form a bulky ligand metallocene-supported catalyst system, and contacting the bulky ligand metallocene-type catalyst compound supported with a carboxylate metal salt. In the most preferred embodiment, the supported bulky ligand metallocene catalyst system and the carboxylate metal salt are in a substantially dry or dried state. In one embodiment, the invention provides a process for polymerizing olefins in the presence of a polymerization catalyst that has been combined, contacted, stirred, or mixed with at least one carboxylate metal salt. Detailed Description of the Invention Introduction The invention is directed to a method for making a catalyst composition to the same catalyst composition. The invention also relates to a polymerization process having improved operability and product capabilities using the catalyst composition. It has surprisingly been found that using a carboxylate metal salt in combination with a catalyst system results in a substantially improved polymerization process. Particularly surprising is when the catalyst system is supported on a vehicle, more so when the catalyst system includes a bulky ligand metallocene catalyst system, and even more so when the bulky ligand metallocene type catalyst is very active and / or is highly comonomer-incorporating. . While not wishing to be bound by any theory, it is believed that these bulky ligand metallocene type catalysts are more prone to lamination and / or scale formation. It is believed that highly active catalysts can result in the generation of local extreme heat to the polymer particle being formed. It is theorized that these extreme conditions lead to increased levels of lamination and / or fouling. It is also hypothesized that polymers produced by metallocene catalysts with bulky ligand form very hard polymer sheets. In this way, it is difficult to break them and remove any of these sheets that can be formed in the reactor. Furthermore, it was very unexpected that the fractional melt index and the higher density polymers could be produced in a polymerization process using the polymerization catalyst and the carboxylate metal salt combination with improved operability. This discovery was especially important because it is well known in the polymer industry that, from the point of view of operability of a process, these types of polymers are difficult to produce. Using the polymerization catalyst described below in combination with a carboxylate metal salt results in a substantial improvement in the operability of the process, a significant reduction of lamination and scale formation, improved catalytic performance, better polymer particle morphology without adverse effect on physical polymer properties, and the ability to produce a wider range of polymers. Catalyst Components and Catalyst Systems All polymerization catalysts including conventional type transition metallocene catalysts are suitable for use in the polymerization process of the invention. However, processes using bulky ligand and / or bulky bridged ligand, metallocene type catalysts, are particularly preferred. The following is a non-limiting discussion of the various polymerization catalysts useful in the invention. Transition Metal Catalyst Conventional Type Conventional type transition metal catalysts are those conventional Ziegler-Natta catalysts and Phillips-type chromium catalysts well known in the art. Examples of conventional type transition metal catalysts are discussed in U.S. Patent Nos. 4,115,639, 4,077,904, 4,482,687, 4,564,605, 4,721,763, 4,879,359 and 4,960,741 all of which are hereby fully incorporated by reference. Conventional type transition metal catalyst compounds that can be used in the present invention include transition metal compounds of groups III to VIII, preferably IVB to VIB of the Periodic Table of the Elements. These conventional type transition metal catalysts can be represented by the formula: MRX, wherein M is a metal of groups IIIB to VIII, preferably group IVB, more preferably titanium; R is halogen or a hydrocarbyloxy group; and x is the valence of the metal M. Non-limiting examples of R include alkoxy, phenoxy, bromide, chloride and fluoride. Non-limiting examples of conventional type transition metal catalysts where M is titanium include TiCl 4, TiBr 4, Ti (OC 2 H 5) 3 Cl, Ti (OC 2 H 5) Cl 3, Ti (0 C 4 H 9) 3, Cl, Ti (OC 3 H 7) 2 C 12, Ti ( OC2H5) 2Br2, TiCl3.l / 3AlCl3 and Ti (OC12H25) Cl3. Compounds of conventional type transition metal catalysts based on magnesium / titanium electron donor complexes which are useful in the invention are described in, for example, U.S. Patent Nos. 4,302,565 and 4,302,566, which are fully incorporated by reference. in the present by reference. The derivative of MgTiCl 6 (ethyl acetate). it is particularly preferred. British patent application 2,105,355, incorporated herein by reference, discloses various conventional type vanadium catalyst compounds. Non-limiting examples of conventional type vanadium catalyst compounds include vanadyl trihalide, alkoxy halides and alkoxides such as V0C13, V0C12 (OBu) wherein Bu is butyl and VO (OC2H5) 3; vanadium tetrahalide and vanadium alkoxyhalides such as VC14 and VC13 (OBu); acetates of vanadium and acetyl acetonate vanadyl and chloroacetyl acetonates such as V (AcAc) 3 and V0C12 (AcAc) wherein (AcAc) is acetyl acetonate. Preferred conventional vanadium catalyst compounds are V0C13, VC14 and V0C12-0R wherein R is a hydrocarbon radical, preferably an aliphatic or aromatic hydrocarbon radical with 1 to 10 carbon atoms such as ethyl, phenyl, isopropyl, butyl, propyl , n-butyl, isobutyl, tertiary butyl, hexyl, cyclohexyl, naphthyl, etc., and vanadium acetyl acetonates. Conventional chromium type catalyst compounds, often known as Phillips type catalysts, suitable for use in the present invention include Cr03, chromocene, silyl chromate, chromyl chloride (Cr02Cl2), chromium-2-ethyl hexanoate, chromium acetylacetonate (Cr (AcAc) 3), and the like. Non-limiting examples are described in U.S. Patent Nos. 2,285,721, 3,242,099 and 3,231,550, which are hereby incorporated by reference in their entirety. Still other conventional type transition metal catalyst compounds and catalyst systems suitable for use in the present invention are described in U.S. Patent Nos. 4,124,532, 4,302,565, 4,302,566 and 5,763,723 and published European Patent EP-A2 0 416 815 A2 and EP-A1 0 420 436, all of which are incorporated herein by reference. The conventional type transition metal catalysts of the invention also have the general formula M'tM '' X2tYuE, where M 'is Mg, Mn and / or Ca; t is a number from 0.5 to 2; M "is a transition metal Ti, V and / or Zr; X is a halogen, preferably Cl, Br or 1; And it can be the same or different and is halogen, alone or in combination with oxygen, -NR2, -OR, -SR, -COOR, or -OSOOR, wherein R is a hydrocarbyl radical, in particular an alkyl, aryl, cycloalkyl or arylalkyl radical, acetylacetonate anion in an amount satisfying the valence state of M '; u is a number from 0.5 to 20; E is an electron donor compound selected from the following classes of compounds: (a) esters of organic carboxylic acids; (b) alcohols; (c) ethers; (d) amines; (e) carbonic acid esters; (f) nitriles; (g) phosphsramides, (h) phosphoric and phosphorous acid esters, and (j) phosphorous oxychloride. Nonlimiting examples of complexes satisfying the above formula include: MgTiCl5-2CH3COOC2H5, Mg3Ti2Cl12'7CH3C00C2H5, MgTiCl5- 6C2H5OH, MgTiCls.100CH3OH, MgTiCl5 • tetrahydrofuran • 7C6H5CN MgTi2Cl12, Mg3Ti2Cl12 • 6C6HSC00C2H5, MgTiCl6-2CH3COOC2H5, MgTiCl6-6C5HsN, MgTiCl5 ( OCH3) -2CH3COOC2H5, MgTiClsN (C6Hs) 2'3CH3COOC2Hs, MgTiBr2Cl4-2 (C2H5) 20, MnTiCl5-4C2HsOH, Mg3V2Cl12-7CH3COOC2H5, MgZrCl6-4 tetrahydrofuran. Other catalysts may include cationic catalysts such as A1C13, and other cobalt and iron catalysts well known in the art. Typically, these conventional type transition metal catalyst compounds excluding some conventional type chromium catalyst compounds are activated with one or more of the conventional type catalysts described below. Co-catalysts Conventional Type Conventional type cocatalyst compounds for the above conventional type transition metal catalyst compounds can be represented by the formula M3M4vX2cR3b.c, wherein M3 is a metal of Group IA, IIA, IIB and IIIA of the Periodic Table of the Elements; M4 is a metal of Group IA of the Periodic Table of the Elements; v is a number from 0 to 1; each X2 is any halogen; c is a number from 0 to 3; each R3 is a monovalent hydrocarbon radical or hydrogen; b is a number from 1 to 4; and wherein b minus c is at least 1. Other organometallic cocatalyst compounds conventional type for the above conventional type transition metal catalysts have the formula M3R3k, wherein M3 is a Group IA, IIA, IIB or IIIA metal, such as lithium, sodium, beryllium, barium, boron, aluminum, zinc, cadmium, and gallium; k is equal 1, 2 or 3 depending on the valence of M3 this valence in turn normally depends on the particular Group to which M3 belongs; and each R3 can be a monovalent hydrocarbon radical. Non-limiting examples of organometallic cocatalyst compounds of the conventional type of Group IA, IIA and IIIA useful with the conventional type catalyst compounds described above include methyl lithium, butyllithium, dihexylmercury, butylmagnesium, diethylcadmium, benzylpotasium, diethyl zinc, tri-n-butylaluminium. , di-isobutyl ethyl boron, diethyl-cadmium, di-n-butyl-zinc and tri-n-amylboron, and, in particular, aluminum alkyls, such as tri-hexyl-aluminum, triethylaluminum, trimethylaluminum, and tri-isobutylaluminum. Other conventional type cocatalyst compounds include mono-organohalides and hydrides of Group IIA metals, and mono- or di-organohalides and hydrides of Group IIIA metals. Non-limiting examples of these conventional type cocatalyst compounds include diisobutylaluminum bromide, isobutylboron dichloride, methyl magnesium chloride, ethylbenyl chloride, ethylcalcium bromide, diisobutylaluminium hydride, methylcadmium hydride, diethylborohydride, hexylberyl hydride, hydride of dipropylboro, octylmagnesium hydride, butylcinc hydride, dichloroborohydride, dibromoaluminum hydride and bromocadmium hydride. Conventional type organometallic cocatalyst compounds are known to those skilled in the art and a more complete discussion of these compounds can be found in U.S. Patent Nos. 3,221,002 and 5,093,415, which are incorporated herein by reference in their entirety. For the purposes of this patent specification and the appended claims, conventional type transition metal catalyst compounds exclude those bulky ligand metallocene type catalyst compounds discussed below. For purposes of this patent specification and the appended claims, the term "cocatalyst" refers to conventional type cocatalysts or conventional type organometallic cocatalyst compounds. Metallocene bulky ligand-type catalyst compounds and catalyst systems for use in combination with a carboxylate metal salt of the invention are described below. Compounds Bulky Ligand Metallocene Catalysts Generally, bulky ligand metallocene-type catalyst compounds include full-walled and sandwich-mediated compounds that have one or more bulky ligands including cyclopentadienyl type structures or other similar functioning structure such as pentadiene., cyclo-octatetratraendi-yl and imides. Typical bulky ligand metallocene-type compounds are generally described as containing one or more ligands capable of? -5 bonding with a transition metal atom, usually, ligands or fractions derived from cyclopentadienyl, in combination with a transition metal selected from the group. 3 to 8, preferably 4, 5 or 6 or from the series of lanthanides or actinides of the Periodic Table of the Elements. Exemplary of these bulky ligand metallocene-type catalyst compounds and catalyst systems are described in, for example, U.S. Patent Nos. 4,530,914, 4,871,705, 4,937,299, 5,017,714, 5,055,438, 5,096,867, 5,120,867, 5,124,418, 5,198,401, 5,210,352, 5,229,478, 5,264,405 , 5278264, 5278119, 5304614, 5324800, 5347025, 5350723, 5384299, 5391790, 5391789, 5399636, 5408017, 5491207, 5455366, 5534473, 5539124, 5554775, 5621126, 5684098, 5693730, 5698634, 5710297, 5712354, 5714427, 5714555, 5728641 , 5,728,839, 5,753,577, 5,767,209, 5, 770, 753 and 5, 770, 664 all of which are incorporated herein by reference in their entirety. Also, descriptions of European publications EP-A-9 591 756, EP-A-0 520 732, EP-A-0 420 436, EP-B1 0 485 822, EP-B1 0 485 823, EP-A2- 0 743 324 and EP-B1 0 518 092 and PCT international publications WO 91/04257, WO 92/00333, WO 93/08221, WO 93/08199, WO 94/01475, WO 96/20233, WO 97/15582, WO 97/19959, WO 97/46567, WO 98/01455, WO 98/06759 and WO 98/011144 all are fully incorporated herein by reference for purposes of the description of typical bulky ligand metallocene-type catalyst compounds and systems catalysts. In one embodiment, the bulky ligand metallocene type catalyst compounds of the invention are represented by the formula: LALBMQ (I) wherein M is a metal of the Periodic Table of the Elements and may be a Group 3 to 10 metal, preferably, a transition metal of Group 4, 5 or 6 or a metal of the lanthanide or actinide series, more preferably M is a transition metal of Group 4, even more preferably zirconium, hafnium or titanium. LA and LB are bulky ligands that include ligands derived from cyclopentadienyl or ligands derived from substituted cyclopentadienyl or substituted heteroatom or heteroatom containing ligands derived from cyclopentadienyl, or ligands derived from substituted cyclopentadienyl or hydrocarbyl, or fractions such as indenyl ligands, benzindenyl ligands , fluoroenyl ligands, octahydrofluoroenyl ligands, cyclo-octatetraendi-yl ligands, ancenyl ligands and borabenze ligands, and the like, including hydrogenated versions thereof. Also, LA and LB can be any other structure of ligands capable of? -5 bonds with M, for example, LA and LB can comprise one or more heteroatoms, for example, nitrogen, silicon, boron, germanium, and phosphorus, in combination with carbon atoms to form a cyclic structure, for example, a heterocyclopentadienyl auxiliary ligand. In addition, each of LA and LB may be other types of bulky ligands including but not limited to bulky amides, phosphides, alkoxides, aryloxides, imides, carbolides, borolides, porphyrins, phthalocyanines, corrins, and other polyazomacrocycles. Each LA and LB may be the same or different type of bulky ligand that is p-linked to M.

Each LA and LB can be substituted by a combination of substituent groups R. Non-limiting examples of substituent groups R include hydrogen or straight, branched alkyl radicals or alkyl, alkenyl, alkynyl or aryl cyclic radicals or combinations thereof having from 1 to 30 carbon atoms or other substituents having up to 50 non-hydrogen atoms which can also be substituted. Non-limiting examples of alkyl substituents R include methyl, ethyl, propyl, butyl, pentyl, hexyl, cyclopentyl, cyclohexyl, benzyl or phenyl groups, halogens and the like, including their isomers, for example, butylotheryl, isopropyl, and the like. Other hydrocarbyl radicals include fluoromethyl, fluoroethyl, difluoroethyl, iodopropyl, bromohexyl, chlorobenzyl, hydrocarbyl substituted organometalloid radicals, including trimethylsilyl, trimethylgermyl, methyldiethylsilyl, and the like; and halocarbyl substituted organometaloid radicals including tris (trifluoromethyl) -silyl, methyl-bis (difluoromethyl) silyl, bromomethyl dimethylgermyl and the like; and disubstituted boron radicals including dimethylboron for example; disubstituted pnictógeno radicals including dimethylamine, dimethylphosphine, diphenylamine, methylphenylphosphine, chalcogen radicals including methoxy, ethoxy, propoxy, phenoxy methylsulfide and ethylsulfide. Non-hydrogen substituents R include carbon, silicon, nitrogen, phosphorus, oxygen, tin, germanium and the like including olefins such as but not limited to olefinically unsaturated substituents include vinyl terminated ligands, eg, but-3-enyl, 2- vinyl, or hexane-1. Also, at least two R groups, preferably two adjacent R groups, are joined to form a ring structure having from 4 to 30 atoms selected from carbon, nitrogen, oxygen, phosphorus, silicon, germanium, boron or a combination thereof. Also, an R group such as 1-butanil can form a carbon sigma bond with the metal M. Other ligands can be ligated to the transition metal, such as the leaving group Q. Q can independently be monoanion labile ligands having a single linkage with M. Non-limiting examples of Q include weak bases such as amines, phosphines, ether, carboxylates, dienes, hydrocarbyl radicals having from 1 to 20 carbon atoms, hydrides or halogens and the like, and combinations thereof. Other examples of Q radicals include those substituents for R as described above and include cyclohexyl, heptyl, tolyl, trifluoromethyl, tetramethylene and pentamethylene radicals, methylidene, methoxy, ethyoxy, propoxy, phenoxy, bis (N-methylanilide), dimethylamide, dimethylphosphide and similar. In addition, the bulky ligand metallocene-type catalyst compounds of the invention are those wherein LA and LB are bridged together by bridging group, A. These bridged compounds are known as bridged, bulky ligand metallocene-type catalyst compounds.

Non-limiting examples of bridging group A are bridging radicals of at least one Group 14 atom, such as but not limited to carbon, oxygen, nitrogen, silicon, germanium and tin, preferably carbon, silicon and germanium , more preferably silicon. Other non-limiting examples of bridging A groups include dime ti 1 si 1 i 1, di i 1 i si 1 i 1, me ti 1 eti 1 si 1 i 1 o, trifluoromethylbutylsilyl, bis (trifluoromethyl) silyl, di -n-butylsilyl, silylcyclobutyl, di-i-propylsilyl, di-cyclohexylsilyl, di-phenylsilyl, cyclohexylphenylsilyl, t-butylcyclohexylsilyl, di-t-butylphenylsilyl, di (p-tolyl) silyl, dimethylgermyl, diethylgermyl, methylene, dimethylmethylene, diphenylmethylene ethylene, 1-2-dimethylethylene, 1,2-diphenylethylene, 1,1,2,2-1-tetramethylethylene, dimethylmethylene dimethylsilyl, methylenediphenylgermyl, methylamine, phenylamine, cyclohexylamine, methylphosphine, phenylphosphine, cyclohexylphosphine and the like. In another embodiment, the bulky ligand metallocene type catalyst of the invention is represented by the formula: (C5H4.dRd) Ax (CsH4.dRd) M Qg-2 (II) where M is a transition metal of Group 4, , 6, (C5H4.dRd) is a bulky ligand derived from unsubstituted or substituted cyclopentadienyl linked to M, each R, which may be the same or different, is hydrogen or a substituent group containing up to 50 non-hydrogen atoms or substituted or unsubstituted hydrocarbyl having from 1 to 30 carbon atoms or combinations thereof, or two or more carbon atoms are bonded together to form a part of a substituted or unsubstituted ring or ring system having 4 to 30 carbon atoms, A is one or more of, or a combination of carbon, germanium, silicon, tin, phosphorus or nitrogen atom containing a radical bond bridging two rings (CsH4_dRd); more particularly, non-limiting examples of A may be represented by R'2C, R'2Si, R'2Si R'2Si, R'2Si R'2C, R'2Ge, R'2Ge, R'2Si R'2Ge, R '2GeR'2C, R'N, R'P, R'2C R'N, R'2C R'P, R'2Si R'N, R'2Si R'P, R'2GeR'N, R'2Ge R'P, where R 'is independently, a radical group which is hydride, hydrocarbyl of 1 to 30 carbon atoms, substituted hydrocarbyl, halocarbyl, halocarbyl-substituted organometalloid hydrocarbyl, halocarbyl substituted organometalloid by, disubstituted boron, pnictogen disubstituted, substituted chalcogen, or halogen; each Q which can be the same or different is a hydride, cyclic or branched hydrocarbyl, linear, substituted or unsubstituted, having from 1 to 30 carbon atoms, halogen, alkoxides, aryloxides, amides, phosphides, or other cualguier anionic ligand univalent or combination thereof; also, two Q together may form a ligand alkylidene or ligand cyclometallated hydrocarbyl or any other divalent anionic chelating ligand, where g is an integer corresponding to the formal oxidation state of M, d is an integer selected from 0, 1, 2 , 3 or 4 denoting the degree of substitution and x is an integer from 0 to 1. in one embodiment, catalysts compounds metallocene-type bulky ligand are those where the R substituents on the bulky ligands LA, LB, (C5H4_dRd) of the formulas (I) and (II) are substituted with the same or different number of substituents in each of the bulky ligands. In a preferred embodiment, the bulky ligand metallocene-type catalyst is represented by formula (II) wherein x is 1. Other metallocene catalysts compounds useful type bulky ligand heteroatom in the invention include monovoluminoso ligand bridged metallocene compounds containing such . These types of catalysts and catalyst systems are described in, for example, international publications WO 92/00333, WO 94/07928, WO 91/04257, WO 94/03506, WO 96/00244 and 29/97/15602 and patents United States Nos. 5,057,475, 5,096,867, 5,055,438, 5,198,401, 5,227,440 and 5,264,405 and European Publication EP-A-0 420 436, all of which are hereby incorporated by reference in their entirety. Other metallocene-type catalysts bulky ligand useful in the invention may include those disclosed in US Nos. 5,064,802, 5,145,819, 5,149,819, 5,243,001, 5,239,022, 5,276,208, 5,296,434, 5,321,106, 5,329,031, 5,304,614, 5,677,401 and 5,723,398 and publications International PCTs WO 93/08221, WO 93/08199, WO 95/07140, WO 98/11144 and European publications EP-A-0 578 838, EP-A-0 638 595, EP-B-0 513 380 and EP -A1-0 816 372, all of which are incorporated herein by reference in their entirety. In another embodiment of this invention, the bridged monovoluminous ligand heteroatom contains metallocene-type catalyst compounds useful in the invention are represented by the formula: where M is Ti, Zr or Hf; (CsH5.y.x.xRx) is a cyclopentadienyl ring or ring system which is substituted with from 0 to 5 substituent groups R, "x" is 0, 1, 2, 3, 4 or 5 denoting the degree of substitution, and each substituent group R is, independently, a radical selected from the group consisting of hydrocarbyl radicals with 1 to 20 carbon atoms, hydrocarbyl radicals with 1 to 20 carbon atoms substituted where one or more hydrogen atoms are replaced by atom of halogen, hydrocarbyl substituted metalloid radicals with 1 to 20 carbon atoms wherein the metalloid is selected from Group 14 of the Periodic Table of the Elements, and halogen radicals or (C5H5_y_xRx) is a cyclopentadienyl ring in which two R groups adjacent ones are joined forming a ring with from 4 to 20 carbon atoms to give a saturated or unsaturated polycyclic cyclopentadienyl ligand such as indenyl, tetrahydroindenyl, fluoroenyl or octahydrofluoroenyl; (JR'z-1_y) is a heteroatom ligand in which J is an element with a coordination number of three from Group 15 or an element with a coordination number of two from Group 16 of the Table of Elements, preferably nitrogen, phosphorus, oxygen or sulfur with nitrogen being preferred, and each R 'is, independently, a radical selected from a group consisting of hydrocarbyl radicals with from 1 to 20 carbon atoms wherein one or more hydrogen atoms are replaced by a halogen atom, y is 0 or 1, and "z" is the coordination number of element J; each Q is, independently, any univalent anionic ligand such as halogen, hydride, or hydrocarbyl with 1 to 30 carbon atoms substituted or unsubstituted, alkoxide, aryloxide, amide or phosphide, with the proviso that two Q may be an alkylidene, a cyclometalated hydrocarbyl or any other divalent anionic chelating ligand and n can be 0.1 O 2; A is a group of covalent bridge former that contains a Group 15 or 14 element such as, but not limited to, a dialkyl radical, alkylaryl or diaryl silicon or germanium, alkyl or aryl phosphine or amine radical, or hydrocarbyl radical such as methylene, ethylene and the like; L 'is a Lewis base such as diethylether, tetraethylammonium chloride, tetrahydrofuran, dimethylaniline, aniline, trimethylphosphine, n-butylamine, and the like; and w is a number from 0 to 3. Additionally, L 'may be linked to any of R, R' or Q and n is 0, 1, 2 or 3. In another embodiment, the bulky ligand-like metallocene type catalyst compound is a complex of a transition metal, a substituted or unsubstituted pi-linked ligand, and one or more heteroalyl fractions, such as those described in U.S. Patent Nos. 5,527,752 and 5,747,406 and European Patent EP-B1-0 735 057, all of which are fully incorporated herein by reference. Preferably, the voluminous ligand-like metallocene type catalyst compound, the monocycloalkaldienyl catalyst compound, can be represented by one of the following formulas: where M is a transition metal of Group 4, 5 or 6, preferably titanium, zirconium or hafnium, more preferably zirconium or hafnium; L is a substituted or unsubstituted pi-linked ligand coordinated with M, preferably L is a bulky cycloalkadienyl ligand, for example, cyclopentadienyl, indenyl or bullous fluorenyl ligands, optionally with one or more hydrocarbyl substituent groups having from 1 to 20 atoms of carbon; each Q independently is selected from the group consisting of -O-, -NR-, -CR2- and-S-, preferably oxygen; And it is either C or S preferably carbon; Z is selected from the group consisting of -OR, -NR2, -CR3, -SR, -SiR3, -PR2, -H, and substituted or unsubstituted aryl groups, with the proviso that when Q is -NR- then Z is selected from the group consisting of -OR, -NR2, -SR, -SiR3, -PR2 and -H, preferably Z is selected from the group consisting of -OR, -CR3 and -NR2; N is 1 or 2, preferably 1; A is a univalent aniope group where n is 2 or A is a divalent anionic group when n is 1; preferably A is carbamate, carboxylate, or other heteroalyl fraction described by the combination Q, Y, and Z; and each R is independently a group containing carbon, silicon, nitrogen, oxygen, and / or phosphorus wherein one or more R groups can be attached to substituent L, preferably R is a hydrocarbon group containing from 1 to 20 carbon atoms. carbon, more preferably an alkyl, cycloalkyl, or an aryl group and one or more can be attached to substituent L; T is a bridging group selected from the group consisting of the alkylene or arylene groups containing from 1 to 10 carbon atoms optionally substituted with carbon or heteroatom or heteroatoms of germanium, silicon and alkyl sofina; and m is 2 to 7, preferably 2 to 6, more preferably 2 or 3. In formulas (IV) and (V) the support substituent formed by Q, Y, and Z is an uncharged polydentate ligand which exerts effects electronic due to its high polarizability, similar to cyclopentadienyl ligand. In the most preferred embodiments of this invention, disubstituted carbamates and carboxylates are employed. Non-limiting examples of these bulky ligand metallocene-type catalyst compounds include indenyl zirconium tris (diethylcarbamate), indenyl zirconium tris (trimethylacetate), indenyl zirconium tris (p-toloate), indenyl zirconium tris (benzoate), tris ( trimethylacetate) (1-methylindenyl) of zirconium, zirconium tris (diethylcarbamate) (2-methylindenyl), zirconium tris (trimethylacetate) (methylcyclopentadienyl), cyclopentadienyl tris (trimethylacetate), zirconium tris (trimethylacetate) tetrahydroindenyl, and tris (benzoate) ) of zirconium (pentamethyl-cyclopentadienyl). Preferred examples are indenyl zirconium tris (diethylcarbamate), indenyl zirconium tris (trimethylacetate), and zirconium (methylcyclopentadienyl) tris (trimethylacetate). In another embodiment of the invention, the metallocene-type bulky ligand-type catalyst compounds are those nitrogen-containing heterocyclic ligand nitrogens, also known as transition metal catalysts based on biodentate ligands containing pyridine or quinoline moieties, such as those described in WO 96. / 33202, WO 99/01481 and WO 98/42664 and U.S. Patent No. 5,637,660, which are incorporated herein by reference. It is within the scope of this invention, in one embodiment, that complexes of metallocene-like catalyst compounds with bulky Ni2 + and Pd2 + ligand described in the articles Johnson and Contributors, "New Pd (II) - and Ni (II) -Based Catalysts for Polymerization of Ethylene and a-Olefins ", J. Am. Chem. Soc. 1995, 117, 6414-6415 and Johnson et al." Copolymerization of Ethylene and Propylene with Functionalized Vinyl Monomers by Palladium (II) Catalys ", J. Am. Chem. Soc., 1996, 118, 267-268, and WO 96/23010 published August 1, 1996, which are hereby incorporated by reference in their entirety, may be combined with a carboxylate metal salt for use in the process of the invention. These complexes can be either alkyl ether adducts, or alkylated reaction products of the described dihalide complexes that can be activated to a cationic state by the conventional type cocatalysts or activators of this invention described below.Also included as bulky ligand metallocene-type catalyst compounds are those di-imine-based ligands for the Group 8 to 10 metal compounds described in PCT international publications WO 96/23010 and WO 97/48735 and Gibson, et al., Chem. Comm. pages 849-850 (1998), all of which are incorporated herein by reference. Other bulky ligand metallocene type catalysts are those metal imide complexes of Group 5 and 6 described in European Patent EP-A2-0 816 384 and U.S. Patent No. 5,851,945, which are incorporated herein by reference . In addition, bulky ligand metallocene type catalysts include bridged Group 4 bis (arylamido) compounds described by D.H. McConville, et al., In Organometallics 1195, 14, 5478-5480, which is incorporated herein by reference. Other bulky ligand metallocene type catalysts are described as bis (aromatic hydroxy nitrogen ligands) in U.S. Patent No. 5,852,146, which is incorporated herein by reference. Other metallocene type catalysts containing one or more Group 15 atoms include those described in WO 98/46651, which is incorporated herein by reference. Still other bulky ligand metallocene type catalysts include those metallocene bulky ligand-like multinuclear catalysts as described in WO 99/20665, which is incorporated herein by reference. Some embodiments are contemplated, that the bulky ligands of the metallocene-type catalyst compounds of the invention described above may be substituted asymmetrically in terms of additional substituents or types of substituents, and / or unbalanced in terms of the number of additional substituents on bulky ligands or the same bulky ligands are different. It is also contemplated that in one embodiment, the bulky ligand metallocene-type catalysts of the invention include their optical or enantiomeric structural isomers (meso and racemic isomers) and mixtures thereof. In another embodiment, the bulky ligand metallocene type compounds of the invention can be chiral and / or bridged bulky ligand metallocene type catalyst compounds. Activator and Activation Methods for the Bulk Ligand Metallocene-type Catalyst Compounds The bulky ligand metallocene-type catalyst compounds described above of the invention are typically activated in various ways to produce catalyst compounds that have a vacant coordination site that will coordinate, insert, and polymerize olefins. For the purposes of this patent specification and appended claims, the term "activator" is defined as being any compound or component or method which can activate any of the bulky ligand metallocene-type catalyst compounds of the invention as described above. Non-limiting activators, for example, may include a Lewis acid or a non-coordinating ionic activator or ionizing activator or any other compound including Lewis bases, aluminum alkyls, conventional type cocatalysts (previously described herein) and combinations of which can convert a bulky neutral ligand metallocene-type catalyst compound into a catalytically active voluminous ligand metallocene type cation. It is within the scope of this invention to use alumoxane or alumoxane modified as an activator, and / or also to use ionizing, neutral or ionic activators, such as tri (n-butyl) ammonium tetrakis (pentafluorophenyl) boron, a metalloid precursor of trisperfluorophenyl boron or a metalloid precursor trisperfluoronaphthyl boron, polyhalogenated heteroborane anions (WO 98/43983) or combinations thereof, which would ionize the bulky ligand-neutral metallocene type catalyst compound. In one embodiment, an activation method using ionizing ionic compounds does not contain an active proton but is capable of producing both a bulky ligand metallocene-like catalyst cation and a non-coordinating anion also contemplated, and is described in European publications EP-A -0 426 637, EP-A-0 573 403 and U.S. Patent No. 5,387,568, which are incorporated herein by reference. There are a variety of methods for preparing alumoxane and modified alumoxanes, non-limiting examples of which are described in U.S. Patent Nos. 4,665,208, 4,952,540, 5,091,352, 5,206,199, 5,204,419, 4,874,734, 4,924,018, 4,908,463, 4,968,827, 5,308,815, 5,329,032 , 5,248,801, 5,235,081, 5,157,137, 5,103,031, 5,391,793, 5,391,529, 5,693,838, 5,731,253, 5,731,451, 5,744,656 and the European publications EP-A-0 561476, EP-B1-0 279 586 and EP-A-0 594-218. And PCT international publication WO 94/10180, all of which are hereby incorporated by reference in their entirety. The ionizing compounds may contain an active proton, or some other cation associated but not coordinated with or uniquely coordinated in a loose manner with the remaining ion of the ionizing compound. These compounds and the like are described in European publications EP-A-0 570 982, EP-A-0 520 732, EP-A-0 495 375, EP-A-500 944, EP-A-0 277 003 and EP-A-0 277 004, and U.S. Patent Nos. 5,153,157, 5,198,401, 5,066,741, 5,206,197, 5,241,025, 5, 384, 299 and 5, 502, 124 and U.S. Patent Application No. Series 08 / 285,380, filed on August 3, 1994, all of which are fully incorporated herein by reference. Other activators describe those described in PCT International Publication WO 98/07515 such as tris (2,2 ', 2"-nonafluorobiphenyl) fluoroaluminate, the publication of which is incorporated herein by reference in its entirety. Combinations of activators are also contemplated by the invention, for example, alumoxanes and ionizing activators in combinations, see for example, European publication EP-B1 0 573 120, PCT international publications WO 94/07928 and WO 95/14044 and patents of the United States Nos. 5,153,157 and 5,453,410 all of which are hereby incorporated by reference in their entirety. WO 98/09996 incorporated herein by reference discloses voluminous ligand metallocene type catalyst compounds with perchlorates, periodates and iodates including their hydrates. WO 98/30602 and WO 98/30603 incorporated by reference describe the use of lithium (2,2'-bisphenyltrimethyl-silicate). 4THF as an activator for the bulky ligand metallocene type catalyst compound. European publication EP-B1-0 781 299 discloses using a silyl salt in combination with a non-coordinating compatible anion. Also, activation methods such as using radiation (see European patent Bl-0 615 981 incorporated herein by reference), electrochemical oxidation, and the like are contemplated as activation methods for the purposes of rendering the metallocene-like ligand-like catalyst compound voluminous neutral or precursor in a bulky ligand metallocene-type cation capable of polymerizing olefins. Other activators or methods for activating a bulky ligand metallocene-type catalyst compound are described in, for example, U.S. Patent Nos. 5,849,852, 5,859,653 and 5,869,723 and PCT International Publication WO 98/32775, which are incorporated herein by reference. by reference. Mixed Catalysts It is also within the scope of this invention that the voluminous ligand metallocene-type catalyst compounds described above can be combined with one or more catalyst compounds represented by the formula (I), (II), (III), (IV) and (V) with one or more activators or activation methods described above. It is also contemplated by the invention that other catalysts can be combined with the bulky ligand metallocene type catalyst compounds of the invention. For example, see U.S. Patent Nos. 4,937,299, 4,935,474, 5,281,679, 5,359,015, 5,470,811, and 5,719,241 all of which are incorporated herein by reference in their entirety. In another embodiment of the invention one or more bulky ligand metallocene type catalyst compounds or catalyst systems can be used in combination with one or more conventional type catalyst compounds or systems. Nonlimiting examples of mixed catalysts and mixed catalyst systems are disclosed in US Nos. 4,159,965, 4,325,837, 4,701,432, 5,124,418, 5,077,255, 5,183,867, 5,391,660, 5,395,810, 5,691,264, 5,723,399 and 5,767,031 and PCT International Publication WO 96 / 23010 published August 1, 1996, all of which are hereby incorporated by reference in their entirety. It is further contemplated that two or more conventional type transition metal catalysts may be combined with one or more cocatalysts of conventional type. Nonlimiting examples of metal catalysts mixed conventional type transition are described in for example, patents US Nos. 4,154,701, 4,210,559, 4,263,422, 4,672,096, 4,918,038, 5,198,400, 5,237,025, 5,408,015 and 5,420,090, all of which are incorporated the present by reference. Method Support The metallocene catalyst compounds type above described bulky ligand and catalyst systems and compounds, and metal catalysts transition conventional type systems can be combined with one or more support materials or carriers using one of the support methods well known in the art or as described below. In the preferred embodiment, the method of the invention uses a polymerization catalyst in a supported form. For example, in a more preferred embodiment, a bulky ligand metallocene type catalyst compound or catalyst system is in a supported form, for example, deposited on, contacted with, or incorporated into, adsorbed or absorbed in a support or vehicle. The terms "carrier" or "carrier" are used interchangeably and are any porous or non-porous carrier material, preferably a porous carrier material eg, talc, inorganic oxides and inorganic chlorides. Other carriers include resinous support materials such as polystyrene, functionalized or crosslinked organic supports such as polystyrene divinyl benzene polyolefins or of polymeric compounds, or any other material of organic or inorganic support and the like, or mixtures thereof. Preferred carriers are inorganic oxides that include those metal oxides of Group 2, 3, 4, 5, 13 or 14. Preferred supports include silicon oxide, aluminum oxide, silicon oxide and aluminum oxide-magnesium chloride , and mixtures thereof. Other useful supports include magnesium oxide, titanium oxide, zirconium oxide, montmorillonite and the like. Also, combinations of these support materials can be used, for example, silicon-chromium oxide and silicon oxide-titanium oxide. It is preferred that the carrier, more preferably an inorganic oxide, have a surface area of the range from about 10 to about 700 m2 / g, pore volume in the range of about 0.1 to about 4.0 cc / g and average particle size in the range from about 10 to about 500 μm. More preferably, the carrier surface area is in the range of from about 50 to about 500 m2 / g, pore volume from about 0.5 to about 3.5 cc / g and average particle size of from about 20 to about 200 μm. More preferably, the carrier surface area is in the range of from about 100 to about 400 m2 / g, pore volume from about 0.8 to about 3.0 cc / g and average particle size of from about 20 to about 100 μm. The average pore size of a carrier of the invention is typically in the range of from about 10 A to 1000 A, preferably 50 A to about 500 A, and more preferably 75 A to about 350 A. Examples of bulky ligand metallocene catalyst support of the invention are described in U.S. Patent Nos. 4,701,432, 4,808,561, 4,912,075, 4,925,821, 4,937,217, 5,008,228, 5,238,892, 5,240,894, 5,332,706, 5,346,925, 5,422,325, 5,466,649, 5,466,766, 5,468,702, 5,529,965, 5,554,704, 5,629,253, 5,639,835, 5,625,015, 5,643,847, 5,665,665, 5,698,487, 5,714,424, 5,723,400, 5,723,402, 5,731,261, 5,759,940, 5,767,032 and 5,770,664, and in U.S. Patent Application Serial No. 271,598 filed on 7 of July 1994 and 788,736 filed January 23, 1997 and the PCT international publications WO 95/32995, WO 95/14044, WO 96/06187 and WO 97/02297 all of which are hereby incorporated by reference in their entirety. Examples of supports of the conventional type catalyst systems of the invention are described in U.S. Patent Nos. 4,894,424, 4,376,062, 4,395,359, 4,379,759, 4,405,495, 4,540,758 and 5,096,869, all of which are incorporated herein by reference. contemplates that the bulky ligand metallocene-type catalyst compounds of the invention can be deposited thereon or separate carriers together with an activator, or the activator can be used in an unsupported form, or it can be deposited on a support different from the compounds supported bulky ligand metallocene type catalysts of the invention, or any combination thereof There are several other methods in the art for supporting a catalyst system or polymerization catalyst compound of the invention, eg, the bulky ligand metallocene type catalyst compound of the invention can contain a ligand bound to polymer as described in U.S. Patent Nos. 5,473,202 and 5,770,755, which are fully incorporated by reference herein, the bulky ligand metallocene-type catalyst system of the invention can be spray-dried as described in U.S. Pat. No. 5,648,310, which is fully incorporated by reference to the present; the support used with the bulky ligand metallocene catalyst-type system of the invention is functionalized as described in European publication EP-A-0 802 203, which is fully incorporated by reference herein; or at least one substituent or leaving group is selected as described in U.S. Patent No. 5,688,880, which is fully incorporated by reference herein. In a preferred embodiment, the invention provides a supported bulky ligand metallocene-type catalyst system that includes a surface modifier that is used in the preparation of a supported catalyst system, as described in PCT International Publication WO 96/11960 which is incorporates completely by reference to the present. A preferred method for producing the supported bulky ligand metallocene catalyst system of the invention is described below and can be found in U.S. Patent Applications Serial Nos. 265,533, filed June 24, 1994 and 265,532, filed on June 24, 1994 and the PCT international publications WO 96/00245 and WO 96/00243 both published on January 4, 1996, all of which are incorporated in full by reference herein. In this preferred method, the bulky ligand metallocene-type catalyst compound is rendered aqueous slurry in a liquid to form a metallocene solution and a separate solution is formed containing an activator and a liquid. The liquid can be any compatible solvent or other liquid capable of forming a solution or something similar with the bulky ligand metallocene-type catalyst and / or activator compounds of the invention. In the most preferred embodiment the liquid is a cyclic or aromatic aliphatic hydrocarbon, more preferably toluene. The bulky ligand metallocene-type catalyst compound and the activating solutions are mixed with each other and added to a porous support or the porous support is added to the solutions so that the total volume of the bulky ligand metallocene-type catalyst solution and the activator solution or the bulky ligand metallocene type catalyst compound and the activating solution is less than five times the pore volume of the porous support, more preferably less than four times, still more preferably less than three times; Preferred ranges are between 1.1 times to 3.5 times the range and more preferably in the range of 1.2 to 3 times. Methods for measuring the total pore volume of the porous support are well known in the art. Details of one of these procedures is discussed in Volume 1, Experimental Methods in Catalytic Research (Academic Press, 1968) (specifically see pages 67-96). This preferred method involves the use of a classic BET apparatus for nitrogen absorption. Another method well known in the art is described in Innes, Total Porosity and Particle Density and Fluid Catalysts by Liquid Ti tration, Vol. 28, No. 3, Analytical Chemistry 332-334 (March, 1956). The molar ratio of the metal of the activating component to the metal of the bulky ligand metallocene type catalyst compounds are in the range of 0.3: 1 to 2000: 1, preferably 20: 1 to 800: 1, and more preferably 50: 1 to 500: 1 When the activator is an ionizing activator such as that based on the tetrakis (pentafluorophenyl) boron anion, the molar ratio of the metal of the activating component against the metal component of the catalyst is preferably in the range of 0.3: 1 to 3: 1. In one embodiment of the invention, the olefin (s), preferably olefin or olefin or alpha-olefin or alpha-olefins with from 2 to 30 carbon atoms, preferably ethylene or propylene or combinations thereof are prepolymerized in the presence of the catalyst system type metallocene with bulky ligand and / or a conventional type transition metal catalyst of the invention prior to the main polymerization. The prepolymerization can be carried out batchwise or continuously in gas phase, solution or sludge including at high pressures. The prepolymerization can be carried out with any olefin monomer or combination and / or in the presence of any agent that controls molecular weight such as hydrogen. For examples of prepolymerization procedures, see U.S. Patent Nos. 4,748,221, 4,789,359, 4,923,833, 4,921,825, 5,283,278 and 5,705,578 and European Publication EP-B-0279 863 and PCT International Publication WO 97/44371 all of which are incorporated by reference. fully incorporated herein by reference. A prepolymerized catalyst system for the purposes of this patent specification and appended claim is a supported catalyst system. Carboxylate Metal Salt The carboxylate metal salts are well known in the art as additives for use with polyolefins, for example, as a film processing aid. These types of post-reactor processing additives are commonly used as emulsifying agents, antistatic and antistirbing agents, stabilizers, foaming aids, lubrication aids, mold release agents, nucleating agents, and slip and antiblocking agents and the like. . Thus, if it was truly unexpected that these post-reactor or auxiliary agents would be useful with a polymerization catalyst to improve the operability of a polymerization process. For the purposes of this patent specification and the appended claims the term "carboxylate metal salt" is any salt of mono- or di- or tri-carboxylic acid with a metal portion of the Periodic Table of the Elements. Non-limiting examples include saturated or unsaturated aliphatic cyclic aromatic or saturated carboxylic acid salts wherein the carboxylate ligand preferably has from 2 to 24 carbon atoms, such as acetate, propionate, butyrate, valerate, pivalate, caproate, isobutylacetate, t -butyl acetate, caprylate, heptane, pelargonate, undecanoate, oleate, octoate, palmitate, myristate, margarate, stearate, aracate and tercosanoate. Non-limiting examples of the metal portion include a metal of the Periodic Table of the Elements selected from the group of Al, Mg, Ca, Sr, Sn, Ti, V, Ba, Zn, Cd, Hg, Mn, Fe, Co, Ni, Pd, Li and Na. In one embodiment, the carboxylate metal salt is represented by the following general formula: M (Q) x (OOCR) and where M is a metal of Groups 1 to 16 and the series of lanthanides and actinides, preferably of the Groups 1 to 7 and 13 to 16, more preferably of Groups 3 to 7 and 13 to 16, even more preferably Groups 2 and 13, and more preferably Group 13; Q is a halogen, hydrogen, hydroxy or hydroxide, alkyl, alkoxy, aryloxy, siloxy, silane sulfonate or siloxane group; R is a hydrocarbyl radical having from 2 to 100 carbon atoms, preferably 4 to 50 carbon atoms; and x is an integer from 0 to 3 and y is an integer from 1 to 4 and the sum of x and y is equal to the valence of the metal. In a preferred embodiment of the above formula and is an integer from 1 to 3, preferably from 1 to 2, especially wherein M is a Group 13 metal. Non-limiting examples of R in the above formula include hydrocarbyl radicals having 2-hydrocarbyl radicals. at 100 carbon atoms including alkyl, aryl, saturated or unsaturated aromatic, aliphatic, cyclic hydrocarbyl radicals. In one embodiment of the invention, R is a hydrocarbyl radical having the same as or more than 8 carbon atoms, preferably more than or equal to 12 carbon atoms and more preferably more than or equal to 17 carbon atoms. In another embodiment R is a hydrocarbyl radical having 17 to 90 carbon atoms, preferably 17 to 72, and more preferably 17 to 54 carbon atoms. Non-limiting examples of Q in the above formula include one or more groups containing the same or different hydrocarbons such as alkyl, cycloalkyl, aryl, alkenyl, arylalkyl, arylalkenyl or alkylaryl, alkylsilane, arylsilane, alkylamine, arylamine, alkyl phosphide, alkoxy having from 1 to 30 carbon atoms. The group containing hydrocarbons can be linear, branched, or even substituted. Also, Q in one embodiment is an inorganic group such as a halide, sulfate or phosphate. In one embodiment, the preferred carboxylate metal salts are those aluminum carboxylates such as aluminum mono, di- and tri-stearates, aluminum octoates, oleates and cyclohexylbutyrates. In still a more preferred embodiment, the carboxylate metal salt is (CH3 (CH2) 16COO) 3A1, an aluminum tri-stearate (preferred melting point 115 ° C), (CH3 (CH2) 16COO) 2-Al- OH, an aluminum di-stearate (preferred melting point 145 ° C), and a (CH3 (CH2) 16COO) 2-Al-OH) 2, an aluminum monostearate (preferred melting point 155 ° C). Commercially available non-limiting carboxylate metal salts, for example, include Witco Aluminum Stearate # 18, Witco Aluminum Stearate # 22, Witco Aluminum Stearate # 132 and Witco Aluminum Stearate EA Food Grade, all of which are available from Witco Corporation, Memphis, Tennessee In one embodiment the carboxylate metal salt has a melting point of about 30 ° C to about 250 ° C, more preferably from about 37 ° C to about 220 ° C, even more preferably from about 50 ° C to about 200 ° C. C, and much more preferably from about 100 ° C to about 200 ° C. In a more preferred embodiment, the carboxylate metal salt is an aluminum stearate having a melting point in the range of from about 135 ° C to about 165 ° C. In another preferred embodiment, the carboxylate metal salt has a melting point higher than the polymerization temperature in the reactor. Other examples of the carboxylate metal salt include titanium stearates, tin stearates, calcium stearates, zinc stearates, boron stearate and strontium stearates. The carboxylate metal salt in one embodiment can be combined with antistatic agents such as fatty amines, for example, Kemamine AS 990/2 zinc additive, a combination of ethoxylated stearylamine and zinc stearate, or Kemamine AS 990/3, a mixture of ethoxylated stearylamine, zinc stearate and octadecyl-3,5-di-tert-butyl-4-hydroxyhydrocinnamate. Both of these combinations are available from Witco Corporation, Memphis, Tennessee. Method for Preparing the Catalyst Composition The method for making the catalyst composition generally involves the combination, contacting, stirring, and / or mixing of a catalyst system or polymerization catalyst with a carboxylate metal salt. In one embodiment of the method of the invention, a conventional type transition metal catalyst and / or a bulky ligand metallocene type catalyst are combined, contacted, stirred, and / or mixed with at least one carboxylate metal salt. In a still more preferred embodiment, the conventional type transition metal catalyst and / or the bulky ligand metallocene type catalyst are supported on a carrier. In another embodiment, the steps of the method of the invention include forming a polymerization catalyst, preferably forming a supported polymerization catalyst, and contacting the polymerization catalyst with at least one carboxylate metal salt. In a preferred method, the polymerization catalyst comprises a catalyst compound, an activator or co-catalyst and a carrier, preferably the polymerization catalyst is a bulky ligand metallocene-supported catalyst. One skilled in the art recognizes that depending on the catalyst system and the carboxylate metal salt used certain temperature and pressure conditions would be required to avoid, for example, a loss in the activity of the catalyst system. In one embodiment of the method of the invention the carboxylate metal salt is contacted with the catalyst system, preferably a supported catalyst system, more preferably a bulky ligand metallocene-type catalyst system supported under ambient temperatures and pressures. Preferably the contact temperature for combining the polymerization catalyst and the carboxylate metal salt is in the range of 0 ° C to about 100 ° C, more preferably 15 ° C to about 75 ° C, more preferably at about the temperature environment and environmental pressure. In a preferred embodiment, contacting the polymerization catalyst and the carboxylate metal salt is carried out under an inert gas atmosphere, such as nitrogen. However, it is contemplated that the combination of polymerization catalyst and the carboxylate metal salt can be made in the presence of one or more olefins, solvents, hydrogen and the like. In one embodiment, the carboxylate metal salt can be added at any stage during the preparation of the polymerization catalyst. In one embodiment of the method of the invention, the polymerization catalyst and the carboxylate metal salt are combined in the presence of a liquid, for example, the liquid may be a mineral oil, toluene, hexane, isobutane or a mixture thereof. . In a more preferred method the carboxylate metal salt is combined with a polymerization catalyst that has been formed in a liquid, preferably in a slurry, or combined with a substantially dry or dried polymerization catalyst, which has been placed in a liquid and mud has re-formed. In one embodiment, the contact time for the carboxylate metal salt and the polymerization catalyst may vary depending on one or more of the conditions, temperature and pressure, the type of mixing apparatus, the amounts of the components that are removed. to be combined, and even the mechanism for introducing the combination of polymerization catalyst / carboxylate metal salt in the reactor. Preferably, the polymerization catalyst, preferably a bulky ligand metallocene-type catalyst compound and a carrier, is contacted with a carboxylate metal salt for a period of time from about one second to about 24 hours, preferably about one minute. to about 12 hours, more preferably from about 10 minutes to about 10 hours, and even more preferably from about 30 minutes to about 8 hours. In a modality, the proportion of the weight of the carboxylate metal salt against the weight of the transition metal of the catalyst compound is in the range of from about 0.01 to about 1000, preferably in the range of from about 1 to about 100, more preferably in the range of from about 2 to about 50, and still more preferably in the range of from 4 to about 20. In one embodiment, the ratio of the weight of the carboxylate metal salt to the weight of the transition metal of the catalyst compound is in the range of from about 2 to about 20, more preferably in the range of from about 2 to about 12, and still more preferably in the range of from 4 to about 10. In another embodiment of the method of the invention, the weight percentage of the carboxylate metal salt based on the total weight of the polymerization catalyst is in the range of from about 0.5 weight percent to about 500 weight percent, preferably in the range of from about 1 weight percent to about 25 weight percent, more preferably in the range of about 2 percent by weight up to about 12 weight percent, and still more preferably in the range of from about 2 weight percent to about 10 weight percent. In another embodiment, the weight percent of the carboxylate metal salt based on the total weight of the polymerization catalyst is in the range of from 1 to about 50 weight percent, preferably in the range of from about 2 percent to about 30 weight percent, and more preferably in the range of from about 2 weight percent to about 20 weight percent. In one embodiment, wherein the process of the invention is producing a polymer product having a density greater than 0.910 g / cc, the total weight percentage of the carboxylate metal salt based on the total weight of the polymerization catalyst is greater than 1 percent by weight. In still another embodiment, wherein the process of the invention is producing a polymer product having a density of less than 0.910 g / cc, the total weight percent of the carboxylate metal salt based on the total weight of the catalyst of polymerization is greater than 3 weight percent. If the polymerization catalyst includes a vehicle, the total weight of the polymerization catalyst includes the weight of the vehicle. It is believed that the more metal of the activator, for example, the total aluminum content or the free aluminum content (the content of alkyl aluminum in the alumoxane), is present in the polymerization catalyst, more carboxylate metal salt is required. . Manipulating the amounts or fillers of the polymerization catalyst components, ie the free aluminum can provide a means for adjusting the level of the carboxylate metal salt. The techniques and mixing equipment contemplated for use in the method of the invention are well known. The mixing techniques can include any means of mechanical mixing, for example shaking, stirring, stirring, and laminating. Another contemplated technique involves the use of fluidization, for example in a fluid bed reactor vessel where circulated gases provide mixing. Non-limiting examples of mixing equipment for combining, in the most preferred embodiment a solid polymerization catalyst and a solid carboxylate metal salt, include a ribbon mixer, a static mixer, a double cone mixer, a drum mixer, a drum mill, a dehydrator, a fluidized bed, a helical mixer and a conical screw mixer. In one embodiment of the method of the invention, a conventional type transition metal catalyst supported, preferably a bulky ligand supported metallocene catalyst, is stirred with a carboxylate metal salt for a period of time such that a substantial portion of the supported catalyst is intimately mixed and / or substantially contacted with the metal salt of carboxylate. In a preferred embodiment of the invention the catalyst system of the invention is supported on a vehicle, preferably the supported catalyst system is substantially dried, preformed, substantially dried and / or allowed to flow freely. In a particularly preferred method of the invention, the preformed supported catalyst system is contacted with at least one carboxylate metal salt. The carboxylate metal salt may be in solution or in mud or in a dry state, preferably the carboxylate metal salt is in a substantially dry or dried state. In a preferred embodiment, the carboxylate metal salt is contacted with a supported catalyst system, preferably a bulky ligand metallocene-type catalyst system supported on a rotary mixer under a nitrogen atmosphere, more preferably the mixer is a stirring mixer, or in a fluidized bed mixing process, in which the polymerization catalyst and the carboxylate metal salt is in the solid state, that is, both are substantially in a dry state or in a dried state. In one embodiment of the method of the invention a conventional type transition metal catalyst compound, preferably a bulky ligand metallocene type catalyst compound, is contacted with a carrier to form a supported catalyst compound. In this method, an activator or co-catalyst for the catalyst compound is contacted with a separate carrier to form a supported activator or supported co-catalyst. It is contemplated in this particular embodiment of the invention, that a carboxylate metal salt is then mixed with the supported catalyst compound or the supported activator or co-catalyst, in any order, mixed separately, mixed simultaneously, or mixed with only one of the supported catalyst, or preferably the supported activator before mixing it with the separately supported catalyst and the co-catalyst activator. As a result of using the combination of the carboxylate metal salt / polymerization catalyst of the invention it may be necessary to improve the flow of the overall catalyst to the reactor. Despite the fact that the catalyst flow is not good as a catalyst without the carboxylate metal salt, the flowability of the catalyst / carboxylate combination of the invention is not a problem. If the catalyst flow needs improvement, it is well known in the art to use vibrating vessels, or catalyst feeder brushes or feeder pressure purges and the like. In another embodiment, the polymerization catalyst / carboxylate metal salt can be contacted with a liquid, such as a mineral oil and introduced to a polymerization process in a mud state. In this particular embodiment, it is preferred that the polymerization catalyst be a supported polymerization catalyst. In some polymerization processes, smaller particle size support materials are preferred. However, the operability of these processes is more challenging. It has been discovered that using the polymerization catalyst and carboxylate metal salt combination of the invention, support materials with smaller particle size can be successfully used. For example, silicon oxide having an average particle size from about 10 microns to 80 microns. Silicon oxide materials of this size are available from Crosfield Limited, Warrington, England, for example, Crosfield ES-70 having an average particle size of 35 to 40 microns. Without wanting to stick to any theory, it is traditionally believed that using supports of smaller average particle size produces finer and results in a supported catalyst more prone to lamination. It is believed that the use of the carboxylate metal salt with the polymerization catalyst provides for a better particle growth during the polymerization. This better particle morphology is believed to result in less fines and a reduced tendency for lamination to occur. Thus, the use of the carboxylate metal salt allows the use of smaller support material. In one embodiment, the method of the invention provides co-injecting an unsupported polymerization catalyst and carboxylate metal salt of the reactor. In one embodiment the polymerization catalyst is used in an unsupported manner, preferably in a liquid form as described in U.S. Patent Nos. 5,317,036 and 5,693,727 and European Publication EP-A-0 593 083, all which are incorporated herein by reference. The polymerization catalyst in liquid form can be fed by a carboxylate metal salt to a reactor using the injection methods described in PCT International Publication WO 97/46599, which is incorporated herein by reference in its entirety. When a combination of the carboxylate metal salt and an unsupported bulky ligand metallocene catalyst system is used, the molar ratio of the metal of the activating component to the metal of the bulky ligand metallocene-type catalyst compound is in the range of 0.3. : 1 to 10,000: 1, preferably 100: 1 to 5,000: 1, and even more preferably 500: 1 to 2000: 1. Polymerization Process The catalysts and catalyst systems of the invention described above are suitable for use in any polymerization process. The polymerization processes include processes in solution phase, gas phase, mud phase and high pressure process or a combination thereof. Particularly preferred is the gas phase or mud phase polymerization of one or more olefins at least one of which is ethylene or propylene. In one embodiment, the process of this invention is directed to solution polymerization, slurry phase or gas phase for one or more olefin monomers having from 2 to 30 carbon atoms, preferably from 2 to 12 carbon atoms, and more preferably from 2 to 8 carbon atoms. The invention is particularly suitable for the polymerization of two or more olefin monomers of ethylene, propylene, butene-1, pentene-1,4-methyl-pentene-1, hexene-1, octene-1 and decene-1. Other monomers useful in the process of the invention include ethylenically unsaturated monomers, diolefins having from 4 to 18 carbon atoms, conjugated or non-conjugated dienes, polyenes, vinyl monomers and cyclic olefins. Non-limiting monomers useful in the invention can include norbornene, norbornadiens, isobutylene, vinylbenzocyclobutane, styrenes, alkyl substituted styrene, norbornene ethylene, isoprene, dicyclopentadiene and cyclopentene. In the most preferred embodiment of the process of the invention, an ethylene copolymer is produced, wherein with ethylene, a comonomer having at least one alpha olefin having from 4 to 15 carbon atoms, preferably from 4 to 12 carbon atoms, carbon, and more preferably from 4 to 8 carbon atoms, is polymerized in a gas phase process. In another embodiment of the process of the invention, ethylene or prspylene are polymerized with at least two different comonomers, optionally one of which may be diene, to form a terpolymer. In one embodiment, the invention is directed to a process, particularly a gas phase or mud phase process, to polymerize propylene alone or with one or more monomers including ethylene, and olefins having from 4 to 12 carbon atoms. The polypropylene polymers can be produced using particularly bridged bulky ligand metallocene type catalysts as described in U.S. Patent Nos. 5,296,434 and 5,278,264, both of which are incorporated herein by reference. Typically in a gas phase polymerization process a continuous cycle is employed wherein a part of the cycle of a reactor system, a cycle gas stream, otherwise known as recycle stream or fluidizing medium, is heated in the reactor by the heat of the polymerization. This heat is removed from the recycle composition in another part of the cycle by cooling the external system to the reactor. Generally, in a gas fluidized bed process for producing polymers, a gaseous stream containing one or more monomers is continuously cycled through a fluidized bed in the presence of a catalyst under reactive conditions. The gas stream is removed from the fluidized bed and recycled back to the reactor. Simultaneously, the polymer product is removed from the reactor and new monomer is added to replace the polymerized monomer (see for example, U.S. Patent Nos. 4,543,399, 4,588,790, 5,028,670, 5,317,036, 5,352,749, 5,405,922, 5,436,304, 5,453,471, 5,462,999 , 5,616,661 and 5,668,228 all of which are incorporated herein by reference in their entirety). The reactor pressure in a gas phase process can vary from about 690 kPa to about 3448 kPa, preferably in the range from about 1379 kPa to about 2759 kPa, more preferably in the range from about 1724 kPa to about 2414 kPa. The temperature of the reactor in the gas phase process can vary from about 30 ° C to about 120 ° C., preferably from about 60 ° C to about 115 ° C, more preferably in the range from about 70 ° C to 110 ° C, and still more preferably in the range from about 70 ° C to about 95 ° C. Other gas phase processes contemplated by the process of the invention include those described in U.S. Patent Nos. 5,627,242, 5,665,818 and 5,677,375, and in European publications EP-A-0 794 200, EP-A-0 802 202 , EP-A2 0 891 990 and EP-B-634 421 all of which are hereby incorporated by reference in their entirety. In a preferred embodiment, the reactor used in the present invention is capable and the process of the invention is producing more than 227 kg / hour of polymer up to about 90,900 kg / hour or more of polymer, preferably more than 455 kg / hour, more preferably more than 4540 kg / hour, even more preferably more than 11.300 kg / hour, still more preferably more than 15.900 kg / hour, still more preferably more than 22,700 kg / hour and more preferably more than 29,000 kg / hour up to more than 45,500 kg / hour. A sludge polymerization process generally uses pressures in the range of from about 1 to about 50 atmospheres and even higher and temperatures in the range of 0 ° C to about 120 ° C. In a sludge polymerization, a solid particulate polymer slurry is formed in a polymerization diluent medium to which ethylene and comonomers and often hydrogen together with the catalyst are added. The suspension including diluent is stirred intermittently or continuously from the reactor where the volatile components are separated from the polymer and recycled, optionally after distillation, to the reactor. The liquid diluent used in the polymerization medium is typically an alkane having from 3 to 7 carbon atoms. The medium used should be liquid under polymerization conditions and relatively inert. When a propane medium is used the process must be operated on the critical temperature and pressure of the reaction diluent. Preferably, a hexane or an isobutane medium is used. A preferred polymerization technique of the invention is known as a particulate polymerization, or a sludge process wherein the temperature is maintained below the temperature at which the polymer becomes a solution. This technique is well known in the field, and is described in, for example, U.S. Patent No. 3,248,179 which is incorporated herein by reference in its entirety. Other mud processes include those that employ a cycle reactor and those that utilize a plurality of series, parallel agitation reactors, or a combination thereof. Non-limiting examples of mud processes include continuous or stirred cycle tank processes. Also, other examples of mud processes are described in U.S. Patent No. 4,613,484, which is incorporated herein by reference in its entirety. In one embodiment the reactor used in the slurry process of the invention is capable of and the process of the invention produces more than 907 kg / hour of polymer, more preferably more than 2268 kg / hour, and more preferably more than 4540 kg / polymer time. In another embodiment, the mud reactor used in the process of the invention produces more than 6804 kilograms of polymer per hour, preferably more than 11.340 kilograms / hour to about 45,500 kilograms of polymer per hour. Examples of processes in solution are described in U.S. Patent Nos. 4,271,060, 5,001,205, 5,236,998 and 5,589,555, which are hereby incorporated by reference in their entirety. A preferred process of the invention is where the process, preferably a mud or gas phase process, is operated in the presence of a bulky ligand metallocene catalyst system and in the absence of or essentially free of any cleaner, such as triethylaluminum, trimethylaluminum, triisobutylaluminum and tri-n-hexylaluminum and diethylaluminum chloride, dibutyl zinc and the like. This preferred process is described in PCT International Publication WO 96/08520 and in U.S. Patent Nos. 5,712,352 and 5,763,543 which are hereby incorporated by reference in their entirety. However, it has been found that a polymerization process using a combination of the catalyst / carboxylate metal salt system of the invention can be operated with a small amount of scavenger with reduced effect or no effect on the process operability and catalyst performance . Thus, in one embodiment, the invention provides a process for polymerizing olefins in a reactor in the presence of a bulky ligand metallocene-type catalyst system, a carboxylate metal salt and a scrubber. In one embodiment, the polymerization catalyst and / or catalyst composition, the polymerization catalyst and the carboxylate metal salt have a productivity greater than 1500 grams of polymer per gram of catalyst, preferably greater than 2000 grams of polymer per gram of catalyst , more preferably greater than 2500 grams of polymer per gram of catalyst, and still more preferably greater than 3000 grams of polymer per gram of catalyst. In another embodiment, the polymerization catalyst and / or catalyst composition, the polymerization catalyst and the carboxylate metal salt have a productivity greater than 2000 grams of polymer per gram of catalyst, preferably greater than 3000 grams of polymer per gram of catalyst , more preferably greater than 4000 grams of polymer per gram of catalyst, and still more preferably greater than 5000 grams of polymer per gram of catalyst. In one embodiment, the polymerization catalyst and / or catalyst composition has a reactivity ratio generally lower than 2, more typically less than 1. The reactivity ratio is defined as the molar ratio of comonomer to monomer entering the reactor, for example , as measured in the gas composition in the gas phase process, divided by the molar ratio of the comonomer to the monomer in the polymer product being produced. In a preferred embodiment, the reactivity ratio is less than 0.6, more preferably less than 0.4, and more preferably less than 0.3. In the most preferred embodiment, the monomer is ethylene and the comonomer is an olefin having 3 or more carbon atoms, more preferably an alpha-olefin having 4 or more carbon atoms, and more preferably an alpha-olefin selected from the group consisting of butene -1, 4-methyl-pentene-1, pentene-1, hexene-1 and octene-1. In another embodiment of the invention, when transitioning a first polymerization catalyst or a second polymerization catalyst, preferably when the first and second polymerization catalysts are bulky ligand metallocene type catalyst compounds, more preferably when the second catalyst Polymerization is a bridged bulky ligand metallocene-type catalyst compound, it may be preferable during the transition to use a catalyst composition of a carboxylate metal salt combined with a bridged bulky ligand metallocene type catalyst. When a polymerization process is started, especially a gas phase process, there is a great tendency for operability problems to arise. Thus, it is contemplated in the present invention that a mixture of polymerization catalyst and carboxylate metal salt is used at the start to reduce or eliminate starting problems. In addition, it is also contemplated that once the reactor operates in a stable state, a transition to the same or a different polymerization catalyst without the carboxylate metal salt can be made. In another modality, during a polymerization process that is being interrupted or is about to be interrupted, the transition can be made to a mixture of polymerization catalyst / carboxylate metal salt. This change of polymerization catalysts is contemplated to occur when operability problems arise. Indications of operability problems are well known in the art. Some of which in the gas phase process include excursions of temperature in the reactor, unexpected pressure changes, excessive generation of static or unusually high static spikes, large chunks, rolling and the like. In one embodiment, the carboxylate metal salt can be added directly to the reactor, particularly when operability problems arise. It has also been found that by using the polymerization catalyst combined with a carboxylate metal salt of the invention it is easier to produce fractional melt index and higher density polymers. In one embodiment, the invention provides a process for polymerizing olefins in a reactor in the presence of a polymerization catalyst in combination with a carboxylate metal salt to produce a polymer product having a melt index of less than about 1 dg / minute. and a density greater than 0.920 g / cc, more preferably the polymer product has a melt index of less than 0.75 dg / minute and a density greater than 0.925 g / cc. Preferably the polymerization catalyst is a bulky ligand metallocene type catalyst, more preferably the process is a gas phase process and the polymerization catalyst includes a carrier. It is contemplated that by using the polymerization catalyst / carboxylate metal salt combination of the invention, making the transition to one or more degrees of polymer difficulty would be simpler. Thus, in one embodiment, the invention is directed to a process for polymerizing olefins in the presence of a first catalyst composition, under steady state conditions, preferably gas phase process conditions, to produce a first polymer product. The first polymer product has a density greater than 0.87 g / cc, preferably greater than 0.900 g / cc, more preferably greater than 0.910 g / cc, and a melt index in the range from 1 dg / minute to approximately 200 dg / minute, preferably in the range of more than 1 dg / minute to about 100 dg / minute, more preferably about more than 1 dg / minute to about 50 dg / minute, more preferably more than 1 dg / minute to about 20 dg / minute . This process further comprises the step of transitioning to a second catalyst composition to produce a second polymer product having a density greater than 0.920 g / cc, preferably greater than 0.25 g / cc, and a melt index of less than 1 dg. / minute, preferably less than 0.75 dg / minute. The second catalyst composition comprising, in combination, a conventional type transition metal catalyst and / or a bulky ligand metallocene type catalyst, and a carboxylate metal salt. It is also within the scope of this particular embodiment to transition from a first polymer product having an I21 / I2 (described below) from less than 25 to a second polymer product having an I21 / I2 greater than 25. , preferably greater than 30, and even more preferably greater than 35. In yet another embodiment, the process of the invention involves alternating between a first catalyst composition comprising a first polymerization catalyst / carboxylate metal salt mixture and a catalyst composition of a second polymerization catalyst without a carboxylate metal salt to improve the operability of the overall process. In another embodiment, the first and second catalyst compositions described above can be used simultaneously, for example, as a mixture or inject in a separate reactor. In any of these embodiments, the first and second polymerization catalysts may be the same or different. Polymer Product of the Invention The polymers produced by the process of the invention can be used in a wide variety of end-use products and applications. The polymers produced by the process of the invention include linear low density polyethylene, elastomers, plastomers, high density polyethylenes, low density polyethylenes, polypropylene and polypropylene copolymers. The polymers, typically ethylene-based polymers, have a density in the range of from 0.86 g / cc to 0.97 g / cc, preferably in the range of from 0.88 g / cc to 0.965 g / cc, more preferably in the range of from 0.900 g / cc to 0.96 g / cc, even more preferably in the range from 0.905 g / cc to 0.95 g / cc, still more preferably in the range of 0.910 g / cc to 0.940 g / cc, and more preferably higher of 0.915 g / cc, preferably greater than 0.920 g / cc, and more preferably greater than 0.925 g / cc. The polymers produced by the process of the invention typically have a molecular weight distribution, a weight average molecular weight versus number average molecular weight (Mw / Mn) greater than 1.5 to about 15, particularly greater than 2 to about 10, more preferably greater than about 2.2 to less than about 8, and still more preferably 2.5 to 8. The ratio of Mw / Mn can be measured by gel permeation chromatography techniques well known in the art. Also, the polymers of the invention typically have a narrow composition distribution as measured by the Composition Distribution Expansion Index (CDBI). Additional details for determining the CDBI of the copolymer are known to those skilled in the art. See, for example, PCT International Patent Application WO 93/03093, published February 18, 1993 which is hereby incorporated by reference in its entirety. The bulky ligand metallocene-type catalyzed polymers of the invention in one embodiment have a CDBI generally in the range of greater than 50 percent up to 99 percent, preferably in the range of 55 percent up to 85 percent, and more preferably 60 percent. percent to 80 percent, even more preferably greater than 60 percent, still more preferably greater than 65 percent. In another embodiment, polymers produced using a conventional type transition metal catalyst have a CDBI of less than 50 percent, more preferably less than 40 percent, and more preferably less than 30 percent. The polymers of the present invention in one embodiment have a melt index (MI) or (I2) as measured by ASTM-D-1238-E in the range from 0.01 dg / minute to 1000 dg / minute, more preferably from about 0.01 dg / minute to about 100 dg / minute, even more preferably from about 0.1 dg / minute to about 50 dg / minute, and more preferably from about 0.1 dg / minute to about 10 dg / minute. The polymers of the invention in one embodiment have a melt index ratio (I21 / I2) (I21 measured by ASTM-D-1238-F) of from 10 to less than 25, more preferably from about 15 to less than 25. The polymers of the invention in a preferred embodiment have a melt index ratio (I21 / I2) (I21 measured by ASTM-D-1238-F) of from preferably greater than 25, more preferably greater than 30, even more preferably higher of 40, still more preferably greater than 50 and much more preferably greater than 65. In yet another embodiment, the propylene-based polymers are produced in the process of the invention. These polymers include atactic polypropylene, isotactic polypropylene, and syndiotactic polypropylene. Other propylene polymers include random propylene copolymers, in block or impact. The polymers produced by the process of the invention are useful for forming cooperations such as film, sheet, fiber extrusion and coextrusion as well as blow molding, injection molding and rotary molding. Films include blown or cast films formed by coextrusion or by lamination useful as shrink film, bonded film, stretched film, sealing films, oriented films, candy packaging, heavy duty bags, market bags, baked food packaging and frozen, medical packaging, industrial coatings, membranes, etc. in applications of contact with food and without contact with food. The fibers include spunbond, spunbond, solution spinning and meltblown spun operations for use in woven or nonwoven form for making filters, diaper fabrics, medical clothing, geotextiles, and the like. Extruded items include medical tubes, wire and cable coatings, geomembranes, and pond linings, molded articles that include single and multi-layer constructions in the form of bottles, tanks, large hollow items, rigid containers for food and toys, etc. Examples In order to provide a better understanding of the example, including the representative advantages thereof, the following examples are offered. The polymer properties were determined by the following test methods: The density was measured according to ASTM-D-1238. The incrustation index in the Tables below illustrates the operability of the catalyst. The higher the value, the greater the formation of scale observed. A zero scale index means that there are substantially no inlays or no visible. An index of incrustations of 1 indicates a slight formation of scale, while a very slight partial coating of the polymer in the stirrer blades of an isobutane polymerization reactor in sludge 2 liters and / or no lamination of the reactor body. An incrustation index 2 indicates a more than light incrustation formation, where the agitator blades have a coating like paint, heavier polymer and / or the reactor body has some lamination in the band of a width of 2.54 to 5.08 centimeters on the reactor wall. An incrustation index of 3 is considered average scale formation, where the agitator blades have a thicker coating, similar to polymer latex on the agitator blade, some soft lumps in the reactor, and / or lamination of the body of the agitator. reactor with a band of 5.08 to 7.62 centimeters wide on the wall of the reactor. An incrustation index of 4 is evidence of a larger than average scale formation, where the agitator has a thick coating, similar to latex, to some harder polymer groups / balls, and / or the reactor body has a band Lamination from 7.62 to 10.2 centimeters wide. The activity in the following Table is measured in grams of polyethylene (PE) per gram of polymerization catalyst per hour (gPE / gCat .h). Comparative Example 1 Preparation of Catalyst A The bridged bulky ligand metallocene type catalyst compound used in this Comparative Example 1 is dimethylsilyl-bis (tetrahydroindenyl) zirconium dichloride (Me 2 Si (H 4 Ind) 2 ZrCl 2) available from Albemarle Corporation, Baton Rouge, Louisiana. The catalyst compound (Me2Si (H4Ind) 2ZrCl2) was supported on Crosfield grade 70 silicon oxide at 600 ° C having approximately 1.0 weight percent ignition loss (LOI). The LOI is measured by determining the weight loss of the support material that has been heated and maintained at a temperature of about 1000 ° C for about 22 hours. Crosfield grade 70 silicon oxide ES has an average particle size of 40 microns and is available from Crosfield Limited, Warrington, England. The first step in the fabrication of the above supported bulky ligand metallocene type catalyst involves forming a precursor solution. 209 kilograms of extended and dry toluene was added to a stirred reactor after which 482 kilograms of a 30 weight percent methylaluminoxane (MAO) in toluene (available from Albemarle, Baton Rouge, Louisiana) was added. 430 kilograms of a 2 weight percent solution of toluene of a dimethylsilyl-bis (tetrahydroindenyl) zirconium dichloride catalyst compound and 272 kilograms of additional toluene were introduced into the reactor. The precursor solution was stirred at 26.7 ° C to 37.8 ° C for one hour. While stirring the previous precursor solution, 386 kilograms of Crosfield silicon oxide dehydrated vehicle at 600 ° C was added slowly to the precursor solution and the mixture was stirred for 30 minutes at 26.7 to 37.8 ° C. at the end of the 30 minutes of agitation of the mixture, 109 kilograms of a 10 percent by weight toluene solution of AS-990 (N, -bis (2-hydroxylethyl) octadecylamine ((C18H37N (CH2CH2OH) 2) available as Kemamine AS-990 from Witco Corporation, Memphis, Tennesse, is added along with an additional 50 kilograms of toluene rinse and the contents of the reactor are then mixed for 30 minutes while heating to 79 ° C. After 30 minutes, vacuum is applied and the polymerization catalyst mixture is dried at 79 ° C for about 15 hours to a free flowing powder The weight of the final polymerization catalyst was 544 kilograms and had a zirconium weight percent of 0.35 and one percent in aluminum weight of 12.0.

Example 1 Preparation of Catalyst B One kilogram of sample of the polymerization catalyst prepared as described in Comparative Example 1, Catalyst A, was weighed into a 3 liter glass flask under an inert atmosphere. 40 grams of Witco # 22 aluminum stearate (AISt # 22) (CH3 (CH2) 16COO) 2Al-ILO available from Witco Corporation, Memphis, Tennessee, was vacuum dried at 85 ° C and added to the flask and the contents were spun / mixed during minutes at room temperature. The aluminum stearate appeared homogeneously dispersed in all the catalyst particles. Example 2 Preparation of Catalyst C One kilogram of sample of the polymerization catalyst prepared as described in Comparative Example 1, Catalyst A, was weighed into a glass flask of 3 liters under an inert atmosphere. 20 grams of Witco # 22 aluminum stearate (AISt # 22) (CH3 (CH2) 16C00) 2A1-0H available from Witco Corporation, Memphis, Tennessee, was vacuum dried at 85 ° C and added to the flask and the contents were stirred / mixed for 20 minutes at room temperature. Aluminum stearate appeared to be dispersed homogeneously through all the catalyst particles. Example 3 Preparation of Catalyst D One kilogram of sample of the polymerization catalyst prepared as described in Comparative Example 1, Catalyst A, was weighed in a 3-liter glass flask under an inert atmosphere. 10 grams of Witco # 22 aluminum stearate (AISt # 22) (CH3 (CH2) 16COO) 2A1-0H available from Witco Corporation, Memphis, Tennessee, was vacuum dried at 85 ° C and added to the flask and the contents were rotated / mixed for 20 minutes at room temperature. The aluminum stearate appeared homogeneously dispersed in all the catalyst particles. Polymerization Process Using Catalyst A to Catalyst D A 2-liter autoclave reactor under a nitrogen purge was charged with 0.16 mmol of triethylaluminum (TEAL), followed by 20 ce of hexane-1 comonomer and 800 ce of diluent of isobutane. The contents of the reactor were heated to 80 ° C, after which, 100 milligrams of each of the above supported polymerization catalysts, Catalysts A, B, C and D, were separately polymerized as follows: each polymerization catalyst was introduced at the same time with ethylene in the reactor to make a total reactor pressure of 2240 kPa. The temperature of the reactor was maintained at 85 ° C and the polymerization was allowed to continue for 40 minutes. After 40 minutes the reactor was cooled, ethylene was vented and the polymer was dried and weighed to obtain polymer production. Table 1 below provides the production activity data, as well as the scale characteristics observed using Catalyst A without aluminum stearate and Catalyst B through D, each with various levels of aluminum stearate.

Table 1 Table 1 i uses the effect of various levels of aluminum stearate on the activity and operability of the catalyst. Comparative Example 2 Preparation of Catalyst E In a 7.57 liter reactor, 2.0 liters of toluene was charged first, then 1060 grams of 30 weight percent methylalumoxane solution in toluene (available from Albermarle, Baton Rouge, Louisiana), followed by 23.1 g of bis (1,3-methyl-n-butylcyclopentadienyl) zirconium dichloride as a 10 percent solution in toluene. The mixture was stirred for 60 minutes at room temperature after which 850 grams of silicon oxide (Davison 948 dehydrated at 600 ° C available from W.R. Grace, Davison Chemical Division, Baltimore, Maryland) was added to the liquid with slow stirring. The stirring speed was increased for approximately 10 minutes to ensure dispersion of the silicon oxide in the liquid and then the appropriate amount of toluene was added to form a slurry from liquid to solid having a consistency of 4 cc / g of silicon oxide . Mixing was continued for 15 minutes at 120 rpm after which 6 grams of Kemamine AS-990 (available from Witco Corporation, Memphis, Tennessee) was dissolved in 100 g of toluene and added and stirred for 15 minutes. The drying was initiated under vacuum and some nitrogen purge at 79.4 ° C. When the polymerization catalyst comprising the carrier, the silicon oxide, appeared to be flowing freely, it was cooled and discharged in a purged nitrogen vessel. A yield of approximately 1 kg of dry polymerization catalyst was obtained due to some losses due to drying. Comparative Example 4 Preparation of Catalyst F A sample of the polymerization catalyst prepared as described in Comparative Example 2, Catalyst E, was mixed dry with an amount of aluminum stearate # 22 (AISt # 22) (available from Witco Corporation, Memphis, Tennessee) equal to 2 weight percent based on the total weight of the supported polymerization catalyst. The AISt # 22 was dried in a vacuum oven for 12 hours at 85 ° C. Under nitrogen, the polymerization catalyst was dry mixed with the AISt # 22. Table 2 illustrates the benefits of adding the carboxylate metal salt in these examples, aluminum stearate, to the polymerization catalyst. These examples also show that the carboxylate metal salt has virtually no effect on the molecular weight properties of the polymer formed. The results of the polymerization runs for catalysts E and F using the same process as previously described for catalysts A to D are shown in Table 2 below. Table 2 Comparative Example 3 Preparation of Catalyst G In a 7.57 liter reactor, 1060 grams of 30 weight percent methylalumoxane (MAO), an activator, in solution in toluene (PMAO, modified MAO available from Akzo Nobel, LaPorte, Texas) was charged. , followed by 1.5 liters of toluene. While stirring 17.3 grams of bis (1,3-methyl-n-butylcyclopentadienyl) zirconium dichloride, a bulky ligand metallocene-like catalyst compound, as an 8 weight percent solution of toluene was added to the reactor and the mixture was stirred for 60 minutes at room temperature to form a catalyst solution. The content of the reactor was discharged into a flask and 850 grams of silicon oxide dehydrated at 600 ° C (available from Crosfield Limited, Warrington, England) was charged to the reactor. The catalyst solution contained in the flask was added slowly to the silicon oxide carrier in the reactor while stirring slowly. More toluene (350 cc) was added to ensure a muddy consistency and the mixture was stirred for an additional 20 minutes. 6 grams of Kemamine AS-990 (available from Witco Corporation, Memphis, Tennessee) as a 10 percent solution in toluene was added and stirring continued for 30 minutes at room temperature. The temperature was raised to 68 ° C and vacuum was applied in order to dry the polymerization catalyst. Drying was continued for about 6 hours with low agitation until the polymerization catalyst appeared to have free flow. It was then discharged into a flask and stored under a nitrogen atmosphere. The production was 1006 grams due to some losses in the drying process. The analysis of the polymerization catalyst was: zirconium = 0.30 weight percent, aluminum = 11.8 weight percent. Examples 5 and 6 In Examples 5 and 6, the polymerization catalyst prepared as described in Comparative Example 3, Catalyst G, was co-injected with 4 weight percent and 8 weight percent of aluminum stearate # 22 from Witco (AISt # 22) (available from Witco Corporation, Memphis, Tennessee) based on catalyst loading and injected into a polymerization reactor. The results of the polymerization runs using Catalysts G, H and I in the same process as previously described for Catalysts A through D are shown in Table 3.

Table 3 Table 3 illustrates that even with a very active scale-prone catalyst, aluminum stearate is effective. It further illustrates that aluminum stearate does not materially change the characteristics of the product. Examples 7 to 11 Examples 7 and 8 use the same catalyst of Comparative Example 3, Catalyst G, with Calcium Stearate (CaSt) (Catalyst J) as the carboxylate metal salt in Example 7 and Zinc Stearate (ZnSt) (Catalyst K) in Example 8. The CaSt and ZnSt are available from Mallinkrodt Corporation, Phillipsbury, New Jersey. The polymerization process used to test the catalyst compositions of Examples 7 and 8 is the same as that described and used above for Catalyst A through D. Examples 9 through 11 use the same catalyst as Comparative Example 1, Catalyst A, with aluminum monostearate (Example 9, Catalyst L) as the metal salt of carboxylate, aluminum distearate (Example 10, Catalyst M) and aluminum tristearate (Example 11, Catalyst N). The polymerization process just described herein and used in Examples 12 to 15 was used to test the catalyst compositions of Example 9 through 11, Catalysts L, M and N. Table 4 below provides these results. Table 4 Examples 7 and 8 illustrate the use of different salts of carboxylate metals. Specifically, Examples 7 and 8, the metal stearate, Ca and Zn, are shown to be effective in reducing fouling. Examples 9, 10 and 11 illustrate various types of carboxylate aluminum salts, specifically that different forms of aluminum stearate are effective. From the data in Table 4 it can be seen that monostearates and distearates are more effective. Examples 12 to 15 In Examples 12 to 15 the dry mixing method described in Example 1 was used with Catalyst A of Comparative Example 1 with various types of carboxylate metal salts. The amount and type of carboxylate metal salt is presented in Table 5. The following polymerization process described below was used for each combination of polymerization catalyst / carboxylate metal salt, catalysts O, P, Q and R. Polymerization Process for Examples 12 to 15 A 2 liter autoclave reactor under a nitrogen purge was charged with 0.16 mmol of triethylaluminum (TEAL), followed by 25 hexene-1 comonomer ce and 800 ct of isobutane diluent. The content of the reactor was heated to 80 ° C, after which, 100 milligrams of each mixture of the supported polymerization catalysts / carboxylate metal salt described above, (Catalyst A with the specific amounts of carboxylate metal salt as reported in Table 5), were separately polymerized as follows: each combination of polymerization catalyst / carboxylate metal salt was simultaneously introduced with ethylene into the reactor to make a total reactor pressure of 2240 kPa. The reactor temperature was maintained at 85 ° C and the polymerization was allowed to continue for 40 minutes. After 40 minutes the reactor was cooled, the ethylene was vented and the polymer was dried and weighed to obtain the polymer production. The results are given in Table 5 below. Of particular interest, these Examples 12, 13, 14, and 15 illustrate a preference for having a bulky R group in the carboxylate metal salts, specifically, the aluminum carboxylates.

Table 5 Examples 16 to 18 and Comparative Example 4 Examples 16, 17 and 18 and Comparative Example 4 illustrate the effectiveness of the use of a carboxylate metal, particularly aluminum stearate, in a fluid bed gas phase process in combination with a bulky ligand metallocene type catalyst system to produce polymer grades that are typically more difficult to produce especially in terms of operability. Traditionally, the rate of fractional melting and higher density grades are difficult to make from the point of view of reactor operability. A polymerization catalyst used in the polymerizations of Examples 16, 17 and 18 and Comparative Example 4 were run in the process described below and the results of which are indicated in Table 6 below. Polymerization Processes The catalysts A, B and F described above were tested separately in a continuous gas phase fluidized bed reactor which comprised 18 nominal inches, program reactor 60 having an internal diameter of 41.9 centimeters. The fluidized bed was made of polymer granules. The gaseous feed streams of ethylene and hydrogen together with the liquid comonomer were mixed together in a mix-in -let arrangement and introduced under the reactor bed in the recycle gas line. Hexene-1 was used as the comonomer. The individual flow rates of ethylene, hydrogen and monomer were controlled to maintain fixed composition targets. The ethylene concentration was controlled to maintain a constant ethylene partial pressure. Hydrogen was controlled to maintain the molar ratio of hydrogen against constant ethylene. The concentration of all gases was measured in an on-line gas chromatograph to ensure the relatively constant composition in the recycle gas stream. The solid supported bulky ligand metallocene catalyst system listed in Table 6 was injected directly into the fluidized bed using purified nitrogen at 0.68 kilograms / hour. The reaction bed for the growing polymer particles was maintained in a fluidized state by the continuous flow of the feed made and the recycle gas through the reaction zone. A superficial gas velocity of 30.5 centimeters / second to 91.4 centimeters / second was used to achieve this. The reactor was operated at a total pressure of 2069 kPa, a reactor temperature of 85 ° C and a superficial gas velocity of 68.6 centimeters / second was used to achieve the fj-uidization of the granules. To maintain a constant reactor temperature, the temperature of the recycle gas was continuously adjusted up or down to accommodate any change in the heat generation rate due to polymerization. The fluidized bed was maintained at a constant height by removing a portion of the bed at a rate equal to the rate of formation of the particulate product. The product was removed semicontinuously with a series of valves to a fixed volume chamber, which was simultaneously ventilated back to the reactor. This allowed the very efficient removal of the product, and at the same time recycled a portion of the unreacted gases back to the reactor. This product was purged to remove the entrained hydrocarbons and treated with a small stream of dampened nitrogen to deactivate any trace amount of residual catalyst. Table 6 1 grams of polymer per grams of polymerization catalyst. By using carboxylate metal salts in combination with the polymerization catalysts, the operability of the reactor improves tremendously. Table 6 illustrates a gas phase reactor that operates without any problem to produce fractional melt index polymers for many bed changes (BTO). Specifically shown is using a polymerization catalyst without the carboxylate metal salt, as in Comparative Example 4 (without aluminum stearate), the reactor was quenched due to scale and lamination in less than 3 bed changes at a melt index of about 1.5 dg / minute and a density of 0.9188 g / cc . In one embodiment of the invention the process is operating for a period greater than 4 bed changes, more preferably greater than 5 bed changes and still more preferably greater than 6 bed changes. A bed change is when the total weight of the polymer discharged from the reactor is approximately equal to or equal to the weight of the bed in the reactor. It is known in the art that reducing the volume density of resin can improve operability in the polymerization process, particularly a gas phase fluidized bed polymerization process. Note from Table 6 that the bulk density of resin does not change much, however, the operability of the process of the invention surprisingly, improved substantially, when carboxylate metal salt was combined with the polymerization catalyst. Example 19 Preparation of a Conventional Type Transition Metal Catalyst A conventional type transition metal catalyst was prepared from a mixture of a generally magnesium compound, for example, MgCl 2, a titanium compound, for example, TiCl 3 -l / 3AlCl3, and an electron donor, for example, tetrahydrofuran (THF), and was supported on silica oxide that was dehydrated at 600 ° C. A detailed description of the preparation process can be found in U.S. Patent No. 4,710,538, which is incorporated herein by reference. The specific catalyst formulation had a molar ratio of TNHAL / THF of 29 and a DEAC / THF molar ratio of 26 where TNHAL is tri-n-hexyl aluminum and DEAC is diethyl aluminum chloride. Polymerization Process Using the Conventional Type Transition Metal Catalyst The free flowing, dry catalyst described above was injected into a continuous gas phase fluid bed reactor comprising a program reactor 60 of 45.7 centimeters, having a diameter inner of 41.9 centimeters, as previously described in this patent specification. The same process and conditions that were previously described were used. However, in this process, a conventional 5% by weight triethylaluminum TEAL co-catalyst solution in hexane was continuously added to the reactor to maintain the TEAL concentration in the fluid bed of approximately 300 ppm. Also, the conventional solid type transition metal catalyst prepared as directly described above was injected directly into the fluidized bed, see Table 7, Run A. A solution of the carboxylate metal salt, Witco Aluminum Stearate # 22 (AISt # 22) in hexane (2000 ppm) was prepared. During the polymerization process, see Table 7, Run A, the solution was pumped into the gas phase reactor, see the results in Table 7, Run B. The productivity of the catalyst per material balance remained virtually the same even after the addition of aluminum stearate. Furthermore, in this example, reactor operability remained stable and continued for more than 4 bed changes before the run ended voluntarily. Table 7 1 gram of polymer per gram of catalyst The above example illustrates that using the carboxylate metal salt together with a conventional type transition metal catalyst system the operability in a continuous gas phase polymerization process does not deteriorate, particularly when the salt of carboxylate metal is introduced separately from the conventional type catalyst system. However, in some runs of batch polymerization slurry it was found that using EA Witco dry grade aluminum stearate mixed with conventional type titanium metal catalyst resulted in a reduction in productivity. Without being bound by any particular theory, it is believed that the reduction in productivity may be partly due to the fact that the aluminum stearate reacts with the conventional type co-catalyst, for example, triethylaluminum, resulting in a less active co-catalyst in the reactor in lot. Examples 20 to 21 below illustrate the use of conventional dry type chromium metal catalyst mixed with a carboxylate metal salt. Example 20 Preparation of a Conventional Type Chromium Metal Catalyst A conventional type chromium metal catalyst, also known as a Phillips type catalyst, was prepared using Crosfield EP510 catalyst (1 weight percent titanium and 0.5 weight percent chromium - from chromium acetylacetonate) available from Crosfield Limited, Warrington, England. The EP 510 catalyst was activated at 800 ° C with 70 percent oxygen / 30 percent nitrogen in a fluidized bed column as is known in the art and used in the following polymerization process. Comparative Example 20A Ethylene Homopolymerization Process 100 μmol of triethylaluminum (25 weight percent of TEAL solution in heptane) was added to a 2.2 liter autoclave reactor as a scrubber to remove trace impurities in the vessel. Isobuthane polymerization grade 800 milliliters available from Phillips Petroleum, Bartlesville, Okla., Was added to the reactor. The content was stirred at 1000 rpm and the reactor temperature was raised from room temperature to 93 ° C and then ethylene was introduced into the reactor until the total reactor pressure was 2586 kPag. 300 milligrams of the activated chromium catalyst prepared above in Example 20 was charged to the reactor and the polymerization of ethylene continued for 60 minutes at this point the reaction was terminated by venting hydrocarbons from the reactor. In this Comparative Example 20A the chromium catalyst as described above was used clean (without aluminum stearate) and resulted in a highly charged static polymer. A solution of Hexane anti-static agent Kemamine AS-990 had to be used to remove the static-forming polymer from the walls of the reactor. The total resin collected was approximately 245 grams. Example 20B In this example, the polymerization catalyst includes 300 milligrams of activated chromium catalyst (prepared as described above in Example 20) mixed dry with 15 milligrams of aluminum stearate, Witco grade EA aluminum stearate, before the polymerization. The polymerization catalyst was charged to the reactor under the same polymerization conditions described above in Comparative Example 20A. After 60 minutes, the polymerization was stopped and the reactor was inspected. The resin produced was not static-forming and the polymer was easily removed from the reactor. The resin produced 133 grams. This run demonstrated that a carboxylate metal salt, an aluminum stearate compound, either prevented or neutralized the charges in the resin made with a conventional type chromium metal catalyst. It is a general belief that the phenomenon of reactor lamination in the polymerization of ethylene in gas phase using chromium catalyst is related to the static charge in the system. EXAMPLES 21 Copolymerization Processes 50 μmol of triethylaluminum was added to the reactor as a scrubber to remove trace impurities in a vessel. Thereafter, 50 milliliters of purified hexene-1 comonomer and 800 milliliters of isobutane were added to the reactor. After raising the reactor temperature to 85 ° C under agitation of 1000 rpm, the ethylene was introduced into the vessel until the pressure reached 2586 kPag). Then, 300 milligrams of a polymerization catalyst was charged to the reactor and the polymerization process continued for a period of time. The reaction was terminated by venting hydrocarbons from the reactor. The following examples were all performed using this polymerization process. However, in some examples the amount of hexene-1 and the reaction times were different. Comparative Example 21A 300 milligrams of an activated chromium catalyst, the polymerization catalyst, were charged to the reactor and the polymerization process as described above in Example 21 continued for about 60 minutes. In this Comparative Example 21A the chromium catalyst was used clean, without aluminum stearate, and resulted in scale. Heavy polymer coatings were observed on the reactor wall, agitator and internal thermocouple. Much of the polymer accumulated at the bottom of the reactor. The total amount of the sticky resin collected was 53 grams. Example 2IB In this example, 300 milligrams of the activated chromium catalyst prepared above in Example 20 was mixed dry with 15 milligrams of aluminum stearate, Witco Aluminum Stearate EA grade. The polymerization process used was as described above in Example 21. After 50 minutes the run was stopped by venting the hydrocarbons. It was found that the scale formation of the reactor was much lighter than in Comparative Example 21A. Only a light coating of polymer was visible on the stirrer, the thermocouple and the reactor wall. The total amount of resin collected was approximately 110 grams. Comparative Example 21C This Comparative Example 21C followed the same polymerization process described in Example 21 except 35 milliliters of hexene-1 was used. 300 milligrams of the activated chromium catalyst as described above in Example 21 was used clean, without any aluminum stearate. The polymerization was continued for 50 minutes, and the reactor was ventilated and inspected. Severe scale formation of the reactor was observed. A polymer ring approximately 7.62 centimeters wide was formed in the upper part of the reactor with a thickness varying from 0.64 to 1.91 centimeters. At the bottom of the reactor wall a polymer sheet was found. The total amount of resin collected was approximately 139 grams. The polymer accumulated too much to determine the density of the polymer. Example 2ID This Example 21D followed the same polymerization process described in Example 21 except that 35 milliliters of hexene-1 was used. 300 milligrams of the same activated chromium catalyst used in Comparative Example 21C was mixed dry with 15 milligrams of aluminum stearate, Witco Aluminum Stearate EA grade. The polymerization was continued for 50 minutes, and the reactor was ventilated and inspected. A minor polymer coating was found on the agitator, the thermocouple and the reactor wall. The polymer production was 139 grams and had a density of 0.9282 g / cc. In one embodiment, the invention is directed to a continuous process for polymerizing ethylene and at least one alphaolefin having from 3 to 20 carbon atoms in the presence of a polymerization catalyst comprising a conventional type chromium metal catalyst and a salt carboxylate metal to produce a polymer product having a density of less than 0.945 g / cc to about 0.910 g / cc, preferably less than Q_940 g / cc, more preferably less than 0.93 g / cc, even more preferably less of 0.928 g / cc, and more preferably less than 0.92 g / cc. In a preferred embodiment the continuous process is a gas phase process which operates at a pressure of 1379 kPag at approximately 2759 kPag and at a temperature above 60 ° C., preferably 70 ° C, up to about 120 ° C, preferably the gas phase process also operates in a condensed mode wherein a liquid and a gas are introduced to a fluidized bed reactor having a fluidizing medium and wherein the condensed level is greater than 8 weight percent, preferably greater than 10 weight percent and more preferably greater than 12 weight percent up to 50 weight percent based on the total weight of the fluidizing medium entering the reactor. For further details of the condensed mode process see U.S. Patent Nos. 5,342,749 and 5,436,304 both of which are hereby incorporated by reference in their entirety. Although the present invention has been described and illustrated with reference to particular embodiments, those of ordinary skill in the art will appreciate that the invention lends itself to variations not necessarily illustrated herein. For example, it is contemplated that the carboxylate metal salt may be added to the reactor in addition to contacting the catalyst system of the invention. It is also contemplated that the process of the invention can be used in serial reactor polymerization processes. For example, a carboxylate metal salt-free bulky ligand metallocene catalyst system is used in a reactor and a bridged, supported, bulky ligand metallocene-type catalyst system that has been contacted with a carboxylate metal salt it can be used in another or vice versa. It is further contemplated that the components of the metal carboxylate carboxylic acid salt and metal compound, for example, a hydroxy metal compound, may be added to the reactor or to the polymerization catalyst to form the reactor on site or with the catalyst . It is also contemplated that the metal salt of the carboxylate can be separately supported on a vehicle other than the polymerization catalyst, preferably a supported polymerization catalyst. For this reason, then, reference should be made only to the appended claims for purposes of determining the true scope of the present invention.

Claims (44)

1. CLAIMS 1. A catalyst composition comprising, in combination, a polymerization catalyst and a carboxylate metal salt, the metal carboxylate salt represented by the formula: MQx (OOCR) and wherein M is a metal of the Periodic Table of the Elements; Q is a halogen or a hydroxy, alkyl, alkoxy, siloxy, silane or sulfonate group; R is a hydrocarbyl radical having from 2 to 100 carbon atoms; x is an integer from 0 to 3; and is an integer from 1 to 4; and the sum of x and y is equal to the valence of the metal M.
2. 2. The catalyst composition of claim 1, wherein the polymerization catalyst comprises a conventional type transition metal catalyst compound.
3. 3. The catalyst composition of any of the preceding claims, wherein M is a metal selected from Groups 1 to 7 and Groups 13 to 16, Q is halogen or a hydroxy group, and R is a hydrocarbyl radical having from 4 to 24 carbon atoms.
4. 4. The catalyst composition of any of the preceding claims, wherein y is either 1 or 2, M is a Group 13 metal, Q is a hydroxy group, and R is a hydrocarbyl radical having more than 12 carbon atoms.
5. 5. The catalyst composition of any of the preceding claims, wherein the carboxylate metal salt has a melting point of 100 to 200"C.
6. The catalyst composition of any of the preceding claims, wherein the carboxylate metal salt is a stearate compound, preferably the stearate compound is selected from the group consisting of aluminum monostearate, aluminum di stearate and aluminum tri-stearate or a combination thereof
7. 7. The catalyst composition of any of the preceding claims, wherein the polymerization catalyst is a supported polymerization catalyst comprising a carrier, preferably an inorganic or organic carrier, more preferably an inorganic carrier, and most preferably an inorganic oxide
8. 8. The catalyst composition of any of the claims above, wherein the polymerization catalyst further comprises a carrier, an activator, preferably an inorganic oxide, and a conventional chromium metal catalyst compound.
9. 9. The catalyst composition of any of the preceding claims, wherein the k polymerization catalyst is represented by the formula: MRX wherein M is a metal of Groups IIIB to VIII, "preferably Group IVB, more preferably titanium or chromium R is a halogen or a hydrocarbyloxy group, and x is the valence of the metal M.
10. 10. The catalyst composition of any of the preceding claims, wherein the weight percent of the carboxylate metal salt based on the total weight of the polymerization is in the range of 0.1 to 500% by weight, preferably 1 to 50% by weight, and more preferably more than 1% by weight, especially more than 2% by weight, less than 25% by weight 11.
11. The catalyst composition according to any of the preceding claims, obtainable by a method comprising: (a) forming the polymerization catalyst, and (b) adding at least one carboxylate metal salt.
12. The catalyst composition of any of the preceding claims, obtainable by a method comprising contacting a dry and free-flowing polymerization catalyst with the carboxylate metal salt in a solid form.
13. 13. A method of making a catalyst composition according to any of the preceding claims 1-10, comprising mixing the polymerization catalyst and the carboxylate metal salt.
14. The method according to claim 13, wherein the mixing period is from 1 minute to 12 hours.
15. 15. The method of claim 13 or 14, wherein the mixing time period is 10 minutes to 10 hours, preferably 30 minutes to 8 hours.
16. 16. A catalyst composition comprising, in combination, a polymerization catalyst and a carboxylate metal salt, wherein the carboxylate metal salt is represented by the formula: MQx (00CR) and wherein M is a metal of the Periodic Table of the Elements; Q is halogen or a hydroxy, alkyl, alkoxy, aryloxy, siloxy, silane or sulfonate group; R is a hydrocarbyl radical having from 2 to 100 carbon atoms; x is an integer from 0 to 3; and is an integer from 1 to 4; and the sum of x and y is equal to the valence of the metal M; and has a melting point of 100-200 * C.
17. 17. A continuous polymerization process, comprising supplying to a reactor the catalyst composition according to any of the preceding claims and olefin monomer (s) to produce a polymer product.
18. 18. A continuous process for polymerizing olefin (s) is a reactor in the presence of a catalyst composition according to any of claims 1-12, which comprises contacting the polymerization catalyst prior to its introduction to the reactor with the salt carboxylate metal.
19. 19. A gaseous phase or slurry process for polymerizing olefin (s) continuously in a reactor in the presence of a catalyst composition according to claim 18, the catalyst composition comprising at least one polymerization catalyst and at least one salt carboxylate metal.
20. 20. A continuous process for polymerizing olefin monomer (s) in a reactor, under polymerization conditions, the process comprising the steps of: (a) introducing olefin monomer (s) into the reactor; (b) (i) introducing a catalyst composition of a polymerization catalyst and a carboxylate metal salt represented by the formula: MQx (OOCR) and wherein M is a metal of the Periodic Table of the Elements; Q is halogen or a hydroxy, alkyl, alkoxy, aryloxy, siloxy, silane or sulfonate group; R is a hydrocarbyl radical having from 2 to 100 carbon atoms; x is an integer from 0 to 3; and is an integer from 1 to 4; and the sum of x and y is equal to the valence of the metal M; and (b) removing a polymer product from the reactor.
21. 21. The process of claim 20, wherein the process is a slurry process.
22. 22. The process of claim 20, wherein the process is a gas phase process.
23. 23. A continuous gas phase process for polymerizing monomer (s) in a reactor, said process comprising the steps of: (a) introducing a recycle stream into the reactor, the recycle stream comprising one or more monomer (s); (b) contacting a polymerization catalyst with a carboxylate metal salt to form a catalyst composition, wherein the carboxylate metal salt is represented by the formula: MQx (OOCR) and where M is a metal of the Periodic Table of the Elements; Q is halogen or a hydroxy, alkyl, alkoxy, aryloxy siloxy, silane or sulfonate group; R is a hydrocarbyl radical having from 2 to 100 carbon atoms; x is an integer from 0 to 3; and is an integer from 1 to 4; and the sum of x and y is equal to the valence of the metal M; and has a melting point of 100 to 200 * C; (c) introducing the catalyst composition to the reactor; (d) removing the recycle stream by introducing a reactor polymerization catalyst; (e) cooling the recycle stream; (f) re-entering the recycle stream to the reactor; (g) introducing additional monomer (s) to the reactor to replace the polymerized monomer (s); and (h) removing a polymer product from the reactor.
24. 24. A continuous gas phase polymerization process, to polymerize ethylene and one or more alpha-olefins having 4 or more carbon atoms at a pressure in the range of about 200 psi (1,379 kPa) to about 400 psi (gauge) (2,759 kPa), a polymerization temperature in the range of about 70 to about 110"C, at a rate or rate of production greater than 10,000 pounds (4,540 kg) of a polymer product per hour, and at a polymerization catalyst productivity of more than 1,500 g of the polymer product per gram of the polymerization catalyst, the process operating in the presence of a carboxylate metal salt represented by the formula: MQx (OOCR) and wherein M is a metal of The periodic table; Q is halogen or a hydroxy, alkyl, alkoxy, siloxy, silane or sulfonate group; R is a hydrocarbyl radical having from 2 to 100 carbon atoms; x is an integer from 0 to 3; and is an integer from 1 to 4; and the sum of x and y is equal to the valence of the metal M; preferably M is a metal selected from Groups 1 to 7 and Groups 13 to 16, Q is halogen or a hydroxy group, and R is a hydrocarbyl radical having from 4 to 24 carbon atoms; and, more preferably, y is either 1 or 2, M is a Group 2 or 13 metal, Q is a hydroxy group, and R is a hydrocarbyl radical having more than 12 carbon atoms.
25. The process of any of claims 20 to 24, wherein the carboxylate metal salt has a melting point of 100 to 200 * C.
26. 26. The process of any of claims 20 to 25, wherein the carboxylate metal salt is a stearate compound, preferably the stearate compound is selected from the group consisting of aluminum mono-stearate, aluminum di-stearate and aluminum tri-stearate, or a combination thereof.
27. The process of any of claims 20 to 26, wherein the polymerization catalyst comprises a conventional type transition metal catalyst compound.
28. The process of any of claims 20 to 27, wherein the polymerization catalyst comprises a carrier, preferably an inorganic carrier, and a conventional type transition metal compound, preferably a conventional type chromium metal compound.
29. 29. The process of any of claims 20 to 28, wherein the polymerization catalyst is represented by the formula: MRX wherein M is a metal of Groups IIIB to VIII, preferably Group IVB, more preferably titanium or chromium; R is a halogen or a hydrocarbyloxy group; and x is the valence of the metal M.
30. 30. The process of any of claims 20 to 29, wherein the weight percent of the carboxylate metal salt based on the total weight of the polymerization catalyst is in the range of 0.1 to 500. % by weight, preferably 1 to 50% by weight, and more preferably more than 1% by weight, especially more than 2% by weight, less than 25% by weight.
31. The process of any of claims 20-28, wherein the process is producing a polymer product having a density greater than 0.910 to 0.945 g / cc.
32. 32. The process of any of claims 20 to 30, wherein the polymer product has a density greater than 0.920 g / cc and an I21 / I2 ratio greater than 30, preferably where the polymer product has a density greater than 0.925. g / cc and a melt index of less than 1 '/ min.
33. 33. The process of any of claims 20 to 32, wherein the carboxylate metal salt is introduced to the process continuously or intermittently.
34. 34. The process of claim 23, wherein the rate or speed of production is greater than 25,000 pounds (11,340 kg) of the polymer product per hour.
35. 35. The process of any of claims 20 to 34, wherein the carboxylate metal salt is contacted with the polymerization catalyst prior to its introduction into the reactor.
36. 36. A polymerization process for producing a first polymer product based on ethylene, having a density greater than 0.87 g / cc and a melt index greater than 1 '/ piin in the presence of a first catalyst composition comprising a first catalyst of polymerization, the HO process-comprising the step of: transitioning to a second catalyst to produce a second ethylene-based polymer product having a density greater than 0.920 g / cc and a melting index less than or equal to 1"/ min, the second catalyst composition comprising a second polymerization catalyst and a carboxylate metal salt
37. 37. A process for polymerizing an olefin olefin, at least one of which is ethylene, in the presence of a first catalyst composition to produce a first polymer product, the process comprising the steps of: "(a) introducing the first catalyst composition comprising a first polymerization catalyst and a carboxylate metal salt to a reactor, where the first catalyst composition is used at the start of the process, after the process has been stabilized; (b) discontinuing the introduction of the first catalyst composition; and (c) introducing a second polymerization catalyst substantially free of carboxylate metal salt to the reactor to produce a second polymer product.
38. 38. The process of any of claims 36 to 37, wherein the second polymerization catalyst is the same as the first polymerization catalyst.
39. 39. The process of any of claims 36 to 38, wherein the first and second polymer products have the same density or a similar density.
40. 40. The process of any of claims 36 to 38, wherein the first polymer product has a density greater than 0.910 g / cc and a melt index greater than 1.5 ° / m-in, and the second polymer product has a density greater than 0.920 g / cc and a melt index lower than 0.75 ° / min.
41. 41. The process of any of claims 36 to 40, wherein the first polymerization catalyst is selected from the group consisting of a conventional type transition metal catalyst, a conventional type chromium metal catalyst, and a metallocene type catalyst of bulky ligand, and the second polymerization catalyst is preferably a bulky ligand metallocene-like catalyst compound, more preferably a bulky, bridged ligand metallocene-like catalyst compound, and a carrier.
42. 42. The use of a solid carboxylate metal salt in conjunction with a polymerization catalyst, preferably a supported polymerization catalyst, to reduce fouling and / or scale formation in a gas phase polymerization process or a polymerization process in the slurry phase, preferably a continuous gas phase polymerization process.
43. 43. A gas phase continuous process for polymerizing ethylene and at least one alpha-olefin having from 3 to 20 carbon atoms in the presence of a polymerization catalyst comprising a conventional type chromium metal catalyst and a carboxylate metal salt, to produce a polymer product having a density of less than 0.945 g / cc to 0.910 g / cc, preferably less than 0.940 g / cc, more preferably less than 0.93 g / cc, even more preferably less than 0.928 g / cc. cc, and most preferably less than 0.92 g / cc.
44. 44. The process of claim 43, wherein the process is operating at a gauge pressure of 200 to 400 psi (1,379 to 2,759 kPa) and at a temperature above 60 * C, preferably 70 * C, at 120 ° C, preferably the gas phase process is also operating in a condensed mode where a liquid and a gas are introduced to a fluidized bed reactor having a fluidization medium and where the level of condensate is greater than 8% by weight, preferably higher of 10% by weight, and most preferably greater than 12% by weight up to 50% by weight based on the total weight of the fluidization medium entering the reactor.