MXPA97006874A - Component of supported catalyst, supported catalyst, preparation process, depolimerization process, complex compounds, and supreparac - Google Patents

Abstract

The present invention relates to a supported catalyst component consisting essentially of: (a) (1) a support material, and (a) (2) an organometallic or metalloid compound, wherein the metal or metalloid is selected from the group consisting of magnesium, zinc, boron, aluminum, germanium, tin, lead and mixtures thereof, and (b) an activating compound comprising: (b) (1) a cation which is capable of reacting with a metallocene compound transition metal to form a transition metal complex which is catalytically active for the polymerization of alpha-olefins, and (b) (2) a compatible anion having up to 100 non-hydrogen atoms and containing, therefore, less, a substituent comprising a fraction having an active hydrogen

Description

SUPPORTED CATALYST COMPONENT. CATALYST SUPPORTED, PROCESS OF PREPARATION, PROCESS OF POLYMERIZATION, COMPLEX COMPOUNDS, AND YOUR PREPARATION The present invention relates to a supported catalyst component comprising a support material, an organometallic compound, and an activating compound, to a supported catalyst comprising this supported catalyst component and a transition metal compound, to a process for preparing this supported catalyst component and catalyst, to a polymerization process employing this supported catalyst, to complex compounds to be used as activator compounds, and to a process for making these complex compounds.

Background of the Invention Homologous or unsupported ionic transition metal catalysts are known for their high catalytic activity in olefin polymerizations. Under polymerization conditions where the polymer is formed as solid particles, these homogeneous (soluble) catalysts form polymer deposits on the walls of the reactor and the agitators, whose deposits must be removed frequently, since they prevent an efficient heat exchange necessary to cool the contents of the reactor, and cause excessive wear of the moving parts of the reactor. The polymers produced by these soluble catalysts also have a low bulk density that limits the commercial utility of both the polymer and the process. In order to solve these problems, several supported ionic catalysts have been proposed for use in particle forming polymerization processes. WO-91/09882 describes a supported ionic metallocene catalyst prepared by the combination of: i) a bis (cyclopentadienyl) metal compound containing at least one ligand capable of reacting with a proton, ii) an activating component comprising a cation capable of donating a proton and a bulky labile anion capable of stabilizing the metal cation formed as a result of the reaction between the metal compound and the activating component; and iii) a catalyst support material. The support material can be subjected to a thermal treatment or chemical dehydration. In some of the examples, triethyl aluminum was added for this purpose. The maximum bulk density reported in the examples of WO91 / 09882 is 0.17 grams / cm 3, and the efficiency of the catalyst is not satisfactory. WO-94/03506 describes a supported ionic catalyst prepared by the combination of: i) a monocyclopentadienyl metal compound, ii) an activating component comprising a cation which will irreversibly react with at least one ligand contained in the metal compound, and an anion, this anion being a chemically stable non-nucleophilic anionic complex, and iii) a catalyst support material, optionally followed by prepolymerization of the supported catalyst system with an olefinic monomer. The support material can be treated with a hydrolyzable organic additive, preferably an alkyl compound of Group 13, such as triethyl aluminum. The catalyst efficiencies obtained in O-94/03506, however, are very low. O-94/03509 suggests the use of supported ionic catalysts such as described in WO-94/03506 for use in a gas phase polymerization process. O-93/21238 discloses tris (pentafluorophenyl) borane complexes of water, alcohols, mercaptans, silanols, oximes, and mixtures thereof. These neutral complexes can be converted into acid salts of their conjugated bases by their reaction with amines. These complexes and the acid salts thereof, together with the Group 4 transition metal compounds, especially metallocenes, were described as being useful as homogeneous olefin polymerization catalysts. O-93/11172 relates to poly-ionic transition metal catalyst compositions. It is suggested that polyanionic activators be used to prepare a catalyst system for improved performance by immobilizing the catalyst on a support material. Nevertheless, it is believed that the teachings of WO-93/11172 are not sufficient for the preparation of a supported catalyst based on support materials containing surface hydroxyl groups. Figure 1, Formula 3, and page 26, line 25, suggest the use of so-called synthon functionalized with alcohols in the manufacture of polyanionic activators. Various methods are suggested for making catalyst supports based on polyanionic activators made from syntheses functionalized with alcohols, as described below. In a first method (page 26, lines 32-36, and Figure 1, Formula 6) the synthon functionalized with alcohol is converted to silylhalide analogs by its treatment with R'jSiCl4_j (j = 0 to 3). As indicated therein, HCl is released, which must be absorbed by a tertiary amine. However, this will give the byproduct of R3NH.Cl. The ammonium chloride thus formed is not a suitable activator compound for a transition metal catalyst, because the chloride anion is not a non-anion. coordinator, which is typically required for this type of catalyst, and the catalyst thus made will not have a substantial catalytic activity. The compound of Formula 6 can be reacted with a hydroxylated substrate such as silica gel, alumina, or metal oxide (page 34, lines 25-28, and Figure 1, route C). When the compound of Formula 6 is used, equivalents of HCl can be released, which compound and ammonium chloride as a possibly suggested byproduct will provide catalyst systems having only negligible catalytic activities. On page 32, lines 11-18, other methods are suggested for making catalyst supports from alcohol-functionalized synthons: acid-catalyzed dehydration of hydroxylated surfaces (such as amorphous silica), and esterification or transesterification of discrete materials or polymeric containing more than one carboxylic acid or ester per molecule, polymer chain, or particle. All these reactions release water, which is a poison for transition metal catalysts. An additional method is described on page 34, line 34, page 35, line 37, and page 37, line 16 through page 38, line 14, as well as in Figure 8. In accordance with this method, a material is provided of support with anionic functionalities by the reaction of a coupling agent of silane halide or silane alkoxide with a hydroxylated surface of silica. On page 35, lines 33-37, it is suggested to mask or protect reactive functionalities, such as hydroxyl functions (on silica). On page 37, lines 20-31, this is further explained, and it is indicated that part of the hydroxyl functions can be masked, and the remaining part can be converted into anionic functionalities. This would make it possible to vary or adjust the concentration of the (finally) anionic functionalities. In this context, a mixture of trimethoxy-bromophenylsilane and trimethoxy-phenylsilane is mentioned. In accordance with the foregoing, the hydroxyl functionalities that are masked or protected are not used for the preparation of the anionic functionalities. In addition, the use of silane halides or silane alkoxides to react with surface hydroxyl groups, would give as a byproduct hydrogen halides and alcohols, which are catalyst poisons. In accordance with the foregoing, it is believed that none of the preferred methods gives effective supported catalysts. It would be desirable to provide a supported catalyst and a supported catalyst component thereof, and a polymerization process that is capable of producing polymers in good catalyst efficiencies, thereby eliminating or reducing some of the drawbacks presented in the prior art.

SUMMARY OF THE INVENTION In one aspect of the present invention, a supported catalyst component is provided comprising: (a) a support material, an organometallic compound wherein the metal is selected from Groups 2-13 of the Table Periodic Elements, germanium, tin, and lead, and (b) an activating compound comprising: bl) a cation that is capable of reacting with a transition metal compound to form a catalytically active transition metal complex, and b.2) a compatible anion having up to 100 non-hydrogen atoms, and containing at least one substituent comprising an active hydrogen moiety. In a second aspect, a supported catalyst comprising the supported catalyst component of the invention is provided, and (c) a transition metal compound containing a substituent capable of reacting with the activating compound (b) to thereby form a catalytically active transition metal complex. In a further aspect, the present invention provides a process for the preparation of a supported catalyst component, which comprises combining a support material (a), an organometallic compound wherein the metal is selected from the groups 2-13. of the Periodic Table of the Elements, germanium, tin, lead, and an activating compound (b) comprising: bl) a cation that is capable of reacting with a transition metal compound to form a catalytically active transition metal complex , and b.2) a compatible anion having up to 100 non-hydrogen atoms, and containing at least one substituent comprising an active hydrogen moiety. In another aspect of the invention, there is provided a process for the preparation of a supported catalyst, which comprises the process for making the supported catalyst component of the present invention, and the additional step of adding a transition metal compound (c). ) containing a substituent capable of reacting with the activating compound (b) to thereby form a catalytically active transition metal complex. In yet a further aspect of the present invention, an adduct of an organometallic compound is provided, wherein the metal is selected from Groups 2-13 of the Periodic Table of the Elements, germanium, tin, and lead, and a activating compound comprising: bl) a cation that is capable of reacting with a transition metal compound to form a catalytically active transition metal complex, and b.2) a compatible anion having up to 100 non-hydrogen atoms , and containing at least one substituent comprising an active hydrogen fraction, obtained by combining the organometallic compound and the activating compound in a suitable diluent or solvent, optionally followed by the removal of the solvent or diluent. In still another aspect, the invention provides an addition polymerization process, wherein one or more polymerizable addition monomers are contacted with a catalyst supported in accordance with the present invention, under addition polymerization conditions. In yet a further aspect, a complex compound comprising a charge equilibrium cation, and a compatible anion corresponding to Formula (I) is provided: [M'm + Qn (Gq (T-Pr) r) z] d- (I) wherein: M 'is a metal or metalloid selected from Groups 5-15 of the Periodic Table of the Elements; Q, independently in each presentation, is selected from the group consisting of hydride, dihydrocarbylamido, halide, hydrocarbyl oxide, hydrocarbyl, and substituted hydrocarbyl radicals, including hydrocarbyl radicals substituted by halogen, and organic metalloid radicals substituted by hydrocarbyl and halogenated hydrocarbyl, the hydrocarbyl portion having 1 to 20 carbon atoms, with the proviso that in no more than one Q presentation is halide; G is a polyvalent hydrocarbon radical having the valences r + 1, linked with M 'and T; T is O, S, NR, or PR, wherein R is a hydrocarbon radical, a trihydrocarbylsilyl radical, a trihydrocarbyl methyl radical, or hydrogen; Pr is hydrogen H or a protecting group; m is an integer from 1 to 7; n is an integer from 0 to 7; q is 1; r is an integer from 1 to 3; z is an integer from 1 to 8; d is an integer from 1 to 7; and n + z-m = d.

In accordance with a further aspect, the present invention provides a method for the preparation of a complex compound containing an anion corresponding to Formula (I): [M, m + Qn (Gq (T-Pr) r) z] d- (I) wherein: M 'is a metal or metalloid selected from Groups 5-15 of the Periodic Table of the Elements; Q, independently in each presentation, is selected from the group consisting of hydride, dihydrocarbylamido, halide, hydrocarbyl oxide, hydrocarbyl, and substituted hydrocarbyl radicals, including hydrocarbyl radicals substituted by halogen, and organic metalloid radicals substituted by hydrocarbyl and by halogenated hydrocarbyl, the hydrocarbyl portion having from 1 to 20 carbon atoms, with the proviso that in no more than one presentation Q is ha, luro; G is a polyvalent hydrocarbon radical having the valences r + 1, linked with M 'and T; T is O, S, NR, or PR, wherein R is a hydrocarbyl radical, a trihydrocarbylsilyl radical, a trihydrocarbyl methyl radical, or hydrogen; Pr is hydrogen H or a protecting group; m is an integer from 1 to 7, n is an integer from 0 to 7, q is an integer of 0 or 1; r is an integer from 1 to 3 z is an integer from 1 to 8, d is an integer from 1 to 7, n + z-m = d; and a load balancing cation; in which complex the anion and the cation are contained in relative amounts such that they provide a neutral compound. Which comprises the steps of combining in a suitable solvent or diluent, a compound M, + Qm with a compound of the formula Z ^ GqTT-Pr) ..), where Z1 is [M * x **] * or [ M **] *, and M * is an element of group 2, M ** is an element of group 1, and X is halogen, G, T, Pr, q, and r have the same meaning as was given for the Formula (I), optionally followed by the recovery of the product complex.

Detailed Description of the Invention All references herein to elements or metals belonging to a certain Group, refer to the Periodic Table of the Elements published and copyrighted by CRC Press, Inc., 1989. Also, any reference to the Group or Groups will be to the Group or Groups that are reflected in this Periodic Table of the Elements, using the IUPAC system for group numbering. Surprisingly, it has been discovered that a complex compound containing at least one substituent comprising an active hydrogen fraction as specified herein can be attached to the support and is capable of activating the transition metal catalysts typically employed. in the addition polymerization processes. This is surprising, since it is known that active hydrogen-containing compounds tend to deactivate typical transition metal catalysts, especially transition metal catalysts containing a cyclopentadienyl fraction or a derivative thereof. The present supported catalysts can be used to produce polymers at satisfactory catalyst efficiencies. An additional benefit is that the formation of polymer deposits in the walls of the reactor and in other moving parts of the reactor is eliminated; and the polymers are in the form of free flowing powder or particles, when a particle forming polymerization process, such as a paste or gas phase polymerization process, is employed, such that the polymers can be transported easily, and that polymers of improved bulk density are obtained in these particulate polymerization processes. In accordance with the present invention, the improved bulk densities, for the ethylene-based polymers and interpolymers, are preferably bulk densities of at least about 0.20 grams / cm 3, and more preferably of at least about 0.25 grams / cm 3. In the supported catalyst components and in the catalysts, the activating complexes are dispersed well throughout the porous structure of the porous support material, which is one of the important factors to maintain both an extended period and a high level of catalyst efficiency. During the formation of the polymer on the supported catalyst particles, the particles tend to fragment and consequently to be made available to the fresh surface for the growth of the polymer. The presence of the catalytically active groups on this fresh surface is very desirable to provide good catalyst efficiencies and polymer morphology. Suitable support materials for use in the present invention include porous resinous materials, for example, polyolefins, such as polyethylene and polypropylenes, or styrene-divinylbenzene copolymers, and solid inorganic oxides, including metal oxides of Groups 2, 4, 13, or 14, such as silica, alumina, magnesium oxide, titanium oxide, thorium oxide, as well as mixed silica oxides. Suitable mixed silica oxides include those of silica and one or more metal oxides of Group 2 or 13, such as mixed silica-magnesia or silica-alumina oxides. Preferred support materials are silica, alumina, and mixed oxides of silica and one or more metal oxides of Group 2 or 13. Preferred examples of these mixed oxides are silica-aluminas. The most preferred support material is silica. The shape of the silica particles is not critical, and the silica may be in granular, spherical, agglomerated, vaporized, or other form. Suitable silicas include those that are available from Grace Davison (W.R. Grace &; Co.) under the designations SD 3216.30, SP-9-10046, Davison Syloid 245, Davison 948, and Davison 952, in Degussa AG under the designation Aerosil 812, and in Crossfield under the designation ES 70X. The support materials suitable for the present invention preferably have a surface area determined by the nitrogen porosimetry, using the method B.E.T. from 10 to about 1000 m2 / gram, and preferably from about 100 to 600 m2 / gram. The pore volume of the support, determined by nitrogen adsorption, is typically up to 5 cm3 / gram, conveniently between 0.1 and 3 cm3 / gram, preferably from about 0.2 to 2 cm3 / gram. The average particle size is not critical, but is typically 0.5 to 500 microns, preferably 1 to 200 microns, more preferably up to 100 microns. The support material can be subjected to a heat treatment and / or chemical treatment to reduce the water content or the hydroxyl content of the support material. Both dehydrated support materials and support materials containing small amounts of water can be used. Typical typical heat treatments are carried out at a temperature of 30 ° C to 1000 ° C for a duration of 10 minutes to 50 hours in an inert atmosphere or under reduced pressure. Typical carrier materials have a surface hydroxyl content of 0.1 micromoles, preferably 5 micromoles, more preferably 0.05 millimoles to no more than 5 millimoles of hydroxyl groups per gram of solid support, more preferably 0.5 to 2 millimoles per gram . The hydroxyl content can be determined by known techniques, such as infrared spectroscopy and titration techniques using metal alkyl or metal hydroxide, for example, by adding an excess of dialkyl magnesium to a paste of the solid support, and determining the amount of magnesium remaining dialkyl in the solution by known techniques. This last method is based on the reaction of S-OH + MgR2? S-OMgR + RH, where S is the solid support. The support material is treated with the organometallic compound. Suitable organometallic compounds are those comprising metals of Groups 2-13, germanium, tin, and lead, and at least two substituents selected from hydride, hydrocarbyl radicals, trihydrocarbyl radicals, and trihydrocarbylmyl radicals. Additional substituents preferably comprise one or more substituents selected from hydride, hydrocarbyl radicals, silyl radicals substituted by trihydrocarbyl, germyl radicals substituted by trihydrocarbyl, and hydrocarbyl substituted metalloid radicals, by trihydrocarbylsilyl, or by trihydrocarbyl bilyl. The term "metalloid", as used herein, includes non-metals, such as boron, phosphorus, and the like, which exhibit semi-metallic characteristics. Examples of these organometallic compounds include organic magnesium, organic zinc, organic boron, organic aluminum, organic germanium, organic tin, and organic lead compounds, and mixtures thereof. Other organometallic compounds are alumoxanes. Preferred examples are alumoxanes and compounds represented by the following formulas: MgR12, ZnR12, BR1XR2, A1R1XR2, wherein R1, independently in each presentation, is hydride, a hydrocarbyl radical, a trihydrocarbylsilyl radical, a trihydrocarbyl methyl radical, or a radical metalloid substituted by trihydrocarbyl, by trihydrocarbylsilyl, or by trihydrocarbyl- bilyl, R2, independently, is equal to R1, x is 2 or 3, is O or 1, and the sum of x and y is 3, and mixtures thereof. Examples of suitable hydrocarbyl fractions are those having from 1 to 20 carbon atoms in the hydrocarbyl portion thereof, such as alkyl, aryl, alkaryl, or aralkyl. Preferred radicals include methyl, ethyl, normal propyl or isopropyl, normal, secondary, or tertiary butyl, phenyl, and benzyl. Preferably, the aluminum component is selected from the group consisting of alumoxane and aluminum compounds of the formula A1R1X wherein R1 in each presentation is independently hydride or a hydrocarbyl radical having from 1 to 20 carbon atoms, and is 3. Suitable trihydrocarbyl aluminum compounds are trialkyl or triaryl aluminum compounds, wherein each alkyl or aryl group has from 1 to 10 carbon atoms, or mixtures thereof, and preferably trialkyl aluminum compounds such as trimethyl aluminum. , triethyl, triisobutyl. Alumoxanes (also referred to as aluminoxanes) are oligomeric or polymeric aluminum oxycomposites containing chains of alternating aluminum and oxygen atoms, whereby aluminum carries a substituent, preferably an alkyl group. It is believed that the structure of alumoxane is represented by the following general formulas (-Al (R) -0) m, for a cyclic alumoxane, and R2Al-0 (-Al (R) -0) m-AlR2, for a compound linear, wherein R, independently in each presentation, is a hydrocarbyl of 1 to 10 carbon atoms, preferably alkyl, or halide, and m is an integer of 1 to about 50, preferably of at least about 4. The alumoxanes are typically the reaction products of water and an aluminum alkyl, which in addition to an alkyl group, may contain halide or alkoxide groups. The reaction of several different aluminum alkyl compounds, such as, for example, trimethyl aluminum and triisobutyl aluminum, with water, produces the so-called modified or mixed alumoxanes. Preferred alumoxanes are methyl alumoxane and modified methyl alumoxane with minor amounts of other lower alkyl groups, such as isobutyl. The alumoxanes generally contain minor to substantial amounts of the starting aluminum alkyl compound. The way in which alumoxane is prepared is not critical. When prepared by the reaction between water and aluminum alkyl, the water can be combined with the aluminum alkyl in different forms, such as in liquid, vapor, or solid, for example, in the form of water of crystallization. Particular techniques for the preparation of alumoxane type compounds by contacting an aluminum alkyl compound with an inorganic salt containing water of crystallization are described in U.S. Patent No. 4,542,199. In a particular preferred embodiment, an aluminum alkyl compound is contacted with a substance containing regenerable water, such as hydrated alumina, silica, or other substance. This is described in European Patent Application Number 338,044. The supported catalyst component and the supported catalyst of the present invention generally comprise a support material combined or treated with the organometallic compound, preferably an aluminum component, and containing at least 0.1 micromoles of the organometallic compound per gram of support, typically at least 5 micromoles per gram of support material, conveniently at least 0.5 percent by weight of the metal, preferably aluminum, expressed in grams of metal, preferably aluminum, atoms per gram of support material. Preferably, the amount of metal, conveniently aluminum, is at least 2 percent by weight, and is generally not more than 40 percent by weight and more preferably not more than 30 percent by weight. In too high amounts of metal, preferably aluminum, the supported catalyst becomes expensive. In too low amounts, the efficiency of the catalyst falls to reach below acceptable levels. The supported catalyst component and the supported catalyst of the present invention, preferably containing a treated support material (a) comprising a support material and an alumoxane wherein no more than about 10 percent of aluminum present in the treated support material can be extracted in a 1 hour extraction with toluene at 90 ° C using approximately 10 milliliters of toluene per gram of previously treated support material. More preferably, no more than about 9 percent of aluminum present in the supported catalyst component can be extracted, and more preferably no more than about 8 percent.

This is especially convenient when the supported catalyst component or the catalyst prepared therefrom is used in a polymerization process where a diluent or solvent that can extract non-fixed alumoxane from the support material is employed. It has been found that when the amount of extractables is below the levels given above, the amount of alumoxane that can diffuse into the polymerization solvent or diluent, if used, is so low that an appreciable amount of polymer will not form in the polymer. the diluent, comparing with the polymer formed on the support material. If too much polymer is formed in the diluent, the bulk density of the polymer will fall below acceptable levels, and reactor contamination problems may occur. The extraction test with toluene is carried out as follows: about 1 gram of supported catalyst component or supported catalyst, with a known aluminum content, is added to 10 milliliters of toluene, and then the mixture is heated to 90 ° C under an inert atmosphere. The suspension is stirred well at this temperature for 1 hour. The suspension is then filtered by applying reduced pressure to assist in the filtration step. The solids are washed twice with about 3 to 5 milliliters of toluene at 90 ° C per gram of solids. The solids are then dried at 120 ° C for 1 hour, and subsequently the aluminum content of the solids is measured. The difference between the initial aluminum content and the aluminum content after the extraction divided by the initial aluminum content and multiplied by 100 percent gives the amount of extractable aluminum. The aluminum content can be determined by forming a paste of approximately 0.5 grams of supported catalyst component or catalyst supported in 10 milliliters of hexane. The paste is treated with 10 to 15 milliliters of 6N sulfuric acid, followed by the addition of a known excess of EDTA. The excessive amount of EDTA is then titrated back with zinc chloride. Without wishing to be bound by any theory, it is believed that the activating compound used in the present invention reacts with the organometallic compound, preferably the aluminum component, through the active hydrogen-containing substituent. It is believed that a R1 group of the organometallic compound, preferably the aluminum component, is combined with the active hydrogen fraction with the activating compound to liberate a neutral organic compound, for example, an alkane, or hydrogen gas, coupling therefrom. chemically the metal, preferably the aluminum atom, with the residue of the activating compound. Accordingly, it is believed that the activator becomes chemically bound to the support material once the support material has been treated with the organometallic compound or adduct of the organometallic compound and the activating compound. After the addition of the transition metal compound, a supported catalyst is formed which has improved properties. The activating compound useful in the present invention contains a compatible anion having up to 100, and preferably up to 50, non-hydrogen atoms, and having at least one substituent comprising an active hydrogen moiety. Preferred substituents comprising an active hydrogen fraction correspond to the formula: Gq (T-H) r wherein G is a polyvalent hydrocarbon radical, T is 0, S, NR, or PR, wherein R is a hydrocarbyl radical, a trihydrocarbylsilyl radical, a trihydrocarbyl methyl radical, or hydrogen, H is hydrogen, q is 0 or 1, and preferably 1, and r is an integer from 1 to 3, the polyvalent hydrocarbon radical G has r + 1 valencies, a valence being with a metal or metalloid of Groups 5-15 of the Periodic Table of the Elements in the compatible anion, the other valence or valencies of G being linked to TH groups. Preferred examples of G include bivalent hydrocarbon radicals such as: alkylene radicals, arylene, aralkylene, or alkarylene containing from 1 to 20 carbon atoms, more preferably from 2 to 12 carbon atoms. Suitable examples of G include phenylene, biphenylene, naphthylene, methylene, ethylene, 1,3-propylene, 1,4-butylene, phenylmethylene (-C6H4-CH2-). The polyvalent hydrocarbyl portion G can be further substituted by radicals that do not interfere with the coupling function of the active hydrogen fraction. Preferred examples of these substituents which do not interfere are alkyl, aryl, silyl and germyl radicals substituted by alkyl or aryl, and fluoro substituents. The TH group in the above formula, can thus be a group -OH, -SH, -NRH, or -PRH, wherein R is preferably a hydrocarbyl radical of 1 to 18 carbon atoms, preferably 1 to 10 carbon atoms, or hydrogen, and H is hydrogen. Preferred R groups are alkyls, cycloalkyls, aryls, arylalkys, or alkylaryls of 1 to 18 carbon atoms, more preferably those of 1 to 12 carbon atoms. The -OH, -SH, -NRH, or -PRH groups can be part of a larger functionality such as, for example, C (0) -OH, C (S) -SH, C (0) -NRH, and C (0) -PRH. More preferably, the TH group is a hydroxy group, -OH, or an amino group, -NRH.

Highly preferred G "(TH) r substituents comprising an active hydrogen moiety include aryl, aralkyl, alkaryl, or alkyl groups substituted by hydroxy and amino, and hydroxyphenyls, especially 3- and 4-hydroxyphenyl groups, are more preferred. , hydroxytolyl, hydroxybenzyl (hydroxymethylphenyl), hydroxybiphenyls, hydroxynaphthyl, hydroxycyclohexyl, hydroxymethyl, and hydroxypropyl, and the corresponding amino-substituted groups, especially those substituted by -NRH, wherein R is an alkyl or aryl radical having from 1 to 10. carbon atoms, such as, for example, methyl, ethyl, propyl, isopropyl, normal butyl, isobutyl, or tertiary butyl, pentyl, hexyl, heptyl, octyl, nonyl, and decyl, phenyl, benzyl, tolyl, xylyl, naphthyl, and biphenyl. The compatible anion containing the substituent containing an active hydrogen fraction may further comprise a single Group 5-15 element or a plurality of elements from group 5-15, but preferably it is a single coordination complex which comprises a core of metal or metalloid that arrives load, whose anion is voluminous. A compatible anion refers specifically to an anion which, when functioning as a charge-balancing anion in the catalyst system of the present invention, does not transfer an anionic substituent or fragment thereof to the transition metal cation, thereby forming a neutral transition metal compound and a neutral metal byproduct. "Compatible anions" are anions that do not degrade to neutrality when the initially formed complex decomposes, and do not interfere with the desired subsequent polymerizations. Preferred anions are those which contain a single coordination complex comprising a metal or metalloid core bearing charge carrying a substituent containing an active hydrogen fraction, whose anion is relatively large (bulky), capable of stabilizing the species of active catalyst (the transition metal cation) that is formed when the activating compound and the transition metal compound are combined, and this anion will be sufficiently labile to be displaced by the olefinic diolefinic compounds, and acetylenically unsaturated or other bases of neutral Lewis such as ethers, nitriles, and the like. Suitable metals for the anions of the activating compounds include, but are not limited to, aluminum, gold, platinum, and the like. Suitable metalloids include, but are not limited to, boron, phosphorus, silicon, and the like. Activator compounds containing anions comprising a coordination complex containing a single boron atom and a substituent comprising an active hydrogen fraction are preferred. Preferably, compatible anions containing a substituent comprising an active hydrogen fraction can be represented by the following general formula (I): [M * m + Qn (Gq (T-Pr) r) z] d- (I) wherein: M 'is a metal or metalloid selected from Groups 5-15 of the Periodic Table of the Elements; Q, independently in each presentation, is selected from the group consisting of hydride, dihydrocarbylamido, preferably dialkylamido, halide, hydrocarbyl oxide, preferably alkoxide and aryloxide, hydrocarbyl, and substituted hydrocarbyl radicals, including hydrocarbyl radicals substituted by halogen, and organic metalloid radicals substituted by hydrocarbyl and halogenated hydrocarbyl, the hydrocarbyl portion having from 1 to 20 carbon atoms, with the proviso that in no more than one presentation, Q is halide; G is a polyvalent hydrocarbon radical having the valences r + 1, and preferably a hydrocarbon radical, linked with M 'and T; T is O, S, NR, or PR, wherein R is a hydrocarbon radical, a trihydrocarbylsilyl radical, a trihydrocarbyl methyl radical, or hydrogen; m is an integer from 1 to 7, preferably 3 n is an integer from 0 to 7, preferably 3 q is an integer of 0 or 1, preferably 1 r is an integer from 1 to 3, preferably 1 z is an integer from 1 to 8, preferably 1 d is an integer from 1 to 7, preferably 1 and n + zm = d. Preferred boron-containing anions that are particularly useful in the present invention may be represented by the following general formula (II): [BQ4_z. (Gq (T-H) r) z.] '(ID where: B is boron in a valence state of 3; z1 is an integer from 1 to 4, preferably 1; d is 1; and Q, G, T, H, q, and r are as defined for formula (I). Preferably, z 'is 1, q is 1, and r is 1. Illustrative, but not limiting, examples of the anions of activating compounds for use in the present invention are boron-containing anions, such as triphenyl (hydroxyphenyl) borate ), diphenyl di (hydroxyphenyl) borate, triphenyl (2, -dihydroxyphenyl) borate, tri (p-tolyl) (hydroxyphenyl) borate, tris (pentafluorophenyl) - (hydroxyphenyl) borate, tris (2, 4-dimethylphenyl) (hydroxyphenyl), tris (3,5-dimethylphenyl) (hydroxyphenyl) borate, tris (3,5-ditrifluoromethylphenyl) (hydroxyphenyl) borate, tris (pentafluorophenyl) (2-hydroxyethyl) borate, tris (pen-tafluorophenyl) borate (4-hydroxybutyl), tris (pentafluorophenyl) borate (4-hydroxycyclohexyl), tris (pentafluorophenyl) borate (4- (4'-hydroxyphenylphenyl), tris (penta-fluorophenyl) borate (6-hydroxy-2-naphthyl), and the like A highly preferred activating complex is tris (pentafluorophene-nyl) (4-hydroxyphenyl) borate. Other preferred anions of activating compounds are the borates mentioned above, wherein the hydroxy functionality is replaced by an amino NHR functionality, wherein R is preferably methyl, ethyl, or tertiary butyl. The cationic portion bl) of the activator compound to be used in association with the compatible anion b.2) can be any cation that is capable of reaction with the transition metal compound to form a catalytically active transition metal complex, especially a cationic transition metal complex. The cations b.l) and the anions b.2) are used in proportions such that they give a neutral activating compound. Preferably, the cation is selected from the group consisting of Bronsted acid cations, carbon cations, silylium cations, and cationic oxidizing agents.

Bronsted acid cations can be represented by the following general formula: (L-H) + wherein: L is a neutral Lewis base, preferably a Lewis base containing nitrogen, phosphorus, or sulfur; and (L-H) + is a bronsted acid. It is believed that the Bronsted acid cations react with the transition metal compound by the transfer of a proton from this cation, which proton is combined with one of the ligands on the transition metal compound to liberate a neutral compound. Illustrative but not limiting examples of the Bronsted acid cations of the activating compounds to be used in the present invention are ammonium cations substituted by trialkyl, such as triethyl ammonium, tripropyl ammonium, normal tri-butyl ammonium. ), trimethyl ammonium, tributyl ammonium, and tri (normal octyl) ammonium. Also suitable are the N, N-dialkyl anilinium cations, such as N, N-dimethyl anilinium, N, N-diethyl anilinium, N, N-2,4,6-pentamethyl anilinium, N, N-dimethylbenzyl ammonium, and Similar; dialkyl ammonium cations, such as di- (isopropyl) ammonium, dicyclohexyl ammonium, and the like; and triaryl phosphonium cations, such as triphenyl phosphonium, tri (methylphenyl) phosphonium, tri (methylphenyl) phosphonium, dimethyl sulfonium, diethyl sulfonium, and diphenyl sulfonium. A second type of suitable cation corresponds to the formula: © +, where © + is a stable carbonium or silicon ion containing up to 30 non-hydrogen atoms, the cation being capable of reacting with a substituent of the transition metal compound, and converting it into a catalytically active transition metal complex, especially a cationic transition metal complex. Suitable examples of the cations include tropylium, triphenylmethylium, benzene (diazonium). Silylium salts have been described above in a generic manner in J. Chem. Soc. Chem. Comm. , 1993, 383-384, as well as Lambert, J.B. and collaborators, Organometallies, 1994, 13, 2430-2443. Preferred silylium cations are triethyl silylium, and trimethyl silyl, and ether-substituted adducts thereof. Another suitable type of cation comprises a cationic oxidizing agent represented by the formula: where 0xe + is a cationic oxidizing agent having a charge of e +, and e is an integer from 1 to 3.

Examples of cationic oxidizing agents include: ferrocenium, hydrocarbyl substituted ferrocenium, Ag +, and Pb2 +. The amount of activator compound in the supported catalyst component and in the supported catalyst is not critical, but is typically 0.1, preferably 1 to 2000 micromoles of activator compound per gram of treated support material. Preferably, the supported catalyst or component contains from 10 to 1000 micromoles of activator compound per gram of treated support material. The supported catalyst component of the present invention as such or in paste form in a diluent can be stored or shipped under inert conditions, or it can be used to generate the supported catalyst of the present invention. The transition metal compounds suitable for use in the supported catalyst of the present invention are those which contain a substituent capable of reacting with the activating compound (b) to thereby form a catalytically active transition metal complex. The transition metal compounds can be derived from any transition metal, including lanthanides, preferably from Groups 3, 4, 5, and 6, more preferably the transition metals from Group 3 or 4, or the lanthanides, whose metals of transition are in the formal oxidation state +2, +3, or +4. The transition metals preferably contain at least one anionic ligand II-linked group which can be a cycloalkyl or non-cyclic delocalized anionic ligand II-linked group. Examples of this II-linked anionic ligand group are thienyl groups, allyl groups, aryl groups, cyclic or non-cyclic, conjugated or non-conjugated, as well as substituted derivatives of these groups. By the term "derivative" when used to describe the above substituted delocalized substituted II groups, it is understood that each delocalized group II-linked atom can be independently substituted by a radical selected from the group consisting of halogen, hydrocarbyl, halogenated hydrocarbyl, and hydrocarbyl substituted metalloid radicals, wherein the metalloid is selected from Group 14 of the Periodic Table of the Elements. Included within the term "hydrocarbyl" are straight chain alkyl radicals of 1 to 20 carbon atoms, branched, and cyclic, aromatic radicals of 6 to 20 carbon atoms, aromatic radicals substituted by alkyl of 7 to 20 carbon atoms. of carbon, and alkyl radicals substituted by aryl of 7 to 20 carbon atoms. In addition, two or more of these radicals can together form a fused ring system or a hydrogenated fused ring system. Suitable hydrocarbyl substituted organic metalloid radicals include mono-, di-, and tri-substituted organic metalloid radicals of Group 14 elements, wherein each of the hydrocarbyl groups contains from 1 to 20 carbon atoms. More particularly, suitable substituted hydrocarbyl organic metalloid radicals include trimethylsilyl, triethylsilyl, ethyldimethylsilyl, methyldiethylsilyl, triphenylgermyl, trimethylgermyl, and the like. The preferred anionic delocalized anionic groups include the cyclopentadienyl and substituted cyclopentadienyl groups. Especially preferred are cyclopentadienyl, indenyl, fluorenyl, tetrahydroindenyl, tetrahydrofluorenyl, and octahydrofluorenyl. Other examples of preferred anionic ligand groups are the pentadienyl, cyclohexadienyl, dihydroanthracenyl, hexahydroanthracenyl, and decahydroanthracenyl groups, and the methyl substituted derivatives thereof. Suitable transition metal compounds (c) can be a cyclopentadienyl or a substituted cyclopentadienyl derivative of any transition metal, including Lantánidos, but preferably of the transition metals of Group 3, 4, or Lantánidos. Transition metal compounds suitable for use in the present invention are transition metal compounds of substituted cyclopentadienyl or mono-, bis-, and tri-cyclopentadienyl bridged or unbridged. Suitable non-bridged monocyclopentadienyl or mono (cyclopentadienyl) transition metal derivatives are represented by the general formula (III): CpMXn (3) wherein C_ is cyclopentadienyl or a derivative thereof, M is a transition metal of Group 3, 4, or 5 having a formal oxidation state of +2, +3, or +4, X, independently in each presentation, represents an anionic ligand group (other than an anionic ligand II-linked cyclic aromatic group) selected from the group of hydrocarbyl, hydrocarbylene, hydrocarbylene, hydrocarbyloxy, hydrocarbyloxy, hydride, halogen, silyl, germyl, amide, and siloxy radicals , having up to 50 non-hydrogen atoms, with the proviso that at least one X is selected from the group of a hydride radical, hydrocarbyl radical, substituted hydrocarbyl radical, or organic metalloid radical, and n, a number equal to 1 less than the formal oxidation state of M, is 1, 2, or 3, preferably 3. Preferably, at least one of X is a hydrocarbyl radical having from 1 to about 20 carbon atoms , a radica The substituted hydrocarbyl having 1 to about 20 carbon atoms, wherein one or more of the hydrogen atoms is replaced by a halogen atom, or an organic metalloid radical comprising a Group 14 element, wherein each one of the hydrocarbyl substituents contained in the organic portion of this organic metalloid, independently, contains from 1 to about 20 carbon atoms. Suitable bridged monocyclopentadienyl or mono (cyclopentadienyl) transition metal compounds include so-called restricted geometry complexes. Examples of these complexes and methods for their preparation are described in U.S. Patent Application Serial Number 545,403, filed July 3, 1990 (corresponding to European Patent Number EP-A-416). , 815), in U.S. Patent Application Serial Number 241,523, filed May 12, 1994 (corresponding to WO-95/00526), as well as in U.S. Patent Nos. North America Numbers 5,055,438; 5,057,475; 5,096,867; 5,064,802; 5,132,380, and 5,374,696, all of which are incorporated herein by reference. More particularly, preferred bridged monocyclopentadienyl or substituted mono (cyclopentadienyl) transition metal compounds correspond to formula (IV): / \ CP * M (IV) Wn wherein: M is a Group 3-5 metal, especially a Group 4 metal, particularly titanium; Cp * is a substituted cyclopentadienyl group bonded with Z1, and, in a? 5 -linking mode, with M, or this group is further substituted by one to four substituents selected from the group consisting of hydrocarbyl, silyl, germyl , halogen, hydrocarbyloxy, amine, and mixtures thereof, this substituent having up to 20 non-hydrogen atoms, or optionally, two of these additional substituents together make Cp * have a fused ring structure; Z 'is a different bivalent moiety of an anionic ligand II-linked cyclic or non-cyclic, comprising this Z' boron, or a member of Group 14 of the Periodic Table of the Elements, and optionally nitrogen, phosphorus, sulfur, or oxygen, said fraction having up to 20 non-hydrogen atoms, and optionally Cp * and Z 'together form a fused ring system; X has the same meaning as in the formula (ni); and n is 1 or 2, depending on the valence of M. In keeping with the above explanation, M is preferably a Group 4 metal, especially titanium; n is 1 or 2; and X is a monovalent ligand group of up to 30 non-hydrogen atoms, more preferably hydrocarbyl of 1 to 20 carbon atoms. When n is 1 and the metal of Group 3-5 (preferably the metal of Group 4) is in the formal oxidation state +3, X is preferably a stabilizing ligand. By the term "stabilizing ligand" is meant that the ligand group stabilizes the metal complex through any of: 1) a nitrogen chelation bond, phosphorus, oxygen, or sulfur, or 2) a link? 3 with a de-localized resonant II-electronic structure. Examples of the stabilizing ligands of group 1) include silyl, hydrocarbyl, amido, or phosphido ligands substituted by one or more aliphatic or aromatic ether, thioether, amine, or phosphine functional groups, especially the amine or phosphine groups that are substituted tertiaryly, this stabilizing ligand having from 3 to 30 non-hydrogen atoms. The most preferred stabilizing ligands of group 1) are the 2-dialkylaminobenzyl or 2- (dialkylaminomethyl) phenyl groups, which contain from 1 to 4 carbon atoms in the alkyl groups. Examples of the stabilizing ligands of group 2) include hydrocarbyl groups of 3 to 10 carbon atoms containing ethylenic unsaturation, such as allyl groups, 1-methylallyl, 2-methylallyl, 1, 1-dimethylallyl, or 1, 2 -trimethylallyl. Still more preferably, these metal coordination complexes correspond to the formula (V): wherein R1 in each presentation is independently selected from the group consisting of hydrogen, hydrocarbyl, silo, germyl, cyano, halogen, and combinations thereof having up to 20 non-hydrogen atoms, or two R * groups together a bivalent derivative thereof; X has the same meaning as defined for formula (III); Y is a bivalent anionic ligand group comprising nitrogen, phosphorus, oxygen, or sulfur, and having up to 20 non-hydrogen atoms, bonding Y with Z and M through nitrogen, phosphorus, oxygen, or sulfur, and optionally Y and Z together form a fused ring system; M is a Group 4 metal, especially titanium; Z is S R, CR 2 / S1R SlR 'CR 2CR 2 CR-CR, CR * 2SiR * 2, GeR * 2, BR *, or BR * 2; wherein: R *, in each presentation, is independently selected from the group consisting of hydrogen, hydrocarbyl, silyl, halogenated alkyl, halogenated aryl groups having up to 20 non-hydrogen atoms, and mixtures thereof, or two or more groups R * of Z, or a group R * of Z together with Y form a fused ring system; and n is 1 or 2. Furthermore, more preferably, Y is -O-, -S-, -NR * -, - PR * -. In a highly preferable manner, Y is a group containing nitrogen or phosphorus corresponding to the formula -N (R ') - or -P (R *) -, wherein R' is as described above, ie a amido or phosphide group. The most highly preferred metal coordination complexes correspond to formula (VI): wherein: M is titanium; R ', in each presentation, is independently selected from the group consisting of hydrogen, silyl, hydrocarbyl, and combinations thereof having up to 10 carbon atoms or silyl, or two R' groups of the substituted cyclopentadienyl moiety. they unite with each other; E is silicon or carbon; X, independently in each presentation, is hydride, alkyl, aryl, of up to 10 carbon atoms; m is 1 or 2; and n is 1 or 2.

Examples of the most highly preferred metal coordination compounds above include compounds wherein R 'on the amido group is methyl, ethyl, propyl, butyl, pentyl, hexyl, (including isomers), norbornyl, benzyl, phenyl, and cyclododecyl; (ER ^) ,,, is dimethylsilane or 1,2-ethylene; R1 on the cyclic linked group II, independently in each presentation, is hydrogen, methyl, ethyl, propyl, butyl, pentyl, hexyl, norbornyl, benzyl, and phenyl, or two R 'groups are joined to form an indenyl, tetrahydroindenyl moiety , Luorenyl. or octahydrofluorenyl; and X is methyl, ethyl, propyl, butyl, pentyl, hexyl, norbornyl, benzyl, and phenyl. Transition metal compounds wherein the transition metal is in the formal +2 oxidation state include those complexes containing one and only one cyclic, delocalized, anionic linked group II, these complexes corresponding to formula (VII): Z / \ (VII) L M X * wherein: M is titanium or zirconium in the formal oxidation state +2; L is a group containing a delocalized cyclic anionic system II through which the group is linked to M, and whose group also links to Z; Z is a moiety linked to M by means of a bond s, which comprises boron, or a member of Group 14 of the Periodic Table of the Elements, and which also comprises nitrogen, phosphorus, sulfur, or oxygen, this fraction having up to 60 atoms that are not hydrogen; and X * is a neutral conjugated or non-conjugated diene, optionally substituted by one or more hydrocarbyl groups, having X up to 40 carbon atoms, and forming a complex II with M. The preferred transition metal compounds of the formula (VII) they include those where Z, M, and X * are as defined above; and L is a C5H4 group bonded to Z and linked in a? 5 linking mode with M, or is a? 5-linked group substituted by one to four substituents independently selected from hydrocarbyl, silyl, germyl, halogen, cyano, and combinations thereof, this substituent having up to 20 non-hydrogen atoms, and optionally, two of these substituents (except cyano or halogen) together form a fused ring structure.

The more preferred +2 transition metal compounds according to the present invention correspond to formula (VIII): wherein: R 'in each presentation, is independently selected from hydrogen, hydrocarbyl, silyl, germyl, halogen, cyano, and combinations thereof, R1 having up to 20 non-hydrogen atoms, and optionally, two R groups '(wherein R1 is not hydrogen, halogen, or cyano) together form a bivalent derivative thereof connected to the adjacent positions of the cyclopentadienyl ring to form a fused ring structure; X * is a neutral 4-linked diene group having up to 30 non-hydrogen atoms, which forms a complex II with M; And it is -O-, -S-, -NR * -, -PR * -; M is titanium or zirconium in the formal oxidation state +2; Z is S1R2, CR2, S1R2S1R, CRCR2, CR = CR, CR * 2SiR * 2, or GeR * 2; wherein: R *, in each presentation, is independently hydrogen, or a member selected from hydrocarbyl, silyl, halogenated alkyl, halogenated aryl, and combinations thereof, R * having up to 10 non-hydrogen atoms, and optionally, two groups R * of Z * (when R * is not hydrogen), or a group R * of Z * and a group R * of Y form a ring system.

Preferably, R ', independently in each presentation, is hydrogen, hydrocarbyl, silyl, halogen, and combinations thereof, R' having up to 10 non-hydrogen atoms, or two R * groups (when R 'is not hydrogen) or halogen) together form a bivalent derivative thereof; more preferably, R 'is hydrogen, methyl, ethyl, propyl, butyl, pentyl, hexyl, (including where all isomers are appropriate), cyclopentyl, cyclohexyl, norbornyl, benzyl, or phenyl, or two R' groups (except hydrogen ) are linked together, the entire group C5R'4 being, for example, an indenyl, tetrahydroindenyl, fluorenyl, tetrahydrofluorenyl, or octahydrofluorenyl group. In addition, preferably, at least one of R1 or R * is an electron donor moiety. By the term "electron donor" is meant that the fraction is more electron donor than hydrogen. Accordingly, in a highly preferable manner, Y is a nitrogen or phosphorus containing group corresponding to the formula -N (R ") - or -P (R") -, where R "is hydrocarbyl of 1 to 10 atoms Examples of suitable X * groups include: s-trans-? 4-l, 4-diphenyl-1,3-butadiene; s-trans-? 4-3-methyl-l, 3-pentadiene; -trans-? 4-l, 4-dibenzyl-l, 3-butadiene; s-trans-? 4-2,4-hexadiene; s-trans-? 4-l, 3-pentadiene; s-trans-? 4 -l, 4-ditolyl-l, 3-butadiene; s-trans-? -l, 4-bis (trimethylsilyl) -1, 3-butadiene; s-cis-? 4-l, 4-diphenyl-l, 3 -butadiene; s-cis-? -3-methyl-1,3-pentadiene; s-cis-? -l, 4-dibenzyl-l, 3-butadiene; s-cis-? 4-2,4-hexadiene; s-cis-? 4-l, 3-pentadiene; s-cis-? -l, 4-ditolyl-l, 3-butadiene; and s-cis-? 4-l, 4-bis (trimethylsilyl) -l, 3-butadiene, this group forming s-cis diene a complex II as defined herein with the metal The most highly preferred transition metal compounds +2 are the amidosilane or amidoalkandiyl compounds of the formula a (VIII) wherein: -Z * -Y- is - (ER "'2) mN (R") -, and R1, in each presentation, is independently selected from hydrogen, silyl, hydrocarbyl, and combinations of having R 'up to 10 carbon or silicon atoms, or two of these R * groups on the substituted cyclopentadiene group (when R' is not hydrogen) together form a bivalent derivative thereof connected to the adjacent positions of the ring of cyclopentadienyl; R "is hydrocarbyl of 1 to 10 carbon atoms, R" ', independently in each presentation, is hydrogen or hydrocarbyl of 1 to 10 carbon atoms; E, independently in each presentation, is silicon or carbon; and m is 1 or 2.

Examples of the metal complexes according to the present invention include compounds wherein R "is methyl, ethyl, propyl, butyl, pentyl, hexyl, (including all isomers of the foregoing, where applicable), cyclododecyl, norbornyl , benzyl, or phenyl; (ER1") m is dimethylsilane or ethanediyl; and the group II-linked from cyclic localized is cyclopentadienyl, tetramethylcyclopentadienyl, indenyl, tetrahydroindenyl, fluorenyl, tetrahydrofluorenyl, or octahydrofluorenyl. Bis (cyclopentadienyl) derivatives of suitable transition metals include those of titanium, zirconium, and hafnium compounds, and may be represented by the following general formulas (IX) - (XII): (A-Cp) MX1X2 (IX) (A-Cp) MX 'K' 2 (X) (A-Cp) ML (XI) (Cp *) (CpRJMX-L (XII) wherein: M is a Group 4 metal, that is, titanium (Ti), zirconium (Zr) and hafnium (Hf); (A-Cp) is either (Cp) (Cp *) or Cp-A'-Cp *, and Cp and Cp * are the same or different cyclopentadienyl radicals, as well as substituted derivatives of cyclopentadienyl radicals, and A 'is a covalent bridge group containing an element of Group 14; L is an olefin, diolefin, or arine ligand; at least one of Xx and X2 is a hydride radical, a hydrocarbyl radical, a substituted hydrocarbyl radical, or an organic metalloid radical, the other being X1 and X2 a hydride radical, a hydrocarbyl radical, a radical of substituted hydrocarbyl, an organic metalloid radical, or a hydrocarbyloxy radical; preferably one or both of X1 and X2 is a hydrocarbyl radical having from 1 to about 20 carbon atoms, a substituted hydrocarbyl radical having from 1 to about 20 carbon atoms, wherein 1 or more of the hydrogen are replaced with a halogen atom, an organic metalloid radical comprising an element of, Group 14, wherein each of the hydrocarbyl substituents contained in the organic portion of the organic metalloid, independently, contains from 1 to about 20. carbon atoms; X '1 and X'2 are bonded and bonded to the metal atom to form a metalacycle, in whose metal, X'? and X'2 form a hydrocarbyl cyclic ring containing from about 3 to about 20 carbon atoms; and R is a substituent, preferably a hydrocarbyl substituent, having 1 to 20 carbon atoms, or one of the cyclopentadienyl radicals, which is also bonded to the metal atom.

When both X x and X 2 are not a hydride radical, a hydrocarbyl radical, a substituted hydrocarbyl radical, or an organic metalloid radical, one of these may be a hydrocarbyloxy radical having from 1 to 20 carbon atoms. Suitable examples of hydrocarbyloxy radicals include alkyloxy, aryloxy, aralkyloxy, and alkaryloxy radicals having from 1 to 20 carbon atoms, more preferably alkyl radicals having from 1 to 6 carbon atoms, and aryl, aralkyl radicals, and alkaryl having from 6 to 10 carbon atoms, still more preferably isopropyloxy, normal butyloxy, or tertiary butyloxy. Examples of these bis (cyclopentadienyl) derivatives of transition metals, and methods for their preparation, are described in U.S. Patent No. 5,384,299 (corresponding to European Patent Number EP-A-277, 004 ), and in U.S. Patent Application Serial Number 459,921, filed January 2, 1990 (corresponding to WO / 09882), which are incorporated herein by reference. Suitable substituted tricyclopentadienyl or cyclopentadienyl transition metal compounds include those that contain a bridging group that binds two cyclopentadienyl groups, and those that do not have these bridging groups. Suitable non-bridged tricyclopentadienyl transition metal derivatives are represented by the general formula (XIII): Cp3MXn "(XIII) wherein Cp, M and X are as defined for Formula (III), and n "is three less than the formal oxidation state of M, and is 0 or 1, preferably 1. Preferred X-ligand groups are hydrocarbyl , hydrocarbyloxy, hydride, halogen, silyl, germyl, amide, and siloxy In general terms, the proportion of moles of the activating compound (b) to gram atoms of the transition metal in the compound (c) in the supported catalyst is 0.05: 1 to 100: 1, preferably from 0.5: 1 to 20: 1, and more preferably from 1: 1 to 5: 1 moles of activator compound per gram-atom of transition metal in the transition metal compound. In too low proportions, the supported catalyst will not be very active, while at too high rates, the catalyst becomes less economical because of the relatively high cost associated with the use of large amounts of the activating compound. The supported catalyst component of the present invention can be prepared by combining the support material with the organometallic compound, preferably an aluminum component, and the activating compound. The order of addition is not critical. The organometallic compound can be combined either first with the support material or with the activating compound, and subsequently the activating compound or support material can be added. A preferred embodiment comprises treating the support material first with the organometallic compound, preferably the aluminum component, by combining the organometallic compound in a suitable solvent, such as a hydrocarbon solvent, with the support material. The temperature, pressure, and contact time for this treatment are not critical, but generally range from -20 ° C to about 150 ° C, from subatmospheric pressure to 10 bar, more preferably at atmospheric pressure, for 5 hours. minutes to 48 hours. Normally the pasta is stirred. After this treatment, solids are typically separated from the solvent. Any excess of the organometallic compound could then be removed by techniques known in the art. This method is especially suitable for obtaining a support material with metal charges, preferably aluminum, relatively low. According to a preferred embodiment, the support material is first subjected to a heat treatment of 100 ° C to 1000 ° C, preferably of about 200 ° C to about 850 ° C. Typically, this treatment is carried out for about 10 minutes to about 72 hours, preferably about 0.5 hours to 24 hours. Then, the thermally treated backing material is combined with the organometallic compound, preferably AIR '3, where R' has the meaning defined hereinbefore, in a suitable diluent or solvent, preferably one in which the compound is soluble organometallic Typical solvents are hydrocarbon solvents having from 5 to 12 carbon atoms, preferably aromatic solvents such as toluene and xylenes, or aliphatic solvents of 6 to 10 carbon atoms, such as hexane, heptane, octane, nonane, decane, and isomers thereof, cycloaliphatic solvents of 6 to 12 carbon atoms such as cyclohexane, or mixtures of any of these. The support material is combined with the organometallic compound at a temperature of -20 ° C to 150 ° C, preferably 20 ° C to 100 ° C. The contact time is not critical, and can vary from 5 minutes to 72 hours, and preferably from 0.5 hours to 36 hours. Preferably stirring is applied. The support material thus treated is then preferably placed in contact with the activating compound. An alternative treatment of the support material, suitable for obtaining charges of alumoxane bonded to the support material, involves one or both of the following steps A and B: A. heating a support material containing alumoxane under an inert atmosphere for a period of time a temperature sufficient to fix the alumoxane to the support material; B. subjecting the support material containing alumoxane to one or more washing steps, to remove the alumoxane not bound to the support material; selecting in this manner the conditions in the heating step A and in the washing step B to form a treated support material in which no more than about 10 percent aluminum present in the treated support material is removable in an extraction one hour with toluene at 90 ° C using about 10 milliliters of toluene per gram of supported catalyst component. High amounts of alumoxane bound to the support material are obtained using first the heating step A, optionally followed by the washing step B. In this process, the support material treated with alumoxane can be obtained by combining in a diluent, of an alumoxane with a support material containing from 0 to not more than 20 percent by weight of water, preferably from 0 to not more than 6 percent by weight of water, based on the total weight of the support material and the Water.

Although support materials that substantially do not contain water give good results with respect to the catalytic properties of the supported catalyst, it has been found that support materials containing relatively small amounts of water can be used without problem in the present process. Water-containing support materials, when combined under identical conditions in the same amount of alumoxane, give, in the present process, a supported catalyst component having an aluminum content slightly higher than the support material substantially free of Water. It is believed that the water reacts with the residual amounts of the aluminum alkyl present in the alumoxane to convert the aluminum alkyl to extra alumoxane. An additional advantage is that in this way less aluminum alkyl will be lost towards the waste or recycle streams. The alumoxane is desirably used in a dissolved form. Alternatively, the support material previously treated with alumoxane can be obtained by combining, in a diluent, a support material containing 0.5 to 50 percent by weight of water, preferably 1 to 20 percent by weight. weight percent water, based on the total weight of the support material and water, with a compound of the Formula R "n * AlX" 3_n * where R ", independently in each presentation, is a hydrocarbyl radical, X "is halogen or hydrocarbyloxy, and n * is an integer of 1 to 3. Preferably, n * is 3. R", independently in each presentation, is preferably an alkyl radical, conveniently one containing the 12 carbon atoms Preferred alkyl radicals are methyl, ethyl, propyl, isopropyl, normal butyl, isobutyl, tertiary butyl, pentyl, isopentyl, hexyl, isohexyl, heptyl, octyl, and cyclohexyl The highly preferred compounds of the Formula R "n * AlX "3_n * are trimethyl aluminum, al Triethyl aluminum, and triisobutyl aluminum. When the alumoxane is prepared in situ by reaction of the compound of the formula R "n * AlX" 3_n * with water, the molar ratio of R "n * AlX" 3_n * to water is typically from 10: 1 to 1: 1 , preferably from 5: 1 to 1: 1. The support material is added to the alumoxane or the compound of the Formula R "n * AlX" 3_n *, preferably dissolved in a solvent, more preferably a hydrocarbon solvent, or the solution of alumoxane or the compound of the Formula R " n * AlX "3_n * is added to the support material. The support material can be used as such in dry form or in paste form in a hydrocarbon diluent. Both aliphatic and aromatic hydrocarbons can be used. Suitable aliphatic hydrocarbons include, for example, pentane, isopentane, hexane, heptane, octane, isooctane, nonane, isononane, decane, cyclohexane, methylcyclohexane, and combinations of two or more of these diluents. Suitable examples of the aromatic diluents are benzene, toluene, xylene, and other aromatic compounds substituted by alkyl or halogen. More preferably, the diluent is an aromatic hydrocarbon, especially toluene. Suitable concentrations of the solid support in the hydrocarbon medium are from about 0.1 to about 15, preferably from about 0.5 to about 10, more preferably from about 1 to about 7 weight percent. Contact time and temperature are not critical. Preferably, the temperature is from 0 ° C to 60 ° C, more preferably from 10 ° C to 40 ° C. The contact time is 15 minutes to 40 hours, preferably from 1 to 20 hours. Before subjecting the alumoxane-treated support material to the heating step or to the washing step, the diluent or solvent is preferably removed to obtain a free-flowing powder. This is preferably done by applying a technique that only removes the liquid and leaves the aluminum compounds on the solids, such as by the application of heat, reduced pressure, evaporation, or a combination thereof. If desired, the removal of the diluent can be combined with the heating step, although care must be taken that the diluent is gradually removed. The heating step and / or the washing step are conducted in such a way that a very large proportion (more than about 90 weight percent) of the alumoxane remaining on the support material is fixed. Preferably, a heating step is employed, more preferably, a heating step followed by a washing step is employed. When used in the preferred combination, both steps cooperate in such a way that, in the heating step, the alumoxane is fixed to the support material, while in the wash step, the alumoxane that was not fixed is removed to a degree substantial. The upper temperature for the heat treatment is preferably lower than the temperature at which the support material begins to agglomerate and form lumps, which are difficult to re-disperse, and less than the decomposition temperature of the alumoxane. When the transition metal compound (c) is added before the heat treatment, the heating temperature must be lower than the decomposition temperature of the transition metal compound. Preferably, the heat treatment is carried out at a temperature of 75 ° C to 250 ° C for a period of 15 minutes to 24 hours. More preferably, the heat treatment is carried out at a temperature of 160 ° C to 200 ° C for a period of 30 minutes to 4 hours. Good results have been obtained while heating for 8 hours at 100 ° C, as well as while heating for 2 hours at 175 ° C. Through preliminary experiments, a person skilled in the art will be able to define the heat treatment conditions that will provide the desired result. It is also noted that the longer the heat treatment, the higher the amount of alumoxane fixed to the support material. The heat treatment is carried out at a reduced pressure or under an inert atmosphere, such as a nitrogen gas, or both, but preferably at reduced pressure. Depending on the conditions in the heating step, the alumoxane can be fixed to the support material to such a high degree that the washing step can be omitted. In the washing step, the number of washes and the solvent used are such that sufficient quantities of unbound alumoxane are removed. The washing conditions must be such that the unfixed alumoxane is soluble in the wash solvent. The support material containing alumoxane, preferably already subjected to a heat treatment, is preferably subjected to one to five wash steps using an aromatic hydrocarbon solvent at a temperature of 0 ° C to 110 ° C. More preferably, the temperature is from 20 ° to 100 °. Preferred examples of the aromatic solvents include toluene, benzene, and xylenes. More preferably, the aromatic hydrocarbon solvent is toluene. At the end of the washing treatment, the solvent is removed by a technique that also removes the alumoxane dissolved in the solvent, such as by filtration or decantation. Preferably, the wash solvent is removed to provide a free flowing powder. The support material treated with the organometallic compound is then typically re-formed into a paste in a suitable diluent, and combined with the activating compound. The activating compound is preferably used in a diluent. Suitable diluents include hydrocarbon and halogenated hydrocarbon diluents. Any type of solvent or diluent that does not react with the catalyst components can be used in such a way that they have a negative impact on the catalytic properties. Preferred diluents are aromatic hydrocarbons, such as toluene, benzene, and xylenes, and aliphatic hydrocarbons, such as hexane, heptane, and cyclohexane. Preferred halogenated hydrocarbons include methylene chloride and carbon tetraeloride. The temperature is not critical, but generally varies between -20 ° C and the decomposition temperature of the activator. The typical contact time varies from a few minutes to several days. Agitation of the reaction mixture is preferred. In a convenient manner, the activating compound dissolves, using heat to assist in dissolution when desired. It may be advisable to make contact between the treated support material with the organometallic and the activating compound at elevated temperatures. Preferably, these elevated temperatures are from 45 ° C to 120 ° C. Instead of first treating the support material with the organometallic compound, preferably the aluminum component, and subsequently adding the activating compound, the organometallic compound, preferably the aluminum component, and the activating compound, can be combined in a diluent. suitable before adding or combining the reaction mixture to or with the support material. Without wishing to be bound by theory, it is believed that an organic group of the organometallic compound reacts with the active hydrogen fraction contained in the activating anion b.2) to form a reaction product (also referred to hereinbelow as "adduct") . For example, when the organometallic compound is trialkyl aluminum A1R3, and the active hydrogen-containing fraction is represented by G-OH, it is believed that the reaction product comprises G-0-AlR2, while also a by-product of alkane RH is formed. . This adduct G-0-AlR2, when combined with the support material containing hydroxyl groups, Si-OH in the case of a silica support material, is believed to form Si-O-Al (R) -OG together with RH alkane as a by-product. It has been found that this method for preparing the supported catalyst component runs very smoothly and provides catalyst and catalyst precursors or components having desirable properties. Typical proportions for use in this reaction are from about 1: 1 to about 20: 1 moles of organometallic compound to molar equivalents of active hydrogen fractions contained in the activating anion b.2). The amount of adduct, formed by combining the organometallic compound with the activating compound to be combined with the support material, is not critical. Preferably, the amount is not greater than that which can be fixed to the support material. Typically, this is determined by the amount of hydroxyls of the support material. The amount of adduct to be used preferably is not greater than the equivalent amount of these hydroxyl groups. Preferably less than the equivalent amount is used, more preferably the ratio between moles of adduct to moles of surface reactive groups such as hydroxyls is between 0.01 and 1, still more preferably between 0.02 and 0.8. Before adding the transition metal compound, it is preferred, especially when less than an equivalent amount of adduct is added with respect to the surface reactive groups, to add a further amount of organometallic compound to the reaction product of the support material and the adduct. , to remove any remaining surface reactive groups, which may otherwise react with the transition metal, and therefore, require higher amounts thereof to achieve equal catalytic activity. Before combining it with the transition metal compound, the supported catalyst component can be washed, if desired, to remove any excess adduct or organometallic compound. The supported catalyst component comprising the support material, the organometallic compound, and the activator, can be isolated to obtain a free flowing powder, by removing the liquid medium, preferably using filtration or evaporation techniques. Although the transition metal compound can be combined with the activating compound, or the adduct of the organometallic compound and the activating compound, before combining the activating compound or its adduct with the support material, this results in reduced catalyst efficiencies. Preferably, the transition metal is first combined with the support material treated with the organometallic component and before adding the activating compound, or the transition metal is added after the treated support material and the activator have been combined, or after the activating adduct and the support material have been combined. More preferably, the transition metal compound (c) is added to the reaction product of the support material treated with the organometallic compound and the activating compound, or after they have been combined in activator adduct and the support material . The transition metal compound is preferably used dissolved in a suitable solvent, such as a hydrocarbon solvent, suitably an aliphatic or cycloaliphatic hydrocarbon of 5 to 10 carbon atoms, or an aromatic hydrocarbon of 6 to 10 carbon atoms. The contact temperature is not critical, since it is below the decomposition temperature of the transition metal and the activator. Good results are obtained on a temperature scale of 0 ° C to 100 ° C. All the steps of the present process must be conducted in the absence of oxygen and humidity. On the combination of the transition metal compound with the supported catalyst component, the supernatant liquid is typically colorless, indicating that the transition metal compound, whose solution is typically colored, substantially remains with the solid supported catalyst. The supported catalyst obtained by the combination of the support material, the organometallic compound, the activator, and the transition metal, can be stored or shipped in free flowing form under inert conditions after the solvent is removed.

The supported catalysts of the present invention can be used in an addition polymerization process, wherein one or more addition polymerizable monomers are contacted with the supported catalyst of the invention under addition polymerization conditions. Suitable addition polymerizable monomers include ethylenically unsaturated monomers, acetylenic compounds, conjugated or non-conjugated dienes, polyenes, and carbon monoxide. Preferred monomers include olefins, for example, alpha-olefins having from 2 to about 20, preferably from about 2 to about 12, more preferably from about 2 to about 8 carbon atoms, and combinations of 2 or more of these alpha -olefins. Particularly suitable alpha-olefins include, for example, ethylene, propylene, 1-butene, 1-pentene, 4-methylpentene-1, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1 -undecene, 1-dodecene, 1-tridecene, 1-tetradecene, 1-pentadecene, or combinations thereof. Preferably, the alpha-olefins are ethylene, propene, 1-butene, 4-methylpentene-1, 1-pentene, 1-hexene, 1-octene, and combinations of ethylene and / or propene with one or more of those other alpha -olefins. Suitable dienes include those having from 4 to 30 carbon atoms, especially those having from 5 to 18 carbon atoms. The typical ones are α, β-dienes, α-internal dienes, including the dienes that are typically used for the preparation of EPDM type elastomers. Typical examples include 1,3-butadiene, 1,3- and 1,4-pentadiene, 1,3-, 1,4-, and 1,5-hexadiene, 1,7-octadiene, 1,9-decadiene, and analogs substituted by lower alkyl of any of these. Other preferred monomers include styrene, styrenes substituted by halogen or alkyl, tetrafluoroethylene, vinylcyclobutene, dicyclopentadiene, and ethylidenebornenes. Suitable addition polymerizable monomers also include any mixtures of the aforementioned monomers. The supported catalyst can be formed on site in the polymerization mixture, by introducing into the mixture both a supported catalyst component of the present invention, or its components, and a suitable transition metal compound (c). The supported catalyst can be used as such or after being subjected to prepolymerization. The prepolymerization can be carried out by any known methods, such as by bridging a small amount of monomers preferably alpha-olefins, in contact with the supported catalyst. The catalyst can be used in the polymerization reaction at a concentration of 10 ~ 9 to 10 ~ 3 moles, based on the transition metal, per liter of diluent or reaction volume, but is preferably used in a concentration of less than 10 ~ 5, preferably 10 ~ 8 to 9 x 10 ~ 6 moles per liter of diluent or reaction volume. The supported catalyst can be conveniently employed in a high pressure, solution, paste, or gas phase polymerization process. A high-pressure process is normally carried out at temperatures of 100 ° C to 400 ° C, and at pressures greater than 500 bar. A pulp process typically utilizes an inert hydrocarbon diluent and temperatures of about 0 ° C to a temperature just below the temperature at which the resulting polymer becomes substantially soluble in the inert polymerization medium. Preferred temperatures are about 30 ° C, preferably about 60 ° C to about 115 ° C, preferably about 100 ° C. The solution process is carried out at temperatures from the temperature at which the resulting polymer is soluble in an inert solvent to approximately 275 ° C. In general, the solubility of the polymer depends on its density. For ethylene copolymers having densities of 0.86 grams / cubic centimeter, solution polymerization can be achieved at temperatures as low as approximately 60 ° C. Preferably, the temperatures of the solution polymerization are about 75 ° C, more preferably about 80 ° C, and typically from about 130 ° C to about 260 ° C, more preferably at about 170 ° C. More preferably, the temperatures in a solution process are between about 80 ° C and 150 ° C. As the inert solvents, hydrocarbons are typically used, and preferably aliphatic hydrocarbons. The processes in solution and in paste are normally carried out at pressures between approximately 1 and 100 bar. Typical operating conditions for gas phase polymerizations are from 20 ° C to 100 ° C, more preferably from 40 ° C to 80 ° C. In gas phase processes, the pressure is typically from subatmospheric to 100 bar. Preferably, for use in gas phase polymerization processes, the support has an average particle diameter of from about 20 to about 200 microns, more preferably from about 30 microns to about 150 microns, and most preferably of about 50 microns. approximately 100 microns. Preferably, for use in the pulp polymerization processes, the support has an average particle diameter of from about 1 micron to about 200 microns, more preferably from about 5 microns to about 100 microns, and most preferably from about 20 microns to about 80 microwaves Preferably, for use in solution or high pressure polymerization processes, the support has an average particle diameter of from about 1 micron to about 40 microns, more preferably from about 2 microns to about 30 microns, and most preferably from about 3 microns to approximately 20 microns. Other details for the polymerization conditions in a gas phase polymerization process can be found in the Patents of the United States of North America Nos. 4,588,790; 4,543,399; 5,352,749; 5,405,922; U.S. Patent Application Serial Number 926,009, filed August 5, 1992 (corresponding to WO-94/03509), and U.S. Patent Application Serial Number 122,582, filed on September 17, 1993 (corresponding to WO-95/07942), which are incorporated herein by reference. Processes in gas phase where the condensed monomer or the inert diluent is present are preferred. The supported catalysts of the present invention, also when used in a pulp process or in a gas phase process, are not only capable of producing ethylene copolymers of typical densities for high density polyethylene, in the scale of 0.970. at 0.940 grams / cubic centimeter, but in a surprising way, they also make possible the production of copolymers having substantially lower densities. Copolymers of densities lower than 0.940 grams / cubic centimeter, and especially lower than 0.930 grams / cubic centimeter and falling to 0.880 grams / cubic centimeter or lower, can be made, while retaining good properties of bulk density, and while that contamination of the reactor is substantially prevented or eliminated. The present invention is capable of producing olefin polymers and copolymers having weight average molecular weights greater than 30,000, preferably greater than 50,000, more preferably greater than 100,000, and up to 1,000,000, and still higher. Typical molecular weight distributions M ^ M-j are from 1.5 to 15, or even higher, preferably between 2.0 and 8.0. In the polymerization process of the present invention, impurity scavengers can be used which serve to protect the supported catalyst from catalyst poisons, such as water, oxygen, and polar compounds. These scavengers can be used in general in amounts that depend on the amounts of impurities. Typical scavengers include organometallic compounds, and preferably trialkyl aluminum or boron compounds and alumoxanes. In the present polymerization process, molecular weight control agents, such as hydrogen or other chain transfer agents can also be used. The polymers that are prepared in accordance with this polymerization process can be combined with any conventional additives, such as ultraviolet stabilizers, anti-oxidants, anti-skid or anti-blocking agents, which can be added in conventional ways, for example, downstream of the polymerization reactor, or in an extrusion or molding step. Upon or after removal of the polymerization mixture or product from the polymerization reactor, the supported catalyst can be deactivated by exposure to air or water, or through any other agent or catalyst deactivating process. In the complex compounds of the present invention, preferably the compatible anion portion b.2) corresponds to the General Formula (I): [M'm + Qn (Gq (T-Pr) r) z] d '(I) where: M ', Q, G, T, m, n, q, r, z, and d have the same definitions as formula 1, and Pr is hydrogen H or a protecting group. Preferred protecting groups and charge balancing cations are illustrated hereinafter.

The complex compounds containing anions b.2) can be prepared by the combination of a neutral compound, such as M, m + Qm, wherein M ', Q, and m have the same meaning as in Formula (I), with an active metal derivative of the substituent comprising an active hydrogen fraction, such as a lithium or Grignard derivative thereof, for example, Z (G (TH) r), wherein Z is Li +, MgCl +, MgBr +, or Mgl +, and G, T, H, q, and r have the same meanings as Formula (I). The T-H group can be protected during preparation by methods that are well known to those skilled in the art. For example, a hydroxy fraction can be protected by a trimethylsilyl group. The method for the preparation of the complex compounds, therefore, comprises combining, in a suitable solvent or diluent, a compound M, m + Qm with a compound of the Formula Z1 (Gq (T-Pr) r), wherein Z1 is [M * X **] + or [M **] + and M * is an element of Group 2, M ** is an element of Group 1, and X is halogen, G, T, Pr, q, yr they have the same meaning as was given for Formula (I), optionally followed by the recovery of the product complex. Suitable examples of the protecting groups Pr include: trialkylsilyl, triarylsilyl, and mixtures thereof, preferably trimethylsilyl, tertiary butyl-dimethylsilyl, triisopropylsilyl, tertiary butyl-diphenylsilyl, and phenyldimethylsilyl; preferably, the protecting group contains a bulky substituent, such as tertiary butyl or phenyl, to stabilize the resulting protected group during the subsequent metallation reaction. The reaction between the compound M, m + Qm and Z1 (Gq (TP * ") r) is typically carried out in an ether or any organic diluent that does not have a negative impact on the desired reaction, and mixtures thereof. preferred are tetrahydrofuran and diethyl ether.The temperature is not critical, and is typically in the range of -20 ° C to 100 ° C. The reaction mixture is preferably stirred and reacted for a period of between 5 minutes and 72 minutes. It has been discovered that it is convenient to use a molar excess of the compound Z1 (Gq (T-Pr) r) with respect to the compound M, m + Qm This excess is preferably from 1.1 to 3 molar equivalents, more preferably from 1.5 at 2.5 molar equivalents of Z1 (Gq (T-Pr) r) per mole of M, m + Qm Preferably, the reaction mixture is heated to a temperature between 40 ° C and 100 ° C, more preferably between 50 ° C C and 95 ° C. It was discovered that the use of these process conditions increases the conversion based on the compound M, m + Qm up to 90 percent and more. Since the compound M'm + Qm is usually the most expensive reagent, it is highly desirable to increase the yield of the reaction with respect to this compound. Then, the product complex is preferably recovered, for example, by decanting, filtration, conveniently followed by washing, preferably with a hydrocarbon, and drying. The protective group Pr, when present in the complex product, is preferably removed by conventional methods, such as reaction of the product complex with water, alcohol, organic acids such as acetic acid, organic anhydride compounds, such as acetic anhydride containing iron trichloride, and tetrahydrocarbyl ammonium fluorides, such as Bu4NF. It has been discovered that it is convenient to use the hydrogen fluoride adduct of a tertiary amine. This adduct is capable of removing the protecting groups, also those containing bulky ligands, such as tertiary butyl or phenyl, and thus gives a by-product of ammonium cation which is a cation which can react with the transition metal compound for give a catalytically active complex. It is preferred to use this adduct on the use of a compound such as Bu4NF, because the BuN cation remaining as a by-product can make the activating anion less effective. More preferably, the HF adduct of this tertiary amine corresponding to the desired ammonium ion of the activating compound is used. For example, the triethyl amine would give a triethyl ammonium cation. Typically, the adduct comprises from 1 to 3 moles of HF per mole of amine, preferably 2. The product complex is preferably subjected to a cation exchange reaction with an additional complex compound comprising a cation capable of reacting with a transition metal compound to form a catalytically active transition metal complex, and a charge equilibration anion, wherein the cation and the anion are contained in relative amounts such that they provide a neutral complex compound. The cation capable of reacting with a transition metal compound to form a catalytically active transition metal complex is preferably selected from the group of Bronsted acid cations, carbonium cations, silylium cations, and cationic oxidizing agents. The charge-balancing anion is preferably a halide, sulfate, nitrate, or phosphate. The complex compounds used in the cation exchange reaction are known compounds or can be prepared according to conventional processes. The exchange of cations can be carried out in a suspension or solution, or on a cation exchange column. The cation exchange reaction and the removal of the optional protective groups Pr can be carried out simultaneously. The product of the cation exchange reaction is recovered, for example, by decanting or filtration, and is preferably washed with a hydrocarbon. Subsequently, the complex product can be dried using conventional methods, such as the application of reduced pressure, heat, use of solvent absorbers or a combination thereof. All reactions are preferably carried out under an inert atmosphere in the absence of oxygen and moisture. The compounds M, m + Qm are known compounds, or they can be prepared according to conventional methods. The compounds of the Formula Z ^ Ggf -Pr) r) are typically prepared by reacting X ** (Gq (T-Pr) r) or H (G (T-Pr) r), wherein X ** has the same definition given above, H is hydrogen, and T-Pr is TH or a protected TH group, with M ** or M *, respectively, where M ** and M * are an element of Group 2 and an element of Group 1, respectively. The starting compounds X ** (Gq (T-Pr) r) and H (G_ (T-Pr) r) can be prepared according to conventional organic synthesis methods. Having described the invention, the following examples are provided as an additional illustration, and should not be construed as limiting. Unless otherwise reported, all parts and percentages are expressed on a weight basis.

EXAMPLES The bulk density of the polymers produced in the present examples was determined according to ASTM 1895. The aluminum content on the support material was determined by treatment with sulfuric acid, followed by addition of EDTA and reverse titration with zinc chloride. , as described above.

Example 1 - Preparation of activator A. To a solution of 4-BrMg (C6H4) OSiMe3 (about 20 millimoles, prepared according to the procedure described in J. Org. Chem., 25, 1063, (1960), but using 1,2-dibromoethane in place of methyl iodide to initiate the reaction) in tetrahydrofuran (20). milliliters), a solution of tris (pentafluorophenyl) borane (4.3 grams, 8.4 mmol) in hexane (200 milliliters) was added slowly with vigorous stirring. A viscous solid was separated, and the mixture was stirred for 16 hours. The upper layer of the solid was then decanted, and the residue was washed with two 200-milliliter portions of hexane. The residue was dried under vacuum for 16 hours to give a pale yellow microcrystalline solid. The solid was quenched with a solution of triethyl ammonium chloride in distilled water (85 millimoles in 200 milliliters), and the mixture was stirred for 1 hour. The solution was decanted from the solid, and the residue was treated with a second portion of triethyl ammonium chloride in distilled water (85 millimoles in 200 milliliters). After stirring for 1 hour, the solution was decanted and the solid was washed with two 200 milliliter portions of distilled water. The residue was dissolved in a mixture of methanol (80 milliliters) and water (4 milliliters), and stirred for 16 hours. The solvents were then removed under reduced pressure, and the solid was dried under vacuum for 16 hours to yield 3.6 grams (60 percent yield based on tris (pentafluorophenyl) borane) of a very pale yellow microcrystalline solid. It was found that the solid, analyzed by 13C and 19F NMR spectroscopy, was tris (pentafluorophenyl) (4-hydroxyphenyl) borate of triethyl ammonium [NEt3H] [HOC6H) B (C6F5) 3]. The NMR data indicated that the compound is 95 percent pure. 19 F NMR (tetrahydrofuran, ppm): -127.1 (doublet, 2F, ortho); -163.8 (triplet, 1F, for); -165.9 (triplet, 2F, goal). 13 C NMR (tetrahydrofuran d-8, ppm): 150.5, J = 235 Hz; 138.7, J = 230 Hz; 140.0, J = 245 Hz; 130, broad; 155.8; 135.8; 115.0; 49.0; 11.0. B. To a solution of 28.7 grams (0.16 moles) of p-bromophenol, and 25.0 grams (0.17 moles) of tertiary butyl-dimethylsilyl chloride in THF, was added 35 milliliters (0.25 moles) of triethyl amine. A white precipitate formed, and the mixture was refluxed. After 4 hours, a sample was analyzed by GCMS (Mass Spectroscopy by Gas Chromatography) and this indicated that the reaction was complete. The precipitate was removed by filtration and washed with THF. The THF was evaporated from the filtrate, and the resulting orange-brown oil was vacuum distilled to yield 44.1 grams (93 percent) of a colorless liquid having a boiling point of 75 ° C to 76 ° C to 0.15 mm Hg. The GCMS showed that the product of tertiary-4-bromophenoxybutyl-dimethylsilane is more than 99 percent pure. A solution containing 92 millimoles of t-BuMe2SiOC6H4MgBr was prepared from 26.4 grams (92 millimoles) of t-BuMe2SiOC6H4Br and 2.7 grams (110 millimoles) of Mg in 100 milliliters of THF. The Grignard solution was decanted from the Mg excess. Approximately 37 millimoles of B (C6F5) 3 were dissolved in THF (100 milliliters), and the resulting solution was added to the Grignard reagent solution. The clear homogenous solution was heated for 40 minutes on a water bath at 80 ° C. The 19 F NMR analysis indicated a quantitative conversion in the desired borate. The reaction mixture was cooled to room temperature, and a solution of 33 grams (250 millimoles) of Et3NHCl in water was added. The THF was evaporated until the water began to distill. So, dichloromethane (200 milliliters) was added, and the water phase was separated. The dichloromethane phase was washed with 2 portions of 100 milliliters of water and 2 portions of 100 milliliters of water containing C02 (solid C02 was added to the two-phase system until the pH was 7). The dichloromethane solution was dried over sodium sulfate, filtered and evaporated, resulting in an oil. Yield: 45 grams. An H NMR spectrum of this material showed the presence of t-BuMe2Si? C6H4B (C6F5) 3.Et3NH and t-BuMe2SiOC6H5 in a molar ratio of about 1: 1. The oil was stirred with pentane (100 milliliters) for 15 minutes. The pentane was decanted and the procedure was repeated with three other 100 milliliter portions of pentane. The resulting oil was dried under vacuum (0.1 mbar) to produce a beige foam. The yield was 33 grams (quantitative). The spectra of 1H and 19F NMR indicated that the material is t-BuMeSiOC6H4B (C6F5) 3. Nearly pure Et3NH. 17 grams (20.7 millimoles) of this product were dissolved in THF (100 milliliters). To this solution, an Et3N.3HF mixture (5 grams, 31.3 mmol) and Et3N (3.1 grams, 31.3 mmol) (effectively Et3N.2HF) were added. After 14 hours, the 1H and 19F NMR of the entire mixture showed that the deprotection was complete, and that no side products were formed. The THF was evaporated and 100 milliliters of 0.5 M NaOH and 200 milliliters of diethyl ether were added to the residue. The aqueous phase was separated and the ether was washed with 3 portions of 50 milliliters of 0.5 M NaOH, two 50 milliliter portions of water, and two 50 milliliter portions of water containing C02. The ether was dried over sodium sulfate, filtered and evaporated. The residue was dissolved in 50 milliliters of dichloromethane, and evaporated again (repeated three times). The resulting beige foam was dried under vacuum (0.1 mbar) overnight, which produced 12.8 grams of HOC6HB (C6F5) 3.Et3NH (a yield of about 90 percent, based on B (C6F5) 3). The spectra of? and 19 F NMR showed that the compound was pure. 19F NMR (solvent: THF-d8) ppm: -126.5 (doublet, 2F, ortho); -163.0 (triplet, 1F, for); -165.5 (double, 2F, goal). AH NMR (solvent: THF-d8): 1.25 (triplet, 9H); 3.15 (quartet, 6H); 6.35; 7.05 (AB, 4H); 7.05 (broad, 2H). C. The starting compound, 4-bromo-N-methylaminobenzene, was synthesized from N-methylaminobenzene according to Organic Syntheses, volume 55, pages 20-24. The next step in the synthesis method is a modified version of the die in J. Org. Chem., 40, 1090, 1975. To a solution of 18.6 grams (0.1 moles) of 4-bromo-N-methylaminobenzene in 200 milliliters of THF, a solution of 67 milliliters of butyl lithium was added at 0 ° C. 1.5 molar normal in hexane. A pale yellow precipitate formed. After 10 minutes, a solution of 15.1 grams (0.1 mole) of tertiary butyl-dimethylsilyl chloride in 20 milliliters of THF was added. The temperature of the reaction mixture was allowed to rise to room temperature, and the mixture was then refluxed for 6 hours. The solvents were evaporated and the distillation of the residue gave 2.0 grams (93 percent) of yellow liquid tertiary-4-bromo-N-butyl-dimethylsilyl-N-methylaminobenzene at a distillation temperature of 100 ° C at 110 ° C at 0.3 mm Hg. The purity determined by GCMS was at least 99.5 percent. To 2.4 grams (0.1 moles) of magnesium turnings, approximately 10 percent of a solution of 28.0 grams (93 millimoles) of 4-bromo-N-butyl tertiary-dimethylsilyl-N-methylaminobenzene in 100 milliliters of THF was added. . 1,2-Dibromomethane (100 microliters) was added, and the reaction was initiated by heating to reflux temperature. The rest of the aniline solution was added in 40 minutes, and the mixture was heated at regular times to keep the reaction continuous. After the addition was complete, the mixture was refluxed for 2 hours. A sample was quenched with water and analyzed by GCMS: main peak: M = 221 (N-butyl tertiary-dimethylsilyl-N-methylaminobenzene). To the THF solution of the Grignard reagent, 780 milliliters of a solution containing 31.2 millimoles of tris (pentafluorophenyl) boron in heptane was added at room temperature and with vigorous stirring. The reaction mixture was stirred for 16 hours at room temperature. A viscous material was separated. The top layer was decanted and the precipitate was washed with three 100-milliliter portions of hexane. The residue was dried under vacuum (0.1 mm Hg) for a few hours to produce a white foam. This product of magnesium bromide (4-N-butyl tertiary-dimethylsilyl-N-aminomethylphenyl) -tris (pentafluorophenyl) borate was used for the next step without further purification. To the reaction product from the previous step was added a solution of 60 grams of triethyl ammonium chloride in 100 milliliters of demineralized water. The mixture was stirred for 2 hours, and a homogeneous emulsion formed. The reaction mixture was extracted with four 50 milliliter portions of dichloromethane, and the combined dichloromethane extracts were washed three times with 50 milliliters of demineralized water. The dichloromethane was dried over magnesium sulfate. Filtration and evaporation of the solvent gave the product of triethyl ammonium (4-N-butyl-tertiary-dimethylsilyl-N-methylaminophenyl) -tris (pentafluorophenyl) borate. The product of the above reaction step was dissolved in a mixture of 150 milliliters of methanol, 50 milliliters of water, and 2 grams of triethyl ammonium chloride, and stirred for 16 hours at room temperature. The methanol was evaporated and 100 milliliters of demineralized water was added to the residue. The suspension was extracted with four 30 milliliter portions of dichloromethane, and the combined dichloromethane extracts were dried over magnesium sulfate. After filtration and evaporation of the solvent, 19.6 grams (76 percent) of a dark brown powder remained. For another purification, the product was washed three times with toluene. To remove the last traces of toluene, the material was mixed twice with 40 milliliters of dichloromethane, and the solvent was evaporated. In the course of this treatment, the material became less soluble in this solvent. For the last purification step, the product was mixed with 100 milliliters of dichloromethane and heated. After cooling, the material was filtered over a Büchner funnel to give, after vacuum drying, 12.8 grams (50 percent) of the pure product of triethyl ammonium (4-N-methylaminophenyl) tris- (pentafluorophenyl) orate. H NMR (THF-d8 and acetone-d6): 1.20 (triplet, 9H); 2.70 (singlet, 3H); 3.10 (quartet, 6H); 5.90 (broad, 2H); 6.35; 7.15 (AB, 4H). 13 C-NMR (THF-d 8): 148.9 (J = 238); 138.3 (J = 233); 136.9 (J = 263); 129.0 (broad); 146.5; 134.2; 111.8; 47.1; 31.0; 9.0. 19 F-NMR (THF-d 8 + benzene-d 6): -127.0 (doublet, 2F, ortho); -163.0 (triplet, 1F, for); -165.5 (triplet, 2F, goal). D. In a manner analogous to the procedure of Example IA, tris (pentafluorophenyl) (4-hydroxymethylphenyl) borate of triethyl ammonium was prepared using 4-MgBr (C6H4) CH2OSi (t-Bu) Me2 prepared by the reaction of 4-bromobenzyl alcohol with t-BuMe2SiCl, and converting the reaction product with magnesium in the Grignard reagent. E. HCl salts of the amines were prepared quantitatively: trioctyl amine, normal dimethyloctyl amine, dimethylphenyl amine, and benzyldimethyl amine, conducting hydrogen chloride gas through a solution of diethyl ether of the amine, until the pH remained acidic. (approximately 5 minutes). The solid material, in each case isolated by filtration, was washed with diethyl ether and dried under vacuum. Tris (pentaf luorofeni 1) (4-hydroxyphenyl) borate of triethyl ammonium (1.4 grams, 2 mmol) was dissolved in 25 milliliters of dichloromethane. An ion exchange reaction was carried out by accepting this solution six times with a solution of 4 millimoles of the respective HCl salt of the above amines in 20 milliliters of water. The dichloromethane solution was washed five times with 20 milliliter portions of water and then dried over magnesium sulfate. The mixture was filtered, and the filtrate was evaporated to dryness in vacuo, to provide the appropriate ammonium salt. The yield in each case was 90 percent, and the multinuclear NMR spectroscopy was in complete agreement with the proposed structures.

Example 2 - Preparation of Support Material Treated with an Aluminum Component A. A 250 milliliter flask was charged with 5 grams of granular silica SD 3216.30 (having a specific surface area of approximately 300 square meters / gram, a volume of pores) of approximately 1.5 cubic centimeters / gram, and an average particle size of 45 microns), available from Grace GmbH, which had been heated at 250 ° C for 3 hours under vacuum, to give a final water content of less than 0.1 percent in weight, determined by differential scanning calorimetry. 101 grams of a 10 weight percent solution of methyl alumoxane (MAO) in toluene, available from Witco GmbH, were added and the mixture was stirred for 16 hours at room temperature. After this time the toluene was removed under reduced pressure at 20 ° C, and the solids were dried under vacuum for 16 hours at 20 ° C, to give a free-flowing powder. The powder was heated at 175 ° C for 2 hours under vacuum. The powder was re-formed into a paste in toluene (130 milliliters), and the mixture was heated to 90 ° C and stirred for 1 hour. The mixture was filtered and the resulting solid was washed with two 50 milliliter portions of fresh toluene at 90 ° C. The support was then dried under vacuum at 120 ° C for 1 hour. 11.1 grams of support were obtained with an aluminum content of 23.8 percent.

B. A 250 milliliter flask was charged with 5 grams of granular silica SD 3216.30, available from Grace GmbH, which had been heated at 250 ° C for 3 hours under vacuum, to give a final water content of less than 0.1 percent by weight. weight, determined by differential scanning calorimetry. 101 grams of a 10 weight percent solution of MAO in toluene was added, and the mixture was stirred for 16 hours. The solid material was isolated by filtration, and then re-formed into toluene (80 milliliters), and the mixture was heated to 90 ° C and stirred for 1 hour. The mixture was filtered and the resulting solid was washed with two 50 milliliter portions of fresh toluene at 90 ° C. The support was then dried under vacuum at 120 ° C for 1 hour. 6.7 grams of support was obtained which had an aluminum content of 13.6 percent. C. A 250 milliliter flask was charged with 5 grams of granular silica SD 3216.30, available from Grace GmbH, containing 2.8 percent water, and 101 grams of a 10 percent by weight solution of MAO in toluene was added. , and the mixture was stirred for 16 hours. The solid material was isolated by decantation, and then re-formed into toluene (80 milliliters), and the mixture was heated to 90 ° C and stirred for 1 hour. The mixture was filtered and the resulting solid was washed with two 50 milliliter portions of fresh toluene at 90 ° C. The support was then dried under vacuum at 120 ° C for 1 hour. 7.3 grams of support having an aluminum content of 15.4 percent was obtained. D. A 250 milliliter flask was charged with 10 grams of granular silica SD 3216.30, available from Grace GmbH, which had been heated at 250 ° C for 3 hours under vacuum, to give a final water content of less than 0.1 weight percent, as determined by differential scanning calorimetry. 36 grams of a 10 weight percent solution of MAO in toluene was added and the mixture was stirred for 16 hours. The solid material was isolated by filtration, and then re-formed into toluene (100 milliliters), and the mixture was heated to 90 ° C and stirred for 1 hour. The mixture was filtered and the resulting solid was washed with two 50 milliliter portions of fresh toluene at 90 ° C. The support was then dried under vacuum at 120 ° C for 1 hour. 13.1 grams of support having an aluminum content of 12.3 percent was obtained. E. A 250 milliliter flask was charged with 10 grams of granular silica SD 3216.30, available from Grace GmbH, which had been heated at 250 ° C for 3 hours under vacuum, to give a final water content of less than 0.1 weight percent, determined by differential scanning calorimetry. 72 grams of a 10 weight percent solution of MAO in toluene was added, and the mixture was stirred for 16 hours. The solid material was isolated by filtration, and then re-formed into a paste in toluene (100 milliliters), and the mixture was heated to 90 ° C and stirred for 1 hour. The mixture was filtered and the resulting solid was washed with two 50 milliliter portions of fresh toluene at 90 ° C. Then the support was dried under vacuum at 120 ° C for 1 hour. 13.3 grams of support having an aluminum content of 11.4 percent was obtained. F. A 250 milliliter flask was charged with toluene (50 milliliters), and trimethyl aluminum (13.5 milliliters, 0.141 mol). Five grams of silica SP-9-10046 (available from Grace Davison) having a water content of 4.5 weight percent was added, based on the combined weights of water and support, and the mixture was stirred for 16 hours. The mixture was filtered and the support was washed with toluene (50 milliliters, approximately at 100 ° C), and dried under a high vacuum. 5.2 grams of the support of an aluminum content of 7.3 percent by weight were obtained. G. A 250 milliliter flask was charged with toluene (50 milliliters) and triethyl aluminum (11 milliliters, 0. 08 moles). 6.3 grams of silica SP-9-10046 having a water content of 4.5 weight percent was added, and the mixture was stirred for 1 hour. The mixture was filtered and the support was washed with toluene (50 milliliters, approximately at 100 ° C), and dried under a high vacuum. 6.3 grams of the support of an aluminum content of 5.3 percent by weight were obtained. H. A 250 milliliter flask was charged with toluene (50 milliliters) and triethyl aluminum (7 milliliters, 0.051 moles). Five grams of silica SP-9-10046 that had been treated at 250 ° C for 3 hours under vacuum was added, and the mixture was stirred for 16 hours. The mixture was filtered and the support was washed with toluene (50 milliliters, approximately at 100 ° C), and dried under a high vacuum. 5.1 grams of the support of an aluminum content of 4.7 weight percent were obtained.

Preparation of Supported Catalyst Example 3 Two grams of the support treated as described in Example 2A, were formed into a paste in toluene (20 milliliters), and to this was added tris (pentafluorophenyl) (4-hydroxyphenyl) borate of triethyl ammonium prepared in Example 1 (0.224 grams, 0.32 mmol) in toluene (10 milliliters). The mixture was stirred for 16 hours, and then filtered and washed with toluene (3 x 10 milliliters), and dried under vacuum at 20 ° C. One gram of the solid was formed in a paste in toluene (15 milliliters), and the mixture was stirred for a few minutes. An aliquot of 0.56 milliliters of a 0.0714 dark orange-brown solution (40 micromoles) of titanium [(butyl tertiary-amido) (dimethyl) (tetramethyl-? 5-cyclopentadienyl) silane] dimethyl (subsequently in the present MCpTi) was added in ISOPAR11 E (registered trademark of Exxon Chemical Company), and the mixture was stirred for a few minutes, filtered, washed with toluene (2 x 10 milliliters), and dried under vacuum to give a bright yellow supported catalyst. . The supported catalyst was re-formed into a paste in 10 milliliters of hexane for use in a paste polymerization reaction.

Example 4 0.5 grams of the treated support as described in Example 2A, were formed into a paste in toluene (10 milliliters), and stirred for a few minutes. This paste was added to a mixture of tris (pentafluorophenyl) (4-hydroxyphenyl) borate of triethyl ammonium prepared in Example 1 (0.042 grams, 60 micromoles) in toluene (10 milliliters), and the mixture was stirred for 16 hours. The solids were filtered and washed with 2 x 10 milliliters of toluene, and re-formed into a paste in toluene (10 milliliters). 20 micromoles of MCpTi were added in ISOPAR E, to give a yellow-brown solid phase and a colorless supernatant. The mixture was stirred for a few minutes before being used in a polymerization reaction.

Example 5 The procedure of Example 4 was repeated, except that 0.028 grams (40 micromoles) of tris (pentafluorophenyl) (4-hydroxyphenyl) borate of triethyl ammonium were employed. A supported catalyst consisting of a yellow-brown solid phase and a colorless supernatant was obtained.

Example 6 The procedure of Example 4 was repeated, except that 0.014 grams (20 micromoles) of tris (pentafluorophenyl) (4-hydroxyphenyl) borate of triethyl ammonium were used. A supported catalyst consisting of a yellow-brown solid phase and a colorless supernatant was obtained.

Example 7 0.25 grams of the support treated as described in Example 2B, were formed into a paste in toluene (5 milliliters), and stirred for a few minutes. This paste was added to a mixture of tris (pentafluorophenyl) (4-hydroxyphenyl) borate of triethyl ammonium (0.014 grams, 20 micromoles) in toluene (5 milliliters), and the mixture was stirred for 16 hours. The toluene was removed by filtration, and the solids were washed with 2 x 10 milliliters of toluene and re-formed into a paste in toluene (10 milliliters). 10 micromoles of MCpTi were added in ISOPAR * ® E, and the mixture was stirred for a few minutes before being used in a polymerization reaction. A supported catalyst consisting of a yellow-brown solid phase and a colorless supernatant was obtained.

Example 8 The procedure of Example 7 was repeated, except that before the addition of the transition metal compound, the supported catalyst component comprising the treated silica and the tris (pentafluorophenyl) (4-hydroxyphenyl) borate of triethyl ammonium, did not it was washed with toluene.

Example 9 The procedure of Example 7 was repeated, except that, before the addition of the transition metal compound, the supported catalyst component comprising the treated silica and the tris (pentafluorophenyl) (4-hydroxyphenyl) borate of triethyl ammonium did not it was washed with toluene. Also, 0.028 grams (40 micromoles) was used instead of 0.014 grams of tris (pentafluorophenyl) (4-hydroxyphenyl) borate of triethyl ammonium.

Example 10 The procedure of Example 9 was repeated except that half the amount of the final supported catalyst, which contained approximately 5 micromoles of MCpTi, was used in a polymerization reaction.

Example 11 The procedure of Example 9 was repeated, except that the support treated was used as in Example 2C.

Example 12 The procedure of Example 9 was repeated, except that the support treated was used as in Example 2D.

Examples 13 and 14 The procedure of Example 9 was repeated, except that the support treated as in Example 2E was used.

Examples 15 and 16 The procedure of Example 9 was repeated, except that the support treated as in Example 2E was used, and 0.021 grams (30 micromoles) of tris (pentafluorophenyl) (4-hydroxyphenyl) borate of triethyl ammonium were used.

Example 17 0.25 grams of the treated support as described in Example 2E, were formed into a paste in toluene (5 milliliters), and stirred for a few minutes. 10 micromoles of MCpTi were added in ISOPAR E, and the mixture was stirred for 15 minutes. The mixture was added to 0.028 grams (40 micromoles) of tris (pentaf luorophenyl) (4-hydroxyphenyl) borate of triethyl ammonium in toluene (10 milliliters), and the mixture was stirred for 16 hours to give a supported catalyst comprising one phase solid yellow-chestnut and a colorless supernatant.

Example 18 0.014 grams (20 micromoles) of tris (pentafluorophenyl) (4-hydroxyphenyl) borate of triethyl ammonium was added to toluene (10 milliliters), and the mixture was stirred for a few minutes. 20 micromoles of MCpTi were added in ISOPAR E, and the mixture was stirred for 30 minutes. The color changed from yellow to red. 0.5 grams of the treated support was added as described in Example 2A in toluene (10 milliliters), and the mixture was stirred for 16 hours.

Example 19 - Preparation of Supported Catalysts 1.5 grams of the supported catalyst components prepared in Examples 2F (Example 19A), 2.G (Example 19B), and 2.H (Example 19C), were formed into a paste in toluene ( 20 milliliters), and the mixture was stirred for a few minutes to disperse the support. The paste was added to a solution of tris (pentafluorophenyl) (4-hydroxyphenyl) borate of triethyl ammonium (0.084 grams, 0.120 millimoles) in toluene (60 milliliters), which had previously been heated to a temperature of 65 ° C to 70 ° C. C. The mixture was stirred for 30 minutes at this temperature, and then the heating was discontinued and the mixture was allowed to cool to room temperature. Stirring was continued for an additional 16 hours. An aliquot of 0.84 milliliters of a 0.0714 M dark violet solution (60 micromoles) of titanium, (Nl, l-dimethylethyl) dimethyl (l- (l, 2, 3,4,5, -eta) -2, 3 was added. , 4,5-tetramethyl-2,4-cyclopentadien-l-yl) silanaminate)) (2-) N) - (? 4-1,3-pentadiene) (subsequently in the present MCpTi (II)) in IS0PARMR E (registered trademark of Exxon Chemical Company), and the mixture was stirred for about 1 hour to give a green supported catalyst. The catalyst was used as such in a paste polymerization.

Example 20 - Preparation of Supported Catalyst Tris (pentaf luoro fen i 1) (4-hydroxyphenyl) borate of triethyl ammonium was dissolved (0.0707 grams, 0.1 mmol) in toluene (100 milliliters), by heating the mixture at 70 ° C for 15 minutes. A solution of triethyl aluminum (50 milliliters of a 0.002 M solution in toluene, 0.1 mmol) was added, and the mixture was stirred for 5 minutes. 1 gram of silica SP-9-10046, which had been treated at 250 ° C for 3 hours under vacuum, was formed into a paste in toluene (20 milliliters) for 15 minutes, and then this paste was added to the adduct solution of borate / triethyl aluminum, and the mixture was stirred for 5 minutes at a temperature of 70 ° C. Triethyl aluminum (0.24 milliliters, 2 mmol) was added, and the mixture was stirred for an additional 5 minutes at 70 ° C. The mixture was filtered and the support washed once with toluene (100 milliliters, 70 ° C), and twice with 100 milliliters of boiling hexane. Then the support was dried under reduced pressure. 0.25 grams of the support were formed in a paste in hexane (10 milliliters), and 0.14 milliliters of a 0.0714 M solution of MCpTi (II) (10 micromoles) in hexane was added. The mixture was stirred for 16 hours to give a supported catalyst consisting of a green solid phase and a colorless supernatant. The catalyst was used as such in a paste polymerization.

Example 21 - Preparation of Supported Catalyst 1.5 grams of a previously treated support prepared as in Example 2H, was formed into a paste in toluene (20 milliliters) for a few minutes to disperse the support. The paste was added to a mixture of tris (pentafluorophenyl) (4- ((N-methyl) amino) phenyl) borate of triethyl ammonium (0.087 grams, 0.120 millimoles) in toluene (40 milliliters), which had previously been heated to a temperature from 65 ° C to 70 ° C. The mixture was stirred for 30 minutes at this temperature, and then the heating was removed and the mixture was allowed to cool to room temperature. Stirring was continued another 16 hours. An aliquot of 0.84 milliliters of a 0.0714 M solution (60 micromoles) of MCpTi (II) in hexane was added, and the mixture was stirred for approximately 16 hours to give a green / tan supported catalyst. The catalyst was used as such in a paste polymerization.

Example 22 - Preparation of Supported Catalyst 30 grams of Si02 SP-9-10046 treated at 250 ° C for 2 hours under vacuum, formed in a paste in toluene (300 milliliters), and a solution of triethyl aluminum (30 milliliters) was added , 0.22 moles) in toluene (200 milliliters). The mixture was stirred for 1 hour, filtered, washed with two 100 milliliter portions of fresh toluene, and dried in vacuo. To 20 grams of the resulting powder were added toluene (200 milliliters). The mixture was stirred for a few minutes to disperse the support. This paste was added to a solution of tris (pentafluorophenyl) (4-hydroxyphenyl) borate of triethyl ammonium (1.125 grams, 1.6 mmol) in toluene (200 milliliters), which had been heated to 70 ° C and maintained at 70 ° C. for 30 minutes. Upon addition, the heating was removed and the mixture was stirred at room temperature for 16 hours. A 40 milliliter aliquot of the resulting paste (containing about 1 gram of the support) was removed, and to this 0.47 milliliters of a 0.0855 M solution of bis (indenyl) zirconium dimethyl (Witco GmbH) (40 micromoles of Zr) was added. The mixture was stirred for a few minutes to give a supported orange catalyst. An aliquot of this supported catalyst containing 14 micromoles of zirconium as such was used in a paste polymerization.

Example 23 - Preparation of Supported Catalyst 20 grams of Si02 (SP-9-10046) treated at 250 ° C for 2 hours under vacuum, formed into a paste in toluene (300 milliliters), and triethyl aluminum (20 milliliters, 0.147 moles). The mixture was stirred for 1 hour, filtered, washed with two 100 milliliter portions of fresh toluene, and dried in vacuo. To 1.5 grams of the resulting powder were added toluene (20 milliliters). The mixture was stirred for a few minutes to disperse the support. This paste was added to a solution of tris (pentafluorophenyl) (4-hydroxymethylphenyl) borate of triethyl ammonium (0.086 grams, 0.12 millimoles) in toluene (40 milliliters), which had been heated to 70 ° C, and maintained at 70 ° C. C for 1 hour. After the addition, the heating was removed, and the mixture was stirred at room temperature for 16 hours. 0.84 milliliters of a 0.0714 M solution of MCpti (II) (60 micromoles of Ti) were added, and the mixture was stirred for 1 hour to give a supported green-brown catalyst. An aliquot of this supported catalyst containing 10 micromoles of titanium as such was used in a paste polymerization.

Example 24 - Copolymerization of Ethylene / l-Octene in Paste Phase A catalyst was prepared as in Example 19C. 20 micromoles of the catalyst were used, based on titanium, in a paste polymerization. 250 milliliters of 1-octene was added to the reactor. An ethylene / 1-octene copolymer of a density of 0.9376 grams / cubic centimeter was prepared.

Examples 25-26 - Preparation of Supported Catalyst 30 grams of Si02 (SP-9-10046) treated at 250 ° C for 2 hours under vacuum, they were formed into a paste in toluene (300 milliliters), and triethyl aluminum (30 milliliters, 0.22 moles) was added. The mixture was stirred for 1 hour, filtered, washed with 2 portions of 100 milliliters of fresh toluene, and dried in vacuo. To 3 grams of the resulting powder were added toluene (20 milliliters). The mixture was stirred for a few minutes to disperse the support. This paste was added to a solution of tris (pentafluorophenyl) (4-hydroxyphenyl) borate of triethyl ammonium (0.126 grams, 0.18 mmol) in toluene (40 milliliters), which had been heated to 80 ° C, and maintained at 80 °. C for 1 hour. After the addition, heating was discontinued, and the mixture was stirred at room temperature for 16 hours. 1.68 milliliters of a 0.0714 M solution of MCpTi (II) was added, and the mixture was stirred for 1 hour to give a green supported catalyst. Another 3 gram portion of the resulting powder was treated according to the same procedure, although using 0.105 grams, 0.15 millimoles of borate which had been treated at 70 ° C and kept at 70 ° C for 1 hour. Aliquots of the resulting supported catalysts containing 10 micromoles of titanium as such were used in a paste polymerization.

Comparative Example 1 0.5 grams of silica SD 3216.30 (dehydrated for 3 hours at 250 ° C under vacuum) were formed into a paste in toluene (10 milliliters), stirred for a few minutes, and then added to tris (pentafluorophenyl) ( 4-hydroxyphenyl) triethyl ammonium borate (0.028 grams, 40 micromoles) in toluene (10 milliliters), and the mixture was stirred for 16 hours. 20 micromoles of MCpTi were added in ISOPAR E, to give a pale yellow solid phase and a colorless supernatant.

Comparative Example 2 Triethyl ammonium tris (pe nt af 1 uorofeni 1) (4-hydroxyphenyl) borate (0.014 grams, 20 micromoles) was treated in 10 milliliters of toluene, with 20 micromoles of MCpTi in ISOPAR E. The mixture of red color The resultant was stirred for a few minutes, and then used as such in a polymerization reaction.

Example 27 - Polymerization Tests A 10 liter autoclave reactor was charged with 6 liters of anhydrous hexane, 1 liter of hydrogen gas, and the contents of the reactor were heated to 80 ° C, unless otherwise indicated, at which temperature the polymerization mixture was maintained during the polymerization. Then ethylene was added in order to raise the pressure to the desired operating level of 10 bar, unless otherwise indicated. A sample of the supported catalyst prepared in the examples and comparative examples above was added to the reactor through a pressurized addition cylinder in the amounts indicated in the table below. Ethylene was supplied to the reactor continuously to maintain constant pressure. After the desired reaction time, the ethylene line was blocked and the contents of the reactor turned to a sample vessel. The hexane was removed from the polymer and the polymer was dried overnight, and then weighed to determine the efficiencies of the catalyst. In none of the examples of the invention did substantial contamination of the reactor occur, and all the examples gave a polymer in a free-flowing powder form. The Table summarizes the specific conditions and results of the paste polymerizations with the supported catalyst prepared above.

Example 28 - Continuous Polymerizations in Paste Phase 20 grams of Si02 treated with triethyl aluminum (prepared as in Example 22) were formed into a paste in toluene (200 milliliters), and the mixture was heated to 80 ° C. In a separate vessel, tris (pentafluorophenyl) (4-hydroxyphenyl) borate of triethyl ammonium (1.125 grams, 1.6 mmol) was added to toluene (400 milliliters), and the mixture was heated to 80 ° C and maintained at 80 ° C. for 1 hour. The borate solution was added to the support stock and the mixture was stirred and maintained at 80 ° C for 2 hours. The mixture was cooled and stirred overnight. The toluene was decanted from the support, and replaced with hexane (800 milliliters). This procedure was repeated. 8 millimoles of type 3A MMAO (20 weight percent solution in heptane from AKZO) were added, and the mixture was stirred for 15 minutes. 11.2 milliliters of a 0.0714 M solution of MCpTi (II) was added, and the mixture was stirred for 2 hours before use. The support contained a boron load of 80 micromoles / gram and a titanium load of 40 micromoles / gram. Isopentane, ethylene, 1-butene (if required), hydrogen, and supported catalyst were continuously fed into a continuously stirred, jacketed 10-liter tank reactor, and the formed paste product was continuously stirred. The total pressure in all the polymerization tests was 15 bar, and the temperature was maintained at 70 ° C. The removed paste was fed to an evaporation tank to remove the diluent, and the free flowing dry polymer powder was collected. In a first test, the following conditions were used: isopentane flow of 2,500 grams / hour; ethylene flow of 1,200 grams / hour; Hydrogen flow of 0.4 1 / hour; temperature of 70 ° C to produce a product with a bulk density of 0.354 grams / cubic centimeter, and a melt flow index, measured at 190 ° C and with a load of 21.6 kilograms of 1.4 grams / 10 minutes, with a efficiency of 1,500,000 grams of PE / gram of Ti. In a second test, the following conditions were used: isopentene flow of 2,500 grams / hour; ethylene flow of 800 grams / hour; butene flow of 42.5 grams / hour; hydrogen flow of 0.45 liters / hour; temperature of 70 ° C to produce a product with a bulk density of 0.300 grams / cubic centimeter, a density of 0.9278 grams / cubic centimeter, a butene content of 1.42 molar percent, and a melt flow index, measured at 190 ° C and with a load of 2.16 kilograms of 0.85 grams / 10 minutes, with an efficiency of 650,000 grams of PE / gram of Ti.

Example 29 - Polymerizations in Solution Phase 30 grams of SiO2 (SP-9-10046) treated at 250 ° C for 3 hours under vacuum, formed in a paste in toluene (300 milliliters), and added triethyl aluminum (30 milliliters) , 0.22 moles). The mixture was stirred for 1 hour, filtered, washed with two 100 milliliter portions of fresh toluene, and dried in vacuo. To 10 grams of the resulting powder were added toluene (150 milliliters). The mixture was stirred for a few minutes to disperse the support. This paste was added to a solution of tris (pentafluorophenyl) (4-hydroxyphenyl) borate of triethyl ammonium (0.565 grams, 0.8 mmol) in toluene (250 milliliters) which had been heated to 70 ° C, and maintained at 70 ° C. for 1 hour. After the addition, the heating was removed, and the mixture was stirred at room temperature for 16 hours. A 50 milliliter aliquot of the pulp was treated with 0.7 milliliters of a 0.0714 M solution of MCpTi (II) (50 micromoles of Ti), followed by 500 micromoles of MMAO, and the mixture was stirred for 1 hour to give a supported catalyst green-brown. Aliquots of this supported catalyst containing 2 and 1.25 micromoles of titanium, respectively, were used. A 3 liter autoclave reactor was charged with the desired amount of 1-octene, followed by an amount of ISOPAR ** 1 * E sufficient to give a total volume of 1,500 milliliters. 300 milliliters of hydrogen gas were added, and the contents of the reactor were heated to the desired temperature. Then enough ethylene was added to bring the system pressure up to 30 bar. A supported catalyst was added to initiate the polymerization, and ethylene was supplied to the reactor continuously on demand. After 10 minutes, the ethylene line was blocked, and the contents of the reactor were flipped in a sample container. The polymer was dried overnight, and then weighed to determine catalyst efficiencies. The specific conditions were: Test 1: 121 milliliters of octene; temperature of 130 ° C; to give 82 grams of the product (efficiency of 854,000 based on grams of PE / gram of Ti) of a melt index (at 190 ° C / 2.16 kilograms of load) of 3.8, and a density of 0.9137. Test 2: 450 milliliters of octene; temperature of 80 ° C; to give 47 grams of the product (efficiency of 785,000 based on grams of PE / gram of Ti) of a melt index (190 ° C / 2.16 kg) of 1.66 grams / 10 minutes, and a density of 0.8725 grams / cubic centimeter. a The pressure was 15 bar. b All proportions and quantities given relate to the proportions / quantities used in the preparation of the supported catalysts according to the particular examples, c The temperature was 60 ° C. d The temperature was 40 ° C and the pressure was 7 bar. 10 e The temperature was 40 ° C and the pressure was 6 bar. f 100 micromoles of Type 3A AKZO MMAO was added to the polymerization reactor before the catalyst. 15 g 300 micromoles of AKZO Type 3A MMAO were added to the polymerization reactor before the catalyst, h The temperature was 30 ° C. 100 micromoles of (i-Bu) 3Al were added to the polymerization reactor before the catalyst.

Claims (23)

1. A supported catalyst component comprising: (a) a support material, an organometallic compound wherein the metal is selected from Groups 2-13 of the Periodic Table of the Elements, germanium, tin, and lead, and ( b) an activating compound comprising: bl) a cation that is capable of reacting with a transition metal compound to form a catalytically active transition metal complex, and b.2) a compatible anion having up to 100 atoms that does not are hydrogen, and which contains at least one substituent comprising an active hydrogen fraction.

2. A supported catalyst component according to claim 1, wherein the support material comprises silica.

3. A supported catalyst component according to claim 1, wherein the organometallic compound is an aluminum component selected from the group consisting of alumoxane, an aluminum compound of the formula A1R1X, wherein R1, independently in each presentation is hydrogen or a hydrocarbyl radical having 1 to 20 carbon atoms, and x is 3, and a combination thereof.

4. A supported catalyst component according to any of claims 1 to 3, wherein, in the anion b.2), the substituent comprising an active hydrogen fraction corresponds to the formula: Gq (T-H) r wherein G is a polyvalent hydrocarbon radical, T is O, S, NR, 6 PR, wherein R is a hydrocarbyl radical, a trihydrocarbylsilyl radical, a trihydrocarbyl methyl radical, or hydrogen, H is hydrogen, q is 0 or 1, and r is an integer from 1 to 3.

5. A supported catalyst component according to any of claims 1 to 4, wherein the compatible anion portion of the activating compound corresponds to the general formula (I): [M'm * Q "(Gq (T-H) r).] '(I) wherein: M * is a metal or metalloid selected from Groups 5-15 of the Periodic Table of the Elements; Q, independently in each presentation, is selected from the group consisting of hydride, dihydrocarbyl ids, halide, hydrocarbyl oxide, . Hydrocarbyl, and substituted hydrocarbyl radicals, including hydrocarbyl radicals substituted by halogen, and organic metalloid radicals substituted by hydrocarbyl and hydrocarbyl halogenated, the hydrocarbyl portion having from 1 to 20 carbon atoms, with the proviso that no more than one presentation Q is halide; G is a polyvalent hydrocarbon radical having the valences r + 1, linked with M 'and T; 10 T is O, S, NR, 6 PR, wherein R is a hydrocarbyl radical, a trihydrocarbylsilyl radical, a trihydrocarbyl methyl radical, or hydrogen; m is an integer from 1 to 7, n is an integer from 0 to 7, 15 q is an integer of 0 or 1; r is an integer from 1 to 3, z is an integer from 1 to 8j d is an integer from 1 to 7 n + z-m = d.

6. A supported catalyst component according to any of claims 1 to 5, wherein the cation b.l) is selected from the group consisting of Bronsted acid cations, cations of 25 carbonium, silylium cations, and cationic oxidizing agents.

7. A supported catalyst comprising the supported catalyst component of any of claims 1 to 6, and (c) a transition metal compound containing a substituent capable of reacting with the activating compound (b) to thereby form a catalytically active transition metal complex.

8. A process for the preparation of a supported catalyst component, which comprises combining a support material (a), an organometallic compound wherein the metal is selected from Groups 2-13 of the Periodic Table of the Elements , germanium, tin, and lead, and an activating compound (b) comprising: bl) a cation that is capable of reacting with a transition metal compound to form a catalytically active transition metal complex, and b.2) a compatible anion having up to 100 non-hydrogen atoms, and containing at least one substituent comprising an active hydrogen moiety.

9. A process according to the claim 8, which comprises: (A) subjecting the support material to a heat treatment of 100 ° C to 1000 ° C; combining the thermally treated support material with the organometallic compound in a suitable diluent or solvent; and subsequently combining the resulting product with the activating compound; or (B) combining the activating compound with the organometallic compound to form an adduct; and combining the adduct with the support material; or (C) combining a support material containing water with the organometallic compound; and combining the resulting product with the activating compound.

A process for the preparation of a supported catalyst according to any of claims 8 or 9, which comprises the additional step of adding a transition metal compound (c) containing a substituent capable of reacting with the activating compound (b) to thereby form a catalytically active transition metal complex.

11. An adduct of an organometallic compound, wherein the metal is selected from Groups 2-13 of the Periodic Table of the Elements, germanium, tin, and lead, and an activating compound comprising bl) a cation which is capable of reacting with a transition metal compound to form a catalytically active transition metal complex, and b.2) a compatible anion having up to 100 non-hydrogen atoms, and containing at least one substituent comprising a active hydrogen fraction, obtained by combining the organometallic compound and the activating compound in a suitable diluent or solvent, optionally followed by the removal of the solvent or diluent.

12. An adduct according to claim 11, wherein, in anion b.2), the substituent comprising an active hydrogen fraction corresponds to the formula: Gq (T-H) r wherein G is a polyvalent hydrocarbon radical, T is or, S, NR, or PR, wherein R is a hydrocarbyl radical, a trihydrocarbylsilyl radical, a trihydrocarbylgermyl radical, or hydrogen, H is hydrogen, q is 0 or 1, and r is an integer from 1 to 3.

13. An adduct according to any of claims 11 or 12, wherein the organometallic compound is an aluminum component selected from the group consisting of alumoxane, a compound of aluminum of the formula A1R1X, wherein R1, independently in each presentation, is hydride or a hydrocarbyl radical having 1 to 20 carbon atoms, and x is 3, and a combination thereof.

14. An addition polymerization process, wherein one or more addition polymerizable monomers are contacted under addition polymerization conditions with a supported catalyst according to claim 7, or prepared according to claim 10.

15. The addition polymerization process according to claim 14, carried out under paste or gas phase polymerization conditions.

16. A complex compound comprising a charge equilibrium cation, and a compatible anion corresponding to formula (I): [M'm + Qn (Gq (T-Pr) r) z] d- (I) wherein: M1 is a metal or metalloid selected from Groups 5-15 of the Periodic Table of the Elements; Q, independently in each presentation, is selected from the group consisting of hydride, dihydrocarbylamido, halide, hydrocarbyl oxide, hydrocarbyl, and substituted hydrocarbyl radicals, including hydrocarbyl radicals substituted by halogen, and organic metalloid radicals substituted by hydrocarbyl and by halogenated hydrocarbyl, the hydrocarbyl portion having from 1 to 20 carbon atoms, with the proviso that in no more than one presentation, Q is halide; G is a polyvalent hydrocarbon radical having the valences r + 1, linked with M 'and T; T is H, S, NR, 6 PR, wherein R is a hydrocarbon radical, a trihydrocarbylsilyl radical, a trihydrocarbyl methyl radical, or hydrogen; Pr is hydrogen H or a protecting group; m is an integer from 1 to 7; n is an integer from 0 to 7; q is 1; r is an integer from 1 to 3; z is an integer from 1 to 8; d is an integer from 1 to 7; and n + z-m = d.

17. A complex compound according to claim 16, wherein the cation b.l) is selected from the group consisting of Bronsted acid cations, carbonium or silillo cations, and cationic oxidizing agents.

18. A method for the preparation of a complex compound containing an anion corresponding to formula (I): [M'm + Qn (Gq (T-Pr) r) z] d- (I) '"where: M * is a metal or metalloid selected from Groups 5-15 of the Periodic Table of the Elements; Q, independently in each presentation, is selected from the group consisting of hydride, dihydrocarbylamido, halide, hydroscarbyl oxide, hydrocarbyl, and substituted hydrocarbyl radicals, including hydrocarbyl radicals substituted by halogen, and organic metalloid radicals substituted by The hydrocarbyl and hydrocarbyl halogenated, the hydrocarbyl portion having from 1 to 20 carbon atoms, with the proviso that in no more than one Q presentation is halide; G is a polyvalent hydrocarbon radical having the valences r + 1, linked with M 'and T; T is O, S, NR, or PR, wherein R is a hydrocarbyl radical, a trihydrocarbylsilyl radical, a trihydrocarbyl methyl radical, or hydrogen; Pr is hydrogen H or a protecting group; 20 m is an integer from 1 to 7, n is an integer from 0 to 7, q is an integer of 0 or 1; ', r is an integer from 1 to 3 z is an integer from 1 to 8, 25 d is an integer from 1 to 7, n + z-m = d; and a load balancing cation; in which complex compound, the anion and the cation are contained in such relative amounts to provide a neutral compound, which comprises the steps of combining, in a suitable solvent or diluent, a compound M, m + Qm with a compound of the formula Z1 (Gq (T.Pr) r), where Z1 is [M * X **] + 6 [M **] +, and M * is an element of Group 2, M ** is an element of Group 1 , and X is halogen, G, T, Pr, q, and r have the same meaning as that given for formula (I), followed by the recovery of the product complex. The method of claim 18, wherein the protecting group Pr is a trialkylsilyl, triarylsilyl, or mixtures thereof. The method of any of claims 18 or 19, wherein a molar excess of the compound Z1 (Gq (T-Pr) r) is used with respect to the compound M? M + Qm. 21. The method of claim 20, wherein the temperature is in the range of 40 ° C to 100 ° C. The method of any of claims 18 to 21, wherein Pr is a protecting group, which comprises the additional step of removing the protecting group Pr using a hydrogen fluoride adduct of a tertiary amine. The method of any of claims 18 to 22, which comprises the additional step 5 of subjecting the complex compound to a cation exchange reaction with an additional complex compound comprising a cation capable of reacting with a metal compound of transition to form a catalytically active transition metal complex, from The preference is selected from the group of Bronsted acid cations, carbonium or silylium cations, and cationic oxidizing agents, and a charge equilibration anion, wherein the cation and the anion are contained in such relative amounts to provide a compound 15 neutral complex.