MXPA99005682A - Catalyst component dispersion comprising an ionic compound and solid addition polymerization catalysts containing the same - Google Patents

Abstract

This invention relates to a dispersion of supported and nonsupported catalyst components comprising:(a) an ionic compound comprising (a)(1) a cation and (a)(2) an anion having up to 100 nonhydrogen atoms and the anion containing at least one substituent comprising a moiety having an active hydrogen, and, optionally, (d) a support material, wherein the supported catalyst component is in solid form dispersed in a diluent in which both(a) and (d) are insoluble or sparingly soluble. The catalyst component is combined with (b) a transition metal compound and wherein the catalyst component is a substantially inactive catalyst precursor;or wherein the catalyst component further comprises (c) an organometal or metalloid compound wherein the metal or metalloid is selected from the Groups 1-14 of the Periodic Table of the Elements and the catalyst component is a reaction product of (a) and (c). (a), (b), (c), and, optionally, (d) are combined to produce catalysts. Included are methods for preparation of the catalyst components, catalysts and reaction products, as well as a polymerization process using the catalysts.

Description

IONIC COMPOUNDS FOR CATALYST COMPONENTS, DISPERSIONS. AND SOLID POLYMERIZATION CATALYSTS BY ADDITION THAT CONTAIN THEM Field of the Invention This invention relates to a dispersion of catalyst components comprising an ionic compound in solid form, with an unsupported solid catalyst comprising a transition metal compound, an ionic compound, and an organometal compound, with a supported solid catalyst comprising a transition metal compound, an ionic compound, an organometal compound, and a support material, with a method for preparing the dispersion of catalyst components, with a method for preparing the solid catalysts, with a method for activating a catalyst suitable for addition polymerization, and with an addition polymerization process using the solid catalysts.

BACKGROUND OF THE INVENTION Homogeneous ionic transition metal catalysts are known for their high catalytic activity in addition polymerizations, especially those of olefins and diolefins, and are capable of providing olefinic polymers of narrow molecular weight distributions and, for example, when ethylene is copolymerized with another alpha-olefin, narrow distributions of comonomers. Under the polymerization conditions where the polymer is formed as solid particles, for example, in gas phase or slurry phase polymerizations, these homogeneous (soluble) catalysts form polymer deposits in the walls of the reactor and the agitators, which Deposits must be removed frequently because they prevent an efficient heat exchange necessary to cool the reactor contents, prevent regular or continuous removal of the polymer from the reactor, and cause excessive wear of moving parts in the reactor. The polymers produced by these soluble catalysts also have undesirable particle characteristics such as low mass density, which limits the commercial utility of both the polymer and the process. Therefore, there is a need to provide catalysts that overcome these problems. Many support catalysts have been proposed for use in particle formation polymerization processes. The support materials in the prior art are typically used in combination with catalyst components to obtain the formation of polymer particles of desirable particle size and morphology. Second, support materials are used to increase the catalytic activity per unit of the active components, by depositing these components in a support material having a relatively high surface area. In addition, support materials are used to anchor the catalytic components therein, in order to avoid the presence of significant amounts of catalyst, which under solubilization conditions are dissolved, and originate particles of undesired size and morphology, these particles contributing to the formation of polymer deposits in the walls of the reactor and other moving parts in the reactor. EP-327649 and EP-725086 describe solid catalysts using alumoxanes as cocatalysts. EP-327649 relates to an unsupported olefin polymerization catalyst, composed of a transition metal compound and an alumoxane having an average particle size of 5 to 200 microns, and a specific surface area of 20 to 1,000 meters square / gram. EP-725086 describes a solid component of a catalyst for the (co) polymerization of ethylene and alpha-olefins, comprising a metallocene supported on an inorganic solid carrier, wherein a carbon atom of one of the ring? -cyclopentadienyl, coordinated with the transition metal, is covalently linked to a metal atom of the inorganic solid carrier. This solid component is typically used with an oxy-derived organic aluminum which is usually alumoxane.

The supported non-alumoxane catalysts are described, for example, in EP-418044, EP-522581, 0-91 / 09882, WO-94/03506, O-9403509, and O-9407927. These describe supported catalysts obtained by the combination of a transition metal compound, an activating component comprising a cation capable of reacting with a transition metal compound and a labile, bulky anion capable of stabilizing the formed metal cation, as result of the reaction between the metal compound and the activating component, and a catalyst support material. In EP-522581 and WO-9407927 an organometal compound, typically an organoaluminum compound, is further employed. EP-727443 discloses an olefin polymerization catalyst which can be obtained by contacting a transition metal compound, an organometallic compound, and a solid catalyst component comprising a carrier and an ionized ionic compound capable of forming a stable anion on the reaction with the transition metal compound, wherein the ionized ionic compound comprises a cationic component and an anionic component, and the cationic component is fixed on the surface of the carrier. O-96/04319 discloses a catalyst composition comprising a metal oxide support having covalently bound to the surface thereof, directly through the oxygen atom of the metal oxide, an activating anion which is also linked ionically to a catalytically active transition metal compound. WO-93/11172 relates to polyanionic fractions comprising a plurality of uncoordinated anionic groups, which hang from, and are chemically linked to, a core component. The core component can be a crosslinked polystyrene or polymeric polydivinylbenzene core, or a basic polyanionic Lewis core substrate that can react with a Lewis acid. Polyanionic fractions are used in an uncoordinated association with cationic transition metal compounds. The pending United States Request for North America with serial number 08 / 610,647, filed on March 4, 1996, corresponding to WO 96/28480, discloses supported catalyst components comprising a support material, an organometal compound, an activating compound comprising a cation which is capable of reacting with a transition metal compound to form a catalytically active transition metal complex, and a compatible anion having up to 100 non-hydrogen atoms, and containing at least one substituent comprising a moiety having an active hydrogen. When combined with a transition metal compound, the resulting supported catalysts are very useful addition polymerization catalysts. It would be desirable to provide a solid catalyst and dispersions of solid catalysts, and components or precursors therefor, which do not require an alumoxane component, and which can be used in polymerization processes by particle formation without requiring a support material. It would also be desirable to provide a solid catalyst, including precursors thereto, that when used in a polymerization process, is capable of producing polymers at good catalyst efficiencies. It is another object to provide a solid catalyst, including precursors thereto, that when used in a polymerization process by particle formation, of small amounts of particles of undesired size and morphology. It is still another objective to provide a solid catalyst, including precursors thereto, which, when used in a particle polymerization process, largely avoids or removes the problem of the formation of polymer deposits in the walls of the reactor and other moving parts in the reactor. It is another object to provide a solid catalyst and a polymerization process that is capable of forming polymers in the form of free flowing powder or particles. It is another object to provide a method for making a solid catalyst without requiring recovery or purification steps. It is another object to provide a solid catalyst that also comprises a support material. One or many of these objects are realized by the modalities of the present invention described hereinafter.

SUMMARY OF THE INVENTION In one aspect of this invention, there is provided a dispersion of a supported catalyst component comprising (a) an ionic compound comprising (a) (1) a cation and (a) (2) an anion having up to 100 non-hydrogen atoms, and the anion contains at least one substituent comprising a fraction having an active hydrogen, and (d) a support material, wherein the supported catalyst component is dispersed in solid form in a diluent in that both (a) and (b) are insoluble or barely soluble, and wherein, (i) the support material is a previously treated support material, and in the supported catalyst component the anion (a) (2) is not chemically bonded to support (d), or (ii) the ionic compound has a solubility in toluene at 22 ° C of at least 0.1 weight percent, the support material used is a support material containing binding groups , and in the catalyst component s The anion (a) (2) is chemically bonded to the support (d). In a related aspect there is provided a dispersion of an unsupported catalyst component comprising (a) an ionic compound comprising (a) (1) a cation and (a) (2) an anion having up to 100 non-hydrogen atoms , and the anion contains at least one substituent comprising a moiety having an active hydrogen, wherein (a) is in solid form in the absence of a support material, and is dispersed in a diluent in which (a) is Insoluble or barely soluble. Desirable embodiments of the aforementioned dispersions are those in which the catalyst component also comprises (b) a transition metal compound, and wherein the catalyst component is a substantially inactive catalyst precursor; or wherein the catalyst component also comprises (c) an organometal or metalloid compound, wherein the metal or metalloid is selected from Groups 1-14 of the Periodic Table of the Elements, and the catalyst component is a product of reaction of (a) and (c), while in other desirable embodiments the catalyst component excludes (b) a transition metal compound, excludes (c) an organometal or metalloid compound, wherein the metal or metalloid is selected from Groups 1-14 of the Periodic Table of the Elements, or excludes both (b) and a (c). In another aspect of this invention, an unsupported catalyst is provided which comprises, in the absence of a support material, (a) an ionic compound comprising (a) (1) a cation and (a) (2) an anion having up to 100 non-hydrogen atoms, and the anion contains at least one substituent comprising a fraction having an active hydrogen, (b) a compound of transition metal, and (c) an organometal or metalloid compound, wherein the metal is selected from Groups 1-14 of the Periodic Table of the Elements. In another aspect of this invention, there is provided a supported solid catalyst comprising (a) an ionic compound comprising (a) (1) a cation and (a) (2) an anion having up to 100 non-hydrogen atoms, and the anion contains at least one substituent comprising a moiety having an active hydrogen, (b) a transition metal compound, and (c) an organometal or metalloid compound, wherein the metal or metalloid is selected from the groups 1-14 of the Periodic Table of the Elements, and (d) a support material, wherein (i) the support material is a previously treated support material, and in the supported catalyst component the anion (a) ( 2) is not chemically bonded to support (d), or (ii) the ionic compound has a solubility in toluene at 22 ° C of at least 0.1 weight percent, the support material used is a support material containing groups of bonding, and in the supported catalyst component the anion (a) (2) is chemically bonded to the support (d); and wherein the solid catalyst is obtained by combining the components (a), (b), (c) and (d) in any order, and wherein during at least one step in the preparation of the solid catalyst, the component (a) is dissolved in a diluent in which (a) is soluble, optionally in the presence of one or more of components (b), (c), and (d), or the contact product of (a) ), with one or more of (b), (c), and (d), and then converted to the solid form. In the aspects mentioned above with respect to an unsupported catalyst, and a supported catalyst, the desirable modalities are those in which the anion (a) (2) corresponds to Formula (II): [M'm + Qn (Gq ( TH) r) z] d- (II) where: M1 is a metal or metalloid selected from Groups 5-15 of the Periodic Table of the Elements; Q is independently selected at each occurrence, from the group consisting of hydride, dihydrocarbylamido, halide, hydrocarbyloxide, hydrocarbyl, and substituted hydrocarbyl radicals, including hydrocarbyl radicals substituted by halo, and hydrocarbyl-substituted hydrocarbyl organo-metalloid radicals and halohydrocarbyl , the hydrocarbyl portion in each of these groups preferably has from 1 to 20 carbons, with the proviso that in not more than one occurrence Q is halide; G is a polyvalent hydrocarbon radical having valences of r + 1 linked to the groups M 'and r (T-H); the group (T-H) is a radical where T comprises 0, S, NR, or PR, whose atom 0, S, N, or P is bonded to the hydrogen atom H, wherein R is a hydrocarbyl radical, a trihydrocarbylsilyl radical, a trihydrocarbylgermyl radical or hydrogen; m is an integer of 1 a; n is an integer from 0 to 7, - q is an integer from 0 to 1; r is an integer from 1 to 3; z is an integer from 1 to 8; d is an integer from 1 to 1, - and n + z-m = d; and wherein the cation (a) (1) of the ionic compound (a) _? _ is represented by the following general formula: [L -H], wherein: L is a nitrogen, oxygen, sulfur or phosphorus containing the Lewis base, containing from one to three alkyl groups of 10 to 40 carbon atoms, with a total of from 12 to 100 carbons. When the catalysts of the present invention include a support material (d), the versatility of the catalyst is improved. The use of a support material allows the particle size of the solid catalyst to be changed between wider ranges. In another aspect of this invention, there is provided a method for preparing a dispersion of a supported catalyst component comprising (a) an ionic compound comprising (a) (1) a cation and (a) (2) an anion having up to 100 non-hydrogen atoms, and the anion contains at least one substituent comprising a fraction having an active hydrogen, and (d) a support material, wherein the supported catalyst component is dispersed in solid form in a diluent in which both (a) and (b) are insoluble or barely soluble, the method comprising converting a solution of the ionic compound (a) into a diluent in which (a) is soluble in the presence of the support material, a dispersion comprising component (a) in solid form, and wherein, (i) the support material used is a previously treated support material, and in the supported catalyst component anion (a) (2) is not chemically bound to the support e (d), or (ii) the ionic compound has a solubility in toluene at 22 ° C of at least 0.1 weight percent, the support material used is a support material containing binding groups, and in the component of supported catalyst the anion (a) (2) is chemically bonded to the support (d). In another aspect of this invention, there is provided a method for preparing a dispersion of an unsupported catalyst component comprising converting a solution of an ionic compound (a) comprising (a) (1) a cation and (a) (2) an anion having up to 100 non-hydrogen atoms, and the anion contains at least one substituent comprising a fraction having an active hydrogen, in a diluent in which (a) it is soluble in the absence of a support material, to a dispersion comprising component (a) in solid form. In another aspect of this invention, there is provided a method for the preparation of a solid catalyst, which comprises combining, in any order, (a) an ionic compound comprising (a) (1) a cation and (a) (2) an anion having up to 100 non-hydrogen atoms, and the anion contains at least one substituent comprising a moiety having an active hydrogen, (b) a transition metal compound, (c) an organometal or metalloid compound, wherein the metal or metalloid is selected from Groups 1-14 of the Periodic Table of the Elements, and, optionally, (d) a support material, wherein during at least one step in the preparation of the solid catalyst, the component (a) is dissolved in a diluent in which (a) is soluble, to produce a solution of (a), optionally in the presence of one or more of components (b), (c), and (d), or the contact product of (a), with one or more of (b), (c), and (d), and then converted to the solid form, optionally followed by recovery of the solid catalyst in particulate form dry, wherein, when a support material (d) is present, (i) the support material used is a previously treated support material, and in the supported catalyst the anion (a) (2) is not chemically bonded to the support (d), or (ii) the ionic compound has a solubility in toluene at 22 ° C of at least 0.1 weight percent, the support material used is a support material containing binding groups, and in the supported catalyst the anion (a) (2) is chemically bonded to the support (d). A highly desirable embodiment of this method for the preparation of a solid catalyst is that wherein the support material used is a support material pretreated with a pore volume of from 0.1 to 5 square centimeters / gram, and in the supported catalyst , the anion (a) (2) is not chemically bound to the support (d), and wherein the volume of the solution of (a), optionally in the presence of one or both of (b) and (c), is from 20 volume percent to 200 volume percent of the total pore volume of the support material used, and wherein the solid catalyst is produced by adding the solution of (a) to previously treated, substantially dry support material , followed by the removal of the diluent. An alternative embodiment of this method for the preparation of a solid catalyst is that wherein during the at least one step in the preparation of the solid catalyst, a dispersion comprising component (a) in solid form is generated, by cooling a solution of (a) in a diluent in which (a) it is soluble, by contacting a solution of (a) in a diluent in which (a) it is soluble, with a diluent in which (a) is insoluble or barely soluble, by evaporating the diluent from a solution of (a), by adding one or more precipitating agents to a solution of (a), or a combination of two or more of these techniques. In another aspect of this invention, there is provided a method for activating a substantially inactive catalyst precursor, to form a catalyst suitable for addition polymerization, wherein a substantially inactive catalyst precursor comprising (a) an ionic compound that comprises (a) (1) a cation and (a) (2) an anion having up to 100 non-hydrogen atoms, and the anion contains at least one substituent comprising a moiety having an active hydrogen, (b) a compound of transition metal, and, optionally, (d) a support material, is contacted with (c) an organometal or metalloid compound, wherein the metal or metalloid is selected from Groups 1-14 of the Table Periodic of the Elements, to form an active catalyst. In another aspect of this invention, an addition polymerization process is provided, wherein one or more addition polymerizable monomers are contacted with one of the solid catalysts mentioned above, under addition polymerization conditions. In another aspect of this invention, there is provided an ionic compound (a) comprising (a) (1) a cation and (a) (2) an anion having up to 100 non-hydrogen atoms, and the anion contains at least one substituent comprising a fraction having an active hydrogen, wherein the cation (a) (1) is represented by the following general formula: [L -H], wherein: L is a nitrogen, oxygen, sulfur or phosphorus containing the Lewis base, containing from one to three alkyl groups of 10 to 40 carbon atoms, with a total of from 12 to 100 carbons, and wherein the anion (a) (2) corresponds to Formula (II): [M'm + Qn (Gq (TH) r) z] d- (II) where: M 'is a metal or metalloid selected from Groups 5-15 of the Periodic Table of the Elements; Q is independently selected at each occurrence from the group consisting of hydride, dihydrocarbyl-a, halide, hydrocarbyloxide, hydrocarbyl, and substituted hydrocarbyl radicals, including hydrocarbyl radicals substituted by halo, and organo-metalloid radicals substituted by hydrocarbyl and halohydrocarbyl , the hydrocarbyl portion in each of these groups preferably has from 1 to 20 carbons, with the proviso that in no more than one occurrence Q is halide; G is a polyvalent hydrocarbon radical having valences of r + 1 linked to the < and r (T-H); the group (TH) is a radical wherein T comprises O, S, NR, or PR, whose O, S, N, or P atom is linked to the hydrogen atom H, wherein R is a hydrocarbyl radical, a trihydrocarbylsilyl radical , a trihydrocarbylgermyl radical or hydrogen; m is an integer from 1 to 7, n is an integer from 0 to 1, q is an integer from 0 to l, r is an integer from 1 to 3, z is an integer from 1 to d is an integer from 1 to 7; and n + z-m = d. Surprisingly, it has been found that the ionic compound (a) can be conveniently used in a solid form dispersed in a diluent in which (a) it is insoluble or barely soluble (to the diluent in which (a) it is insoluble or barely soluble also it is referred to as "non-solvent", the diluent in which (a) is soluble is also referred to as "solvent"). By using the dispersed solid ionic compound (a), in combination with the transition metal compound (b) and the organometal compound (c), an active particulate polymerization active solid catalyst results, preferably in dispersed form. This dispersed solid catalyst can be conveniently used in a particle-forming polymerization process, such as a slurry or gas phase polymerization process, without requiring an additional support material to produce the polymer of the particle size and morphology. desired. The solid dispersed catalysts of the present invention can produce polymers in the form of free flowing powder or particles, without causing substantial polymer deposits in the walls of the reactor and other moving parts in the reactor. The free-flowing ethylene-based polymers and interpolymers preferably have mass densities of at least about 0.20 grams / square centimeter, and most preferably at least about 0.25 grams / square centimeter. In another aspect of this invention, there is provided a compound which is the reaction product of (a) an ionic compound described above and (c) an organometal or metalloid compound, wherein the metal or metalloid is selected from Groups 1 -14 of the Periodic Table of the Elements. A desirable modality is one in which the compound corresponds to the formula [L * -H] + [(C6F5) 3BC6H4-0-M ° Rc? .1Xay] X wherein M ° is a metal or metalloid selected from Groups 1-14 of the Periodic Table of the Elements, Rc is independently at each occurrence hydrogen or a group having from 1 to 80 non-hydrogen atoms which is hydrocarbyl, hydrocarbylsilyl, or hydrocarbylsilyl-hydrocarbyl; Xa is a non-interfering group having from 1 to 100 non-hydrogen atoms, which is hydrocarbyl substituted by halo, hydrocarbyl substituted by hydrocarbylamino, hydrocarbyl substituted by hydrocarbyloxy, hydrocarbylamino, di (hydrocarbyl) amino, hydrocarbyloxy or halide; x is an integer that is not zero 'that can vary from 1 to an integer equal to the valence of M °; and is zero or a non-zero integer that can vary from 1 to an integer equal to 1 less than the valence of M °; and x + y is equal to the valence of M °. In another aspect of this invention, there is provided a substantially inactive catalyst precursor comprising (a) an ionic compound described above, and (b) a transition metal compound.

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 registered as intellectual property by CRC Press, Inc., 1989. In addition, any reference to the Group or Groups must be to the Group or Groups as they are reflected in this Periodic Table of the Elements, using the IUPAC system for the numbering of the groups. The term "unsupported" as used in the present application means in the absence of a material that can typically be used as a support or carrier in an addition polymerization catalyst, more particularly as an addition polymerization catalyst. olefins. Conversely, the term "supported" as used in the present application means in the presence of a material that typically can be used as a support or carrier in an addition polymerization catalyst, more particularly as a polymerization catalyst. by the addition of olefins. Where the term "solid catalyst" is used in the present application, it encompasses both unsupported and supported solid catalysts, unless this is observed differently by context. Wherein in the present invention a composition is defined by its starting components or starting compounds optionally in combination with certain steps of the process, such as for example the contacting and combining steps, this means that the composition encompasses the components starting materials or starting compounds, but also the reaction product or the reaction products of the starting components or starting compounds, to the extent that the reaction has taken place. The dispersion of (a) of the present invention is preferably characterized by an average particle size of (a), as measured by laser diffraction, in the range from 0.1 to 200 μm, most preferably in the range from 0.5 to 50 μm. The dispersion of (a) preferably contains from 0.00001 to 10 moles of the solid compound (a) / l, more preferably from 0.0001 to 1 mol / l. The particle size of the dispersion of (a) was measured using a Malvern Mastersizer particle size analyzer. Some ionic compounds (a) to be used in the present invention, and their methods of preparation, are described in U.S. Patent Application No. 08 / 610,647, filed March 4, 1996 (corresponding to "O"). -96/28480) which is incorporated herein by reference. Other ionic compounds are more closely related to those described in U.S. Patent Application Number, filed [42808A], some of which may be useful in various aspects of this invention. The preferred ionic compounds of this invention have not been previously described, and have the advantage of being highly soluble in the solvents and diluents used in different methods using these ionic compounds, while at the same time, the preferred ionic compounds contain a fraction having an active hydrogen. The term used in the anion (a) (2) of the ionic compound "at least one substituent comprising a fraction having an active hydrogen" means, in the present application, a substituent comprising a hydrogen atom linked to a hydrogen atom. oxygen, sulfur, nitrogen or phosphorus. The presence of at least one fraction that has an active hydrogen, in the ionic compound, imparts an unprecedented versatility to it in the catalytic technique, because it is able to enter different reactions mainly through covalent bond, such as , for example, binding to a binding group, such as, for example, a surface hydroxyl group of a support material, or in the formation of a reaction product with an organometal or metalloid compound, or in the formation of a complex or reaction product with a transition metal compound. When different chemical formulas are used in the present to represent different chemical compounds, it must be recognized that the formula is empirical and not necessarily molecular. In particular, with respect to different organometal or metalloid compounds, especially those containing aluminum, and with the different alumoxanes, it is understood that a single empirical formula can be used, as is conventional in the art of catalysts to represent what can be be different dimers, trimers and other higher oligomers, depending on the physical environment, including different solvents or diluents in which the compound is used. The anion (a) (2) comprises a single element of Group 5-15, or a plurality of elements of Group 5-15, but is preferably a single coordination complex comprising a metal core or metalloid charge carrier. The anions (a) (2) preferred are those which contain a single coordination complex comprising a metal or metalloid charge carrying core, which carries the at least one substituent containing a fraction having an active hydrogen. The metals suitable for anions of ionic compounds (a) include, but are not limited to, aluminum, gold, platinum and the like. Suitable metalloids include, but are not limited to, elements of Groups 13, 14 and 15, of the Periodic Table of the Elements, preferably, boron, phosphorus, and silicon. Ionic compounds containing anions comprising a coordination complex containing a single boron atom, and one or more substituents comprising a moiety having an active hydrogen are preferred. Examples of suitable anions comprising a single element of Group 5-15 are described in EP-277 004, and examples of those having a plurality of elements of Group 5-15 are described in EP-0 277 003, with the proviso that at least one of the substituents on the anions described therein is substituted by a substituent comprising a moiety having an active hydrogen, preferably Gq (TH) r. Preferably, the anions (a) (2) can be represented by a single coordination complex of the following general Formula (II): [M'm + Qn (Gq (T-H) r) z] d- (II) wherein: M 'is a metal or metalloid selected from Groups 5-15 of the Periodic Table of the Elements; Q is independently selected at each occurrence from the group consisting of hydride, dihydrocarbyl amido, preferably dialkylamido, halide, hydrocarbyloxide, preferably alkoxide and aryloxide, hydrocarbyl, and substituted hydrocarbyl radicals, including hydrocarbyl radicals substituted by halo, and radicals of organo-metalloid substituted by hydrocarbyl and halohydrocarbyl, the hydrocarbyl portion in each of these groups preferably has from 1 to 20 carbons, with the proviso that in not more than one occurrence Q is halide; G is a polyvalent hydrocarbon radical having valences of r + 1, and preferably a divalent hydrocarbon radical, linked to the groups M "and r (TH), - the group (TH) is a radical wherein T comprises 0, S, NR, or PR, whose 0, S, N, or P atom is linked to the hydrogen atom H, wherein R is a hydrocarbon radical, a trihydrocarbylsilyl radical, a trihydrocarbylgermyl 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 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 or 2, d is an integer from 1 to 7, preferably 1, and n + zm = d When q is 0 and the polyvalent hydrocarbon radical G is not present, T is linked to M '. Preferred boron-containing anions (a) (2), which are particularly useful in this invention, can be represented by the following general formula (III): [BQ4.zXGq (TH) r) z-] d "(III) where: B is boron in a valence state of 3; z 'is an integer from 1 to 4, preferably 1 or 2, most preferably 1; d is 1; and Q, G, T, H, q, and r are as defined for Formula (II). Preferably, z 'is 1 or 2, q is 1, and r is 1. In anion (a) (2), the at least one substituent comprising a moiety that has an active hydrogen, corresponds preferably to Formula I: Gq (TH) r (I) wherein G is a polyvalent hydrocarbon radical, the group (TH) is a radical wherein T comprises 0, S, NR, or PR whose O, S, N, or P atom is linked to the hydrogen atom H, wherein R is a hydrocarbyl radical, a trihydrocarbylsilyl radical, a trihydrocarbylgermyl radical or hydrogen, H is hydrogen, q is 0 or 1, and preferably 1, yr is an integer from 1 to 3, preferably 1. The polyvalent hydrocarbon radical G has r + 1 valencies, a valence being associated with a metal or metalloid of Groups 5-15 of the Periodic Table of the Elements in the anion, the other valences r of G being joined to the groups r (T-H). Preferred examples of G include di- or trivalent hydrocarbon radicals such as: alkylene, arylene, aralkylene, or alkarylene radicals containing from 1 to 20 carbon atoms, more preferably from 2 to 12 carbon atoms. Suitable examples of divalent hydrocarbon radicals G include phenylene, biphenylene, naphthylene, methylene, ethylene, 1,3-propylene, 1,4-butylene, phenylmethylene (-CgH-CH2). The polyvalent hydrocarbyl portion G can be further substituted with radicals that have no negative impact on the effect that will be achieved by the present invention. Preferred examples of these non-interfering substituents are alkyl, aryl, silyl and germyl radicals substituted by alkyl or aryl, and fluoro substituents. The group (TH) in the above formula can be a group -OH, -SH, -NRH, or -PRH, wherein R is preferably a hydrocarbyl radical of 1 to 18 carbon atoms, preferably 1 to 12 atoms of carbon, 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. Alternatively, the group (TH) comprises a group -OH, -SH, -NRH, or -PRH, which is part of a larger functional fraction such as, for example, C (0) -OH, C (S) ) -OH, C (S) SH, C (0) -SH, C (0) -NRH, C (S) -NRH, and C (0) -PRH, and c (S) -PRH. More preferably, the group (T-H) is a hydroxy group, -OH, or an amino group, -NRH. The most preferred substituents Gq (T-H) in the anion (a) (2) include aryl, aralkyl, alkaryl or alkyl groups substituted by hydroxy and amino, and most preferred are hydroxyphenyls, especially the 3- and 4-hydroxyphenyl groups, and 2,4-dihydroxyphenyl, hydroxytolyl, hydroxybenzyl ( hydroxymethylphenyl), hydroxybiphenyls, hydroxynaphthyl, hydroxynylohexyl, hydroxymethyl, and hydroxypropyl, and the corresponding amino-substituted groups, especially those substituted with -NRH wherein R is an alkyl or aryl radical having from 1 to 10 carbon atoms, such as example methyl, ethyl, propyl, i-propyl, n-, i-, or t-butyl, pentyl, hexyl, heptyl, octyl, nonyl, and decyl, phenyl, benzyl, tolyl, xylyl, naphthyl, and biphenyl. Illustrative, but not limiting, examples of the anions (a) (2) of the ionic compounds to be used in the present invention are boron-containing anions such as triphenyl (hydroxyphenyl) borate, triphenyl borate (2) , 4-dihydroxyphenyl), tri (p-tolyl) (hydroxyphenyl) borate, tris- (p-tolyl) (hydroxyphenyl) borate, tris- (pentafluorophenyl) (hydroxyphenyl) borate, tris- (3-4) borate -dimethylphenyl) (hydroxyphenyl), tris- (3,5-dimethylphenyl) (hydroxyphenyl) borate, tris- (3,5-di-trifluoromethyl-phenyl) (hydroxyphenyl) borate, tris- (penta-fluorophenyl) borate (2-hydroxyethyl), tris (pentafluorophenyl) (4-hydroxybutyl) borate, tris (pentafluorophenyl) (4-hydroxy-cyclohexyl) borate, tris (pentafluorophenyl) (4- (4'-hydroxyphenyl) phenyl) borate), tris (pentafluorophenyl) (6-hydroxy-2-naphthyl) borate, and the like. Other preferred anions (a) (2) include those containing two substituents containing a moiety having an active hydrogen, for example: diphenyldi (hydroxyphenyl) borate, diphenyldi (2,4-dihydroxyphenyl) borate, di ( p-tolyl) di (hydroxyphenyl), di (pentafluorophenyl) di (hydroxyphenyl) borate, di (2,4-dimethylphenyl) di (hydroxyphenyl) borate, di (3, 5-dimethylphenyl) di (hydroxyphenyl) borate ), di (3, 5-di-tri-fluoromethylphenyl) di (hydroxyphenyl) borate, di (pentafluorophenyl) di (2-hydroxyethyl) borate, di (pentafluorophenyl) di (4-hydroxybutyl) borate, di borate (pentafluorophenyl) di (4-hydroxy-cyclohexyl), di (pentafluorophenyl) di (4- (4'-hydroxyphenyl) phenyl) borate, di (pentafluorophenyl) di (6-hydroxy-2-naphthyl) borate, and the like . Other preferred anions are those borates mentioned above, wherein the hydroxy functionality is replaced by an amino NHR functionality, wherein R is preferably methyl, ethyl, or t-butyl. A highly preferred anion (a) (2) is tris (pentafluorophenyl) (4-hydroxyphenyl) borate. The cationic portion (a) (1) of the ionic compound is preferably selected from the group consisting of Bronsted acidic cations, especially ammonium and phosphonium cations, or sulfonium cations, carbonium cations, silylium cations, cations of oxonium, organometallic cations and cationic oxidizing agents. The cations (a) (1) and the anions (a) (2) are used in proportions such as to give a neutral ionic compound. The acidic cations of Bronsted can be represented by the following general formula .- (L-H) + where: L is a neutral Lewis base, preferably a Lewis base containing nitrogen, phosphorus, oxygen, or sulfur; and (L-H) + is a Bronsted acid. Illustrative but not limiting examples of the Bronsted acidic cations are ammonium cations substituted by trihydrocarbyl, and preferably by trialkyl, such as triethylammonium, tripropylammonium, tri (n-butyl) ammonium, trimethylammonium, tri (i-butyl) ammonium , and tri (n-octyl) ammonium. Also suitable are N, N-dialkylanilinium cations such as N, N-dimethylanilinium, N, N-diethyl anilinium, N, N-2,4,6-pentamethylanilinium, N, N-dimethylbenzyl ammonium and the like; dialkylammonium cations such as di- (i-propyl) ammonium, dicyclohexylammonium and the like; and triarylphosphonium cations such as triphenylphosphonium, tri (methylphenyl) phosphonium, tri (dimethylphenyl) phosphonium, dimethylsulfonium, diethylsulfonium, and diphenylsulfonium. In a highly preferred embodiment, the Bronsted acidic cation can be represented by the following general formula: [L * H] +, wherein, L is a Lewis base containing nitrogen, oxygen, sulfur or phosphorus, which comprises when minus one relatively long chain alkyl group. Preferably these L groups contain from one to three alkyl groups of 10 to 40 carbon atoms, with a total of from 12 to 100 carbons, more preferably two alkyl groups of 10 to 40 carbon atoms, and from 21 to 90 carbons totals It is understood that the cation may comprise a mixture of alkyl groups of different lengths. For example, a suitable cation is the protonated ammonium salt derived from the commercially available long chain amine, which comprises a mixture of two alkyl groups of 14, 16 or 18 carbon atoms, and a methyl group. These amines are available with Witco Corp., under the registered trademark Kemamina1 ^ T 701, and with Akzo-Nobel under the registered trademark ArmeenMR M2HT. These preferred cations are disclosed in U.S. Patent Application Serial No. 60/014284, filed March 27, 1996, which is incorporated herein by reference. The ionic compounds (a) comprising the [L -H] + cation can be easily prepared by subjecting an ionic compound comprising the cation [LH] + and the anion (a) (2), as prepared in U.S. Patent Application Number 08 / 610,647, filed March 4, 1996 (corresponding to WO-96/28480), to a cation exchange reaction with a salt of [L * -H] +. Generally, the preferred ionic compounds have a solubility in toluene at 22 ° C, at least 0.1 weight percent, desirably, at least 0.3 weight percent, more desirably at least 1 weight percent, preferably at least 5 percent by weight, more preferably at least 10 percent by weight, and in some cases up to more than 15 percent by weight. Illustrative but not limiting examples of the highly preferred cations (a) (1) are the tri-substituted ammonium salts such as: decildi (methyl) ammonium, dodecyldi (methyl) ammonium, tetradecyldi (methyl) ammonium, hexadecyl- di (methyl) ammonium, octadecildi (methyl) ammonium, eicosil-di (methyl) ammonium, metildi (decyl) ammonium, metildi (dodecyl) ammonium, nmethyldi (tetradecyl) ammonium, metildi (hexadecyl) ammonium, metildi (octadecyl) ammonium, methyldi (eicosyl) ammonium, tridecylammonium, tridodecylammonium, tritetradecylammonium, trihexadecylammonium, trioctadecylammonium, trieicosylammonium, decildi (n-butyl) ammonium, dodecyldi (n-butyl) ammonium, octadecyldi (n-butyl) ammonium, N, N-didodecylanilinium, N- methyl-N-dodecylanilinium, N, -di (octadecyl) (2,4,6-trimethylanilinium), cyclohexyldi (dodecyl) monium, and methyldi (dodecyl) ammonium. Also suitable are suitable substituted sulfonium or phosphonium cations such as, di (decyl) sulfonium, (n-butyl) dodecyl sulfonium, tridecylphosphonium, di (octadecyl) methylphosphonium, and tri (tetradecyl) phosphonium. Preferred ionic compounds (b) are di (octadecyl) methylammonium tris (pentafluorophenyl) (hydroxyphenyl) borate, octadecyldimethylammonium tris (pentafluorophenyl) borate and di (octadecyl) (n-butyl) tris (pentafluorophenyl) (hydroxyphenyl) borate. ammonium, as well as the amino analogues (-NHR) of these compounds, wherein the hydroxyphenyl group is replaced by the aminophenyl group. A second type of suitable cation corresponds to the formula: ® +, where ® + is a stable carbonium or silylium ion containing up to 30 non-hydrogen atoms. Suitable examples of cations include tropylium, triphenylmethylium, benzene (diazonium). Silylium salts have been previously described generically in J. Chem. Soc. Chem.

Comm., 1993, 383-384, as well as Lambert, J. B. et al., Organometallics, 1994, 13, 2430-2443. Preferred silylium cations are triethylsilylium, and trimethylsilylium and ether-substituted adducts thereof. Another suitable type of cation comprises a cationic oxidation agent represented by the formula: 0xe + wherein O is a cationic oxidation agent having a charge of e +, and e is an integer of 1 to 3. Another suitable type of cation comprises a cation organometallic, such as, for example, IR ^ "1", wherein R is a hydrocarbyl or substituted hydrocarbyl having from 1 to 100 non-hydrogen atoms, or S-AlRt +, wherein S is a support material or other substrate which has an AIR group attached to it, where R is as defined above. Examples of cationic oxidation agents include: ferrocenium, ferrocenium substituted by hydrocarbyl, Ag +, and Pb2 +. In accordance with another aspect of the present invention, there is provided an unsupported catalyst comprising the ionic compound (a), (b) a transition metal compound, and (c) an organometal compound, wherein the metal is selected from Groups 1-14 of the Periodic Table of the Elements. The unsupported catalyst can be formed from the soluble components (a), (b) and (c), and used in a diluent in which it is soluble, such as, for example, in a solution polymerization process , or it can be recovered as a solid in the form of solid particles. In one aspect of this invention, unsupported solid catalysts are preferably dispersed in a diluent in which the solid catalyst is insoluble or barely soluble. The present invention further provides a supported solid catalyst comprising the ionic compound (a), the transition metal compound (b), the organometal compound (c), and a support material (d). The suitable ionic compounds (a) have been described hereinabove.

Transition metal compounds (b) suitable for use in the present invention include any compound or complex of a metal of Groups 3-10 of the Periodic Table of the Elements, capable of being activated upon insertion and olefin polymerization, when it is combined with the components (a) and (c), and optionally (d) of the present invention. Examples include the transition metal diimine derivatives of Group 10, which are described in WO-96/23010. Additional catalysts include derivatives of Group 3, 4, 5, or 6 or the Lanthanide metals that are in the formal oxidation state +2, +3, or +4. Preferred compounds include metal complexes containing from 1 to 3 anionic or neutral ligand groups linked by 71", which may be ligand groups linked by delocalized, cyclic or noncyclic p.Examples of these ligand groups linked by TG are dienyl groups conjugated or non-conjugated, cyclic or non-cyclic, allyl groups, boratabenzene groups, and arene groups By the term "linked by TG" it is meant that the ligand group is bound to the transition metal by means of delocalized TG electrons thereof. Each atom in the group linked by delocalized p can be independently substituted with a radical selected from the group consisting of hydrogen, halogen, hydrocarbyl, halohydrocarbyl, hydrocarbyl substituted, hydrocarbyloxy, dihydrocarbylamino metalloids, wherein the metalloid is selected from of Group 14 of the Periodic Table of the Elements and of radicals hid rocarbyl, or hydrocarbyl substituted metalloid radicals, also substituted with a group-containing heteroatom of Group 15 or 16. Included within the term "hydrocarbyl" are alkyl radicals of 1 to 20 carbon atoms, straight, branched and cyclic, radicals aromatics of 6 to 20 carbon atoms, aromatic radicals substituted by alkyl of 7 to 20 carbon atoms, 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, a hydrogenated fused ring system, or a metallocycle with the metal. Suitable hydrocarbyl substituted organometalloid radicals include mono-, di-, and tri-substituted organometalloid radicals of Group 14 elements, wherein each of the hydrocarbyl groups contains from 1 to 20 carbon atoms. Examples of suitable hydrocarbyl substituted organometalloid radicals include trimethylsilyl, triethylsilyl, ethyldimethylsilyl, methyldiethylsilyl, triphenylgermyl, and trimethylgermyl groups. These hydrocarbyl and organometaloid radicals substituted by hydrocarbyl can be further substituted with a fraction containing a heteroatom of Group 15 or 16. Examples of fractions containing a heteroatom of Group 15 or 16 include fractions of amine, phosphine, ether or thioether ( see for example the compounds described in WO-96/13529) or divalent derivatives thereof, for example, amide, phosphide, ether or thioether groups linked to the transition metal or the Lanthanide metal, and linked to the hydrocarbyl group or the group containing metalloid substituted by hydrocarbyl. Examples of suitable anionic, delocalized TG bonded groups include cyclopentadienyl, indenyl, fluorenyl, tetrahydroindenyl, tetrahydrofluorenyl, octahydrofluorenyl, pentadienyl, cyclohexadienyl, dihydroanthracenyl, hexahydroanthracenyl, decahydroanthracenyl, and boratabenzene groups, as well as hydrocarbyl substituted germyl derivatives of 1 to 10 carbon atoms, substituted by silyl substituted by hydrocarbyl of 1 to 10 carbon atoms thereof, and divalent derivatives of the above substituents. The delocalized p-ammonia bonded groups are cyclopentadienyl, pentamethylcyclopentadienyl, tetramethylcyclopentadienyl, tetramethylsilylcyclopentadienyl, indenyl, 2,3-dimethylindenyl, fluorenyl, 2-methylindenyl, 2-methyl-4-phenylindenyl, tetrahydrofluorenyl, octahydrofluorenyl, and tetrahydroindenyl.

Boratabenzenes are anionic ligands that are boron containing benzene analogues. These were previously known in the art and have been described by G. Herberich, et al., In Oraanometallies. 14,1,471-489 (1995). The preferred boratabenzenes correspond to the formula: wherein R1 'is selected from the group consisting of hydrocarbyl, silyl, or germyl, R1' having up to 20 non-hydrogen atoms. A suitable class of transition metal compounds useful in the present invention corresponds to formula (V): LjMXmX'nX '', or a dimer thereof (V) wherein: L is a 7 anionic, linked group, delocalised, which is linked to M, which contains up to 50 non-hydrogen atoms, optionally two L groups can be joined together, forming a bridge structure, and optionally an L can be linked to X; M is a metal of Group 4 of the Periodic Table of the Elements in the formal oxidation state +2, +3 or +4.

X is an optional, divalent substituent of up to 50 non-hydrogen atoms which together with L forms a metallocycle with M; X 'is an optional neutral ligand base, having up to 20 non-hydrogen atoms; X '' in each occurrence is a monovalent, anionic fraction having up to 40 non-hydrogen atoms, optionally, two X '' groups can be covalently linked together, forming a divalent dianionic fraction, which has both valencies linked to M, or, optionally, two X1 'groups may be covalently linked together to form a neutral, conjugated or unconjugated diene, which is linked by TG to M, or in addition, optionally one or more X "groups and one or more groups X 'can be linked together, thereby forming a fraction that is both covalently linked to M, and coordinated thereto by means of the Lewis base functionality; 1 is 0, 1 or 2; m is 0 or 1; n is a number from 0 to 3; p is an integer from 0 to 3; and the sum, 1 + m + p, is equal to the formal oxidation state of M, except when two groups X '' together form a neutral conjugated or unconjugated diene, which is linked by pa M, in which case the sum of 1 + m is the same as the formal oxidation state of M. Preferred complexes include those that contain either one or two L groups. The last complexes include those that contain a bridge group that binds to both L groups. preferred bridges are those corresponding to the formula (ER2) X / wherein E is silicon, germanium, tin, or carbon, R is independently in each occurrence hydrogen or a group selected from silyl, hydrocarbyl, hydrocarbyloxy, and combinations of the same, R having up to 30 carbon or silicon atoms, and x is from 1 to 8. Preferably, R is independently in each occurrence methyl, ethyl, propyl, benzyl, tert-butyl, phenyl, methoxy, ethoxy or phenoxy. Examples of the complexes containing two L groups are compounds corresponding to Formula (VI) and (VII): where: M is titanium, zirconium or hafnium, preferably zirconium or hafnium, in the formal oxidation state +2 or +4, - R independently at each occurrence is selected from the group consisting of hydrogen, hydrocarbyl, silyl, germyl, cyano , halo and combinations thereof, R having up to 20 non-hydrogen atoms, or adjacent R groups together form a divalent derivative (i.e., a hydrocarbyldiyl, siladiyl or germadiyl group), thereby forming a fused ring system, and X "independently in each occurrence is an anionic ligand group of up to 40 non-hydrogen atoms, or two X" groups together form an anionic divalent ligand group of up to 40 non-hydrogen atoms, or together they are a conjugated diene having from 4 to 30 non-hydrogen atoms, which form a TG complex with M, over which M is in the formal oxidation state +2, and R, E and x are as defined above for the bridge groups (ER2) X - The comp away from previous metal are especially suitable for the preparation of polymers having stereoregular molecular structure. In this capacity, it is preferred that the complex possess Cs symmetry or that it possess a chiral, stereorigid structure. Examples of the first type with compounds possessing different systems linked by delocalized it, such as a cyclopentadienyl group and a fluorenyl group. In Ewen, et al., J. Am. Chem. Soc. 110, 6255-6256 (1980) similar systems based on Ti (IV) or Zr (IV) were described for the preparation of syndiotactic olefin polymers. Examples of chiral structures include bis-indenyl complexes rae. In Wild et al, J. Organómet. Chem., 232, 233-47, (1982) similar systems based on Ti (IV) or Zr (IV) were described, for the preparation of isotactic olefin polymers. Bridged Exemplary ligands containing two groups linked by p are: (dimethylsilyl-bis (cyclopentadienyl)), (dimethylsilyl-bis (methylcyclopentadienyl)), (dimethylsilyl-bis (ethylcyclopentadienyl)), (dimethylsilyl-bis (t-butylcyclopentadienyl)) , (dimethylsilyl-bis (tetrametilciclo-pentadienyl)), (dimethylsilyl-bis (indenyl)), (dimethylsilyl-bis (tetrahydroindenyl)), (dimethylsilyl-bis (fluorenyl)), (dimethylsilyl-bis (tetrahydrofluorenyl)), (dimethylsilyl -bis (2-methyl-4-phenylindenyl)), (dimethylsilyl-bis (2-methylindenyl)), (dimethylsilyl-cyclopentadienyl fluorenyl), (dimethylsilyl-cyclopentadienyl-octahydrofluorenyl), (dimethylsilyl-cyclopentadienyl-tetrahydrofluorenyl), (1, 1, 2, 2-tetramethyl-l, 2-disilyl-bis-cyclopentadienyl), (1, 2-bis (cyclopentadienyl) ethane, and (isopropylidene-cyclopentadienyl-fluorenyl). the groups X '' preferred in the Formula (VI) and (VII) are selected from hydride, hydrocarbyl, silyl, germyl, hal ohidrocarbilo, halosilyl, silylhydrocarbyl, and aminohydrocarbyl, or two groups X1 'together form a divalent derivative of a conjugated diene or else together they form a conjugated diene, linked by TG, neutral. The most preferred groups X "are hydrocarbyl groups of 1 to 20 carbon atoms. Another class of metal complexes used in the present invention corresponds to the above formula (V) LjMXmX'nX ", or a dimer thereof, wherein X is a divalent substituent of up to 50 non-hydrogen atoms, which together with L forms a metallocycle with M. Preferred divalent X substituents include groups containing up to 30 non-hydrogen atoms comprising at least one atom which is oxygen, sulfur, boron, or a member of Group 14 of the Periodic Table of the Elements , directly linked to the group linked by delocalized TG, and a different atom, selected from the group consisting of nitrogen, phosphorus, oxygen or sulfur, which is covalently linked to M.

(VIII) A preferred group of these Group 4 metal coordination complexes, used in accordance with the present invention, corresponds to formula (VIII): wherein: M is titanium or zirconium, preferably titanium in the oxidation state formal +2, +3, or +4; R in each occurrence is independently selected from the group consisting of hydrogen, hydrocarbyl, silyl, germyl, cyano, halo, hydrocarbyloxy, dihydrocarbylamino, and combinations thereof, R having up to 20 non-hydrogen atoms, or the adjacent R3 groups together form a divalent derivative (i.e., a hydrocarbyldiyl, siladiyl or germadiyl group), thereby forming a fused ring system, each X "in the formula (VIII) is a hydride, halide, hydrocarbyl, hydrocarbyloxy, or silyl group, this group having up to 20 non-hydrogen atoms, or two X "groups together form a neutral conjugated diene of 5 to 30 carbon atoms, or a divalent derivative of the same. mo; Y is -0-, -S-, -NR * -, -PR * -, -NR * 2 or -PR * 2; and Z is SiR * 2, CR * 2, SiR * 2SiR * 2, CR * 2CR * 2, CR * = CR *, CR 2SiR 2, or GeR * 2, where R is as defined above.

In accordance with the present invention, metal complexes corresponding to formula (I) are provided: wherein M is titanium, zirconium, or hafnium in the formal oxidation state +2, +3 or +4; R 'is an aryl ligand or a derivative substituted by halo-, silyl-, alkyl-, cycloalkyl-, dihydrocarbylamino-, hydrocarbyloxy-, or hydrocarbylene-amino- thereof, R' having from 6 to 40 non-hydrogen atoms; Z is a divalent moiety, or a moiety comprising a bond s and a pair of two neutral electrons, capable of forming a coordinate-covalent bond with M, Z comprising boron, or a member of Group 14 of the Periodic Table of the Elements, and Z also comprising nitrogen, phosphorus, sulfur or oxygen; X is a monovalent anionic ligand group having up to 60 atoms exclusive of the class of ligands which are cyclic, delocalised ligand groups linked by TG.

X 'independently in each occurrence is a neutral Lewis base ligation compound, having up to 20 atoms; X "is an anionic divalent ligand group having up to 60 atoms; p is zero, 1, 2, or 3; q is zero, 1 or 2; and r is zero or 1. Another class of preferred metal complexes for use in the present invention correspond to the formula: where M is a metal of one of Groups 3 to 13 of the Periodic Table of the Elements, the lanthanides or actinides, which is in the formal oxidation state +2, +3 or +4, and which is bound by TG to a cyclopentadienyl group (Cp) which is a ligand group linked by TG, cyclic, delocalised, having 5 substituents: RA; (RB): - T where j is zero, 1 or 2; RC; RD and Z, - where R, RB, Rc and RD are R groups; and wherein T is a heteroatom that is covalently linked to the Cp ring, and to RD when j is 1 or 2, and when j is 0, T is F, Cl, Br, or I; when j is l, T is O or S, Ó N or P, and R has a double bond to T; when j is 2, T is N or P; and wherein R independently at each occurrence is hydrogen, or is a group having from 1 to 80 non-hydrogen atoms which is hydrocarbyl, hydrocarbylsilyl, hydrocarbyl substituted by halo, hydrocarbyl substituted by hydrocarbyloxy, hydrocarbyl substituted by hydrocarbylamino, hydrocarbylsilylhydrocarbyl, hydrocarbylamino, di (hydrocarbyl) amino, hydrocarbyloxy, each RB being optionally substituted with one or more groups independently in each occurrence are hydrocarbyloxy, hydrocarbylsiloxy, hydrocarbylsilylamino, di (hydrocarbylsilyl) amino, hydrocarbyl-amino, di (hydrocarbyl) amino, di (hydrocarbyl) phosphino, hydrocarbylsulfide, hydrocarbyl, hydrocarbyl substituted by halo, hydrocarbyl substituted by hydrocarbyloxy, hydrocarbyl substituted by hydrocarbylamino, hydrocarbylsilyl or hydrocarbylsilylhydrocarbyl having 1 to 20 non-hydrogen atoms, or a non-interfering group having from 1 to 20 atoms not hydrogen; and each of R, R and R is hydrogen, or is a group having from 1 to 80 non-hydrogen atoms which is hydrocarbyl, hydrocarbyl substituted by halo, hydrocarbyl substituted by hydrocarbyloxy, hydrocarbyl substituted by hydrocarbylamino, hydrocarbylsilyl or hydrocarbylsilylhydrocarbyl , each of R, Rc or RD being optionally substituted with one or more groups independently in each occurrence are hydrocarbyloxy, hydrocarbylsiloxy, hydrocarbylsilylamino, di (hydrocarbylsilyl) amino, hydrocarbylamino, di (hydrocarbyl) amino, di (hydrocarbyl) phosphino , hydrocarbylsulfide, hydrocarbyl, hydrocarbyl substituted by halo, hydrocarbyl substituted by hydrocarbyloxy, hydrocarbyl substituted by hydrocarbylamino, hydrocarbylsilyl or hydrocarbylsilylhydrocarbyl having from 1 to 20 non-hydrogen atoms, or a non-interfering group having from 1 to 20 non-hydrogen atoms, - u, optionally, two or more of R, R, R and R are linked covalently e with each other to form one or more fused rings or ring systems having from 1 to 80 non-hydrogen atoms for each R group, the one or more rings or fused ring systems being unsubstituted or substituted with one or more groups that independently in each occurrence are hydrocarbyloxy, hydrocarbylsiloxy, hydrocarbylsilylamino, di (hydrocarbylsilyl) amino, hydrocarbylamino, di (hydrocarbyl) amino, di (hydrocarbyl) phosphino, hydrocarbyl sulphide, hydrocarbyl, hydrocarbyl substituted by halo, hydrocarbyl substituted by hydrocarbyloxy, hydrocarbyl substituted by hydrocarbylamino, hydrocarbylsilyl or hydrocarbylsilylhydrocarbyl having 1 to 20 non-hydrogen atoms, or a non-interfering group having from 1 to 20 non-hydrogen atoms; Z is a divalent moiety linked to both Cp and M, via s bonds, wherein Z comprises boron, or a member of Group 14 of the Periodic Table of the Elements, and also comprises nitrogen, phosphorus, sulfur or oxygen; X is an anionic or dianionic ligand group having up to 60 atoms exclusive of the class of ligands which are ligand groups linked by TG, cyclic, delocalised; X 'independently in each occurrence is a neutral Lewis base ligation compound, having up to 20 atoms; p is zero, i or 2, and is two less than the formal oxidation state of M, when X is an anionic ligand; when X is a dianionic ligand group, p is 1; and q is zero, 1 or 2. Another class of preferred metal complexes for use in the present invention corresponds to the formula: where M is a metal of one of Groups 3 to 13 of the Periodic Table of the Elements, the lanthanides or actinides, which is in the formal oxidation state +2, +3 or +4, and which is linked by 7T to a cyclopentadienyl group (Cp) which is a cyclical, delocalized 7T linked ligand group having 5 substituents: (RA) jT where j is zero, 1 or 2; where RA, RB, RC and RD are R groups; and wherein T is a heteroatom that is covalently linked to the Cp ring, and to R when j is 1 or 2, and when j is 0, T is F, Cl, Br, or I; when j is l, T is O or S, Ó N or P, and R? A has a double bond to T; when j. is 2, T is N or P; and wherein R independently at each occurrence is hydrogen, or is a group having from 1 to 80 non-hydrogen atoms which is hydrocarbyl, hydrocarbylsilyl, hydrocarbyl substituted by halo, hydrocarbyl substituted by hydrocarbyloxy, hydrocarbyl substituted by hydrocarbylamino, hydrocarbylsilylhydrocarbyl, hydrocarbylamino, di (hydrocarbyl) amino, hydrocarbyloxy, each RA being optionally substituted with one or more groups which independently at each occurrence are hydrocarbyloxy, hydrocarbylsiloxy, hydrocarbylsilylamino, di (hydrocarbylsilyl) amino, hydrocarbylamino, di (hydrocarbyl) amino, di (hydrocarbyl) phosphino, hydrocarbylsulfide, hydrocarbyl, hydrocarbyl substituted by halo, hydrocarbyl substituted by hydrocarbyloxy, hydrocarbyl substituted by hydrocarbylamino, hydrocarbylsilyl or hydrocarbylsilylhydrocarbyl having 1 to 20 non-hydrogen atoms, or a non-interfering group having from 1 to 20 non-hydrogen atoms of hydrogen; and each of RB, R and R is hydrogen, or is a group having from 1 to 80 non-hydrogen atoms which is hydrocarbyl, hydrocarbyl substituted by halo, hydrocarbyl substituted by hydrocarbyloxy, hydrocarbyl substituted by hydrocarbylamino, hydrocarbylsilyl or hydrocarbylsilylhydrocarbyl , each of RB, RC or RD being optionally substituted with one or more groups that independently in each occurrence are hydrocarbyloxy, hydrocarbylsiloxy, hydrocarbylsilylamino, di (hydrocarbylsilyl) amino, hydrocarbylamino, di (hydrocarbyl) amino, di (hydrocarbyl) ) phosphino, hydrocarbylsulfide, hydrocarbyl, hydrocarbyl substituted by halo, hydrocarbyl substituted by hydrocarbyloxy, hydrocarbyl substituted by hydrocarbylamino, hydrocarbylsilyl or hydrocarbylsilylhydrocarbyl having from 1 to 20 non-hydrogen atoms, or a non-interfering group having from 1 to 20 non-hydrogen atoms of hydrogen; or, optionally, two or more of R, R, R and R are covalently bonded to each other to form one or more fused ring or ring systems having from 1 to 80 non-hydrogen atoms for each R group, the one or more rings or fused ring systems being unsubstituted or substituted with one or more groups which independently at each occurrence are hydrocarbyloxy, hydrocarbylsiloxy, hydrocarbylsilylamino, di (hydrocarbylsilyl) amino, hydrocarbylamino, di (hydrocarbyl) amino, di (hydro- carbyl) phosphino, hydrocarbylsulfide, hydrocarbyl, hydrocarbyl substituted by halo, hydrocarbyl substituted by hydrocarbyloxy, hydrocarbyl substituted by hydrocarbylamino, hydrocarbylsilyl or hydrocarbylsilylhydrocarbyl having 1 to 20 non-hydrogen atoms, or a non-interfering group having from 1 to 20 non-hydrogen atoms; Z is a divalent moiety linked to both Cp and M, via s bonds, wherein Z comprises boron, or a member of Group 14 of the Periodic Table of the Elements, and also comprises nitrogen, phosphorus, sulfur or oxygen; X is an anionic or dianionic ligand group having up to 60 atoms exclusive of the class of ligands which are ligand groups linked by p, cyclic, delocalized; X 'independently in each occurrence is a neutral Lewis base ligation compound, which has up to atoms, - p is zero, i or 2, and is two less than the formal oxidation state of M, when X is an anionic ligand; when X is a dianionic ligand group, p is 1; and q is zero, 1 or 2.

Specific examples of some of the transition metal compounds of the types described above can be found in EP-0 129 368; EP-0 277 004; EP-0 416 815; WO 93/19104; WO-95/00526; WO 96/00734; W0-96 / 04290; WO96 / 08498; while others, especially metal complexes of restricted geometry and methods for their preparation, are described in the United States Patent Application Serial Number 545,403, filed July 3, 1990; U.S. Patent Application Serial Number 547,718, filed July 3, 1990 (EP-A-468, 651); U.S. Patent Application Serial Number 702,475, filed May 20, 1991 (EP-A-514,828); U.S. Patent Application Serial Number 876,268, filed May 1, 1992 (EP-A-520, 732); and U.S. Patent Application Serial Number 8,003, filed January 21, 1993; as well as US-A-5, 055, 438; US-A-5, 057,475; US-A-5, 096, 867; US-A-5, 06, 802; US-A-5,132,380; WO 96/28480; WO 97/15583, U.S. Patent Application Serial Number 08 / 818,530, filed March 14, 1997; WO 97/35893; U.S. Patent Application Serial Number 60 / 017,147, filed May 17, 1996; PCT Application Number PCT / US97 / 08206 filed on May 16, 1997; PCT Application Number PCT / US97 / 08466 filed on May 16, 1997; U.S. Patent Application Serial Number 60 / 034,819, filed December 19, 1996; U.S. Patent Application Serial Number 60 / 023,768, filed August 8, 1996; PCT Application Number PCT / US97 / 13170 filed July 28, 1997; PCT Application Number PCT / US97 / 13171 filed on July 28, 1997; and U.S. Patent Application Serial Number 08 / 768,518, filed December 18, 1996. Also found therein, teachings related to different polymerization processes of -olefins, and the products produced in those processes, which are relevant to the processes described herein, for the use of different aspects of this invention. The teachings of all of the above patents and the corresponding U.S., EP, and WO patent applications are hereby incorporated by reference. The organometal or metalloid compounds (c) suitable for use in the present invention are those which comprise a metal or metalloid of Groups 1-14. In one aspect, component (c) contains at least one substituent selected from hydride, hydrocarbyl groups, tri? Iidrocarbylsilyl groups, and trihydrocarbylgermyl groups. It is desirable that this at least one substituent be capable of reacting with the fraction having an active hydrogen of the anion (a) (2) of the ionic compound. The additional substituents preferably comprise one or more substituents selected from hydride, halide, hydrocarbyloxide, dihydrocarbylamide hydrocarbyl groups, silyl groups substituted by trihydrocarbyl, germyl groups substituted by trihydrocarbyl, and substituted metalloid groups by hydrocarbyl, trihydrocarbylsilyl, or trihydrocarbyl bilyl. The organometal or metalloid compound (c) desirable corresponds to the formula: M ° Rc? Xay, wherein M ° is a metal or metalloid selected from Groups 1-14 of the Periodic Table of the Elements, Rc independently at each occurrence is hydrogen, or a group having from 1 to 80 non-hydrogen atoms, which is hydrocarbyl, hydrocarbylsilyl, trihydrocarbylsilyl, trihydrocarbylgermyl, or hydrocarbyl -silylhydrocarbyl; Xa is a non-interfering group having from 1 to 100 non-hydrogen atoms which is hydrocarbyl substituted by halo, hydrocarbyl substituted by hydrocarbylamino, hydrocarbyl substituted by hydrocarbyloxy, hydrocarbylamino, di (hydrocarbyl) amino, hydrocarbyloxy or halide; x is an integer that is not zero, which can vary from 1 to an integer equal to the valence of M °; and is zero or an integer that is not zero, which can vary from 1 to an integer equal to 1 less than the valence of M °; and x + y is equal to the valence of M °. Preferred organometal compounds (c) are those wherein M ° is selected from Groups 2, 12, 13 or 14 of the Periodic Table of the Elements, most desirably, Mg, Zn, B, Al, Ga, Si , Ge, Sn, or Pb, with aluminum and magnesium being preferred, and aluminum being most preferred. Examples of organometal compounds (c) include organolithium, organosodium, organomagnesium, organoscandium, organotitanium, organovanadium, organochromium, organomanganese, organo-iron, organocobalt, organo-nickel, organo-copper, organoplata, organozinc, organoboron, organoaluminium, organosilicon, organogermanium, organotin, and organolead, and mixtures thereof. Preferred organometal (c) examples include organolithium, organomagnesium, organozinc, organoboron, organoaluminum, organosilicon, organogermanium, organotin, and organolead compounds, and mixtures thereof. The most preferred examples are the compounds represented by the following formulas: MgR 2, ZnR ^, BR *? R2, IR ^ R2 where R independently in each occurrence is hydride, a hydrocarbyl radical, a trihydrocarbylsilyl radical, a trihydrocarbylgermyl radical, or a metalloid radical substituted by trihydrocarbyl, trihydrocarbylsilyl, or tphydrocarbyl bilyl, R independently is the same as R, x is 2 or 3, and is O or l, 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, n- or i-propyl, n-, s- or t-butyl, phenyl, and benzyl. The preferred components (c) are the aluminum and magnesium compounds, and especially the aluminum compounds. Preferably, the aluminum component is an aluminum compound of the formula AIR?, Wherein R at each occurrence is independently hydride or a hydrocarbyl radical having from 1 to 20 carbon atoms, and x is 3. Suitable trihydrocarbylaluminum compounds they are trialkyl or triarylaluminum compounds, wherein each alkyl or aryl group has from 1 to 10 carbon atoms, or mixtures thereof, and preferably trialkylaluminium compounds such as trimethyl, triethyl, tri-isobutylaluminum.

Alumoxanes (also referred to as aluminoxanes) can also be used as the component (c), or (c) can be a mixture of one of the compounds mentioned in the preceding paragraphs and an alumoxane. The alumoxanes are oligomeric or polymeric aluminoxy compounds, which contain chains of alternating aluminum and oxygen atoms, whereby the 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 linear compound, wherein R independently at each occurrence is hydrocarbyl of 1 to 10 carbon atoms, preferably alkyl, or halide, and m is an integer that ranges from 1 to about 50, preferably 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 many different aluminum alkyl compounds, such as, for example, trimethylaluminum and tri-isobutylaluminum, with water, produces the so-called modified or mixed alumoxanes. Preferred alumoxanes are methylalumoxane and modified methylalumoxane with minor amounts of other lower alkyl groups such as isobutyl. Alumoxanes generally contain minor to substantial amounts of 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 ways, such as 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 Number 4,542,199. In a particularly preferred embodiment, an aluminum alkyl compound is contacted with a substance containing regenerable water such as alumina, silica or other hydrated substance. This is described in European Patent Application Number 338,044. According to another aspect, the invention provides a supported solid catalyst comprising (a), (b), and (c) as described hereinabove, as well as (d) a support material. Suitable support materials (d), also referred to as carriers or carrier materials, can optionally be used in the present invention include those carrier materials that are typically used in the supported catalyst art., and more particularly the technique of supported olefin addition supported polymerization catalysts. Examples include porous resinous materials, for example, polyolefins such as polyethylenes and polypropylenes or styrene-divinylbenzene copolymers, and solid inorganic oxides, including oxides of Group 2, 3, 4, 13, or 14 metals, such as silica, alumina , magnesium oxide, titanium oxide, thorium oxide, as well as mixed oxides of silica. Suitable mixed oxides of silica include those of silica, and one or more metal oxides of Group 2 or 13, such as mixed oxides of silica-magnesium or silica-alumina. Silica, alumina, and mixed oxides of silica and one or more metal oxides of Group 2 or 13 are preferred support materials. Preferred examples of these mixed oxides are the silica-aluminas. The most preferred support material is silica. The shape of the silica particles is not critical, and the silica can be in granular, spherical, agglomerated, smoked, or other form. Suitable support materials for the present invention preferably have a surface area as determined by nitrogen porosimetry, using the BET method, from 10 to approximately 1000 square meters / gram, and preferably from approximately 100 to 600 square meters / gram The pore volume of the support, as determined by nitrogen adsorption, is typically up to 5 cubic centimeters / gram, conveniently between 0.1 and 3 cubic centimeters / gram, preferably from about 0.2 to 2 cubic centimeters / gram. The average particle size is not critical, but is typically from 0.5 to 500 μm, preferably from 1 to 200 μm, most preferably up to 100 μm. Preferred supports for use in the present invention include highly porous silica, aluminas, aluminosilicates, and mixtures thereof. The most preferred support material is silica. The support material may be in granular, agglomerated form, in pills, or in any other physical form. Suitable materials include, but are not limited to, silica available with Grace Davison (division of W.R. Grace &; Co.) under the designations SD 3216.30, Davison Syloid R245, Davison 948 and Davison 952, and with Crosfield under the designation ES70, and with 'Degussa AG under the designation Aerosil MR812; and aluminas available with Akzo Chemicals Inc., under the designation KetzenM Grade B. The support material can be subjected to heat treatment and / or chemical treatment to reduce the water content or hydroxyl content of the support material. Both dehydrated support materials and support materials containing small amounts of water can be used. Typically, chemical dehydration or dehydroxylation agents are hydrides, alkyls and reactive metal halides such as aluminum alkyls, alkylsilicon halides, and the like. Prior to use, the support material can be subjected to a heat treatment at 100 ° C to 1000 ° C, preferably at about 200 ° C to about 850 ° C in an inert atmosphere or under reduced pressure. Typically, this treatment is carried out for about 10 minutes to about 72 hours, preferably from about 0.5 hours to 24 hours. The support material, optionally heat treated, may be preferably combined with another organometal metalloid compound, more preferably an organoaluminum compound, more preferably a trialkylaluminum compound in a suitable diluent or solvent, preferably one in which the organometal compound is soluble. 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 organometal 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. An alternative pretreatment of the support material involves a treatment with alumoxane. The alumoxane can be contacted with the support material in the manner described above, or the alumoxane itself can be generated in the support material by contacting an alkyl aluminum, preferably a trialkylaluminium compound, with a Support that contains water. Preferably, the previously treated support material is recovered before its subsequent use. The previously treated support materials do not contain binding groups, such as, for example, surface hydroxyl groups, which are typically found in different support materials, especially silica and support materials containing silica. The previously treated support materials may contain terminal residues of a material used for pretreatment, such as, for example, an alumoxane residue, or the residue of a trialkylaluminum compound, such as -A1R2. Certain of these residues, in particular an alumoxane residue, or the residue of a trialkylaluminum compound, are capable of reacting with the fraction having an active hydrogen of the anion (a) (2) of the ionic compound. However, if a previously treated silica is used in a process, and at some point in the process a compound is contacted which is the reaction product of (a) an ionic compound and (c) an organometal or metalloid compound, or a substantially inactive catalyst precursor, the reaction to form a covalent bond with binding to the support is not possible, since all potentially reactive groups that could enter a reaction resulting in a binding have been blocked or capped. In various aspects of this invention where a support material is used, including catalyst components and catalysts, as well as corresponding aspects that are not supported, either as homogeneous solutions, solids or dispersions, an alternative expression of each of these aspects is one that is essentially free of alumoxane. In accordance with the present invention, the ionic compound (a) can be formed in a dispersion of solid particles (a) by controlled precipitation. This dispersion can be used as such in the preparation of a solid catalyst suitable for addition polymerization processes, thereby maintaining the dispersed nature. A range of suitable particle sizes can be obtained for the solid dispersed catalyst, by selecting solvents and non-solvents, temperature conditions and specific catalyst components. No intermediate step of recovery or separation is required, and the final solid catalyst, preferably still in the dispersed form, can be employed as such in an addition polymerization process. Alternatively, the particulate solid (a) and the solid catalyst, and any solid intermediate, can be recovered from the diluent in which they are dispersed, by removing the liquid or non-solvent, using techniques such as filtration, drying vacuum, spray drying, and combinations thereof. Before use, the particulate solid (a), the solid catalyst, and any solid intermediate may be redispersed in a suitable liquid diluent. The dispersion of catalyst components of the present invention can be prepared by converting a solution of the ionic compound (a), in a diluent (solvent) in which (a) is soluble, to a dispersion comprising the component (a) ) in solid form. It may be desirable to use a method wherein the conversion is made in the presence of (b) a transition metal compound, and wherein the catalyst component is a substantially inactive catalyst precursor.; or wherein the conversion is made in the presence of (c) an organometal or metalloid compound wherein the metal or metalloid is selected from Groups 1-14 of the Periodic Table of the Elements, and the catalyst component is a reaction product of (a) and (c), or, alternatively, it may be desirable to employ the method in such a manner that the catalyst component excludes (b) a transition metal compound, excludes (c) an organometal or metalloid compound, where the metal or metalloid is selected from Groups 1-14 of the Periodic Table of the Elements, or exclude both (b) and a (c). A solution of the ionic compound (a) in diluent can be obtained by the use of an appropriate solvent in which (a) it is soluble. The diluent in which it is dissolved (a) is not critical. Preferably, the diluent is compatible with the other catalyst components and under polymerization conditions, so there is no need for it to be removed before further use. Suitable solvents for (a) include aromatic hydrocarbons, such as toluene, benzene, ethylbenzene, propylbenzene, butylbenzene, xylenes, chlorobenzene, and the like. When a solvent is used in which (a) it is not sufficiently soluble, or in order to assist in or accelerate the dissolution of (a), heating may be applied or solubilization agents may be used, or a combination of both . The solubilizing agent that is used is compatible with the catalyst components, in a sense that this does not adversely affect the beneficial properties of the catalyst. Heating is preferably done at temperatures no higher than the decomposition temperature of (a). During the dissolution of (a) stirring is conveniently applied. Preferably, the solution of (a) contains from 0.0001 to 100 moles of (a) per liter, more preferably from 0.001 to 10 moles per liter. Preferably any undissolved (a) is removed by, for example, filtration techniques, before subsequently using the solution of (a). The solution of (a) is then converted to a dispersion comprising (a) in solid form. The conversion of the solution from (a) to a dispersion of (a) can be carried out, for example, by a process wherein the dispersion comprising the component (a) is generated by cooling a solution of (a) in a diluent in which (a) is soluble, by contacting a solution of (a) in a diluent in which (a) it is soluble, with a diluent in which (a) it is insoluble or barely soluble, by evaporating the diluent from a solution of (a), by adding one or more precipitating agents to a solution of (a), or a combination of two or more of these techniques, to achieve a precipitation or solidification controlled, so that a dispersion of (a) is formed. It will be clear to a person skilled in the art that the distinction between a solvent and a non-solvent for a particular ionic compound (a) will depend primarily on the nature of the particular compound (a), the temperature, and the relative amount of (a) a) that is going to dissolve. For a given ionic compound (a), the skilled person can easily determine which solvent and what temperature conditions will be used to obtain a solution of the desired concentration. On the other hand, given the solution of (a), the skilled person can easily determine the conditions and means to obtain the dispersion of (a) having the desired solids concentration. When precipitation agents are used, preferably they are compatible with the catalyst components, so that the beneficial properties of the catalyst are not adversely affected. The non-solvent used to generate the dispersion of (a) is not critical. Preferably, the non-solvent is compatible with the other catalyst components and under polymerization conditions, so that it is not necessary to remove it before further use. Preferred non-solvents are, for example, pentane, hexane, heptane, decane, dodecane, kerosene, and higher aliphatic hydrocarbons of up to 30 carbon atoms. The dispersion including component (a) is preferably generated by contacting a solution of (a) in a diluent in which (a) it is soluble with a diluent in which (a) it is insoluble or sparingly soluble . The diluent in which (a) is soluble, is preferably selected from the group consisting of toluene, benzene, and xylenes, and the diluent in which (a) is insoluble or sparingly soluble, is preferably selected from from the group consisting of pentane, hexane, heptane, and octane. Upon contacting the solution of (a) with the non-solvent, the amount of non-solvent is usually from 10 to 10,000 parts by weight, preferably from 100 to 1,000 parts by weight per 100 parts by weight of solution of (a) . The contact temperature is usually 100 to 300 ° C, preferably -50 to 130 ° C, and more preferably 10 to 110 ° C. When it is necessary to remove the solvent, in which it is dissolved (a), after putting it in contact with the non-solvent, the solvent is preferably selected so that it has a lower boiling point than that of the non-solvent. The solvent can be easily removed by heating the dispersion or by applying reduced pressure. Solid catalysts, whether supported or unsupported, in accordance with the present invention can be prepared by combining, in any order, the components (a), (b), (c), and optionally (d) in the in the case of a supported catalyst, wherein at least one step in the preparation of the solid catalyst, the component (a) dissolved in a diluent in which (a) is soluble, optionally in the presence of one or more components (b) , (c), and (d) or the contact product of (a) with one or more of (b), (c), and (d), is converted to a solid form, optionally followed by catalyst recovery solid. After this step, the other components (b), (c) and optionally (d) are brought into contact, to the extent they have not been previously added, with (a) in solid form, preferably dispersed in solid form. According to a step of this invention, the methodology of which is similar to that described above for the preparation of the dispersions of catalyst components, it is desirable that during the at least one step in the preparation of the solid catalyst, a dispersion comprising component (a) in solid form by cooling a solution of (a) in a diluent in which (a) is soluble, by contacting a solution of (a) in a diluent in the which (a) is soluble with a diluent in which (a) it is insoluble or sparingly soluble, by evaporating the diluent from a solution of (a), by the addition of one or more precipitating agents to a solution of (a), or a combination of two or more of these techniques.

In accordance with a preferred embodiment for the preparation of the unsupported or supported solid catalyst, during the at least one step in the preparation of the solid catalyst, a dispersion comprising component (a) in solid form is generated by contacting a solution of (a) in a diluent in which (a) is soluble, optionally in the presence of one or more of the components (b), (c), and (d), or the contact product of (a) with one or more of (b), (c), and (d), with a diluent in which (a) is Insoluble or sparingly soluble. In all the steps of the process subsequent to the dispersion formation step, it is preferred not to use temperature conditions or types or amounts of solvents that could again dissolve the compound (a). The methods that can be used to generate the dispersion of (a) are essentially those that have been described above in connection with the formation of the dispersion of catalyst components. In the method for the preparation of the unsupported or supported solid catalyst, the dispersion comprising component (a) can first be formed after which the other components (b), (c), and optionally (d) can be combined in arbitrary order. In addition, the dispersion comprising component (a) can be formed in the presence of one or more of the other components (b), (c), and optionally (d). Following are the modalities ej emplares. In an embodiment for preparing the unsupported or supported solid catalyst, first the dispersion comprising the component (a) is contacted with the component (b) and the resulting product is subsequently contacted with the component (c). Preferably, the component (b) dissolved in a suitable solvent, such as a hydrocarbon solvent, is conveniently employed, an aliphatic or cycloaliphatic hydrocarbon having 5 to 10 carbon atoms or an aromatic hydrocarbon having 6 to 10 carbon atoms. The contact temperature is not critical as long as it is lower than the decomposition temperature of the transition metal. Component (c) can be used in a clean manner, that is, as it is, or dissolved in a hydrocarbon solvent, which can be similar to that used to dissolve component (b). In a further embodiment for preparing the unsupported or supported solid catalyst, the components (b) and (c) are first contacted, preferably in a suitable solvent, and then contacting the resulting product with the dispersion comprising the component (a). The solvent or solvents used to contact (b) and (c) are of such nature or are used in such amounts, or a combination thereof, as when the resulting product is contacted with the dispersion comprising (a) ), component (b) does not dissolve again substantially. In some of the methods for preparing a supported solid catalyst, including the precipitation methods described above, the manner in which the component (d) is added is not critical. Component (d) can be added during one of the steps in the preparation of the solid catalyst. The support material (d) can be added after the components (a), (b), and (c) have been combined with one another, or can be combined (d) with at least one of the components before combine the resulting product with the rest of the component or components. According to a preferred embodiment for the preparation of a supported solid catalyst, first the component (a) dissolved in a solvent is combined with the component (d), after which the dispersion of (a) in the manner described above in relation to the generation of the dispersion of (a). The combination of component (d) with the solution of component (a) can be performed while forming a slurry, that is, using an excess amount of liquid, or alternatively, only so much of the solution of component (a) is used that no slurry is formed. Conveniently in the latter situation, the volume of the solution of component (a) is not substantially exceeded, and is preferably equal to the pore volume of component (d). After this contact step, the component (a) is converted to a solid form, preferably by combining the contact product of (a) and (d) with a diluent in which (a) it is insoluble or barely insoluble . The amount of solids relative to the amount of non-solvent is not critical but is typically 0.001 to 50 weight percent. When component (d) is contacted with a solution of (a), preferably (d) is used after it has been pretreated to substantially remove all water and surface hydroxyl groups, and especially by treatment with an aluminomalkyl, more preferably with an aluminotrialkyl compound. It is convenient to contact the solution of (a) with component (c), preferably with a molar equivalent of (c), before contacting it with component (d). A highly preferred support material for use in these embodiments is the silica previously treated. Typical, but not critically, temperatures for any of the steps except the dispersion formation step are -50 to 150 ° C. Preferably, each of the contact steps is performed while agitating or moving. All steps in the present process must be conducted in the absence of oxygen and moisture. In an alternative method for the preparation of the supported solid catalyst, it is desirable that the support material used be a previously treated support material with pore volume of from 0.1 to 5 cubic centimeters / gram and that in the supported catalyst, the anion ( a) (2) is not chemically bound to the support (d), and wherein the volume of the solution of (a), optionally in the presence of one or both (b) and (c), is from 20 volume percent up to 200 volume percent of the total pore volume of the support material used. Preferred embodiments are those in which the volume of the solution is from 70 volume percent up to 130 volume percent of the total pore volume of the support material used, or where the volume of the solution is substantially equal to the volume of the solution. Total pore of the support material used. Some aspects of this method may be similar to the different aspects of the processes for the preparation of the supported catalyst, variously referred to as incipient impregnation techniques, or incipient moisture, as described in U.S. Patents Nos. 5,602,067; 5,625,015; and PCT applications WO-95/12622; WO 96/23005; WO 96/16093; WO97 / 02297; and WO-97/24375, all of which are incorporated herein by reference. In alternative aspects of this modality, as mentioned in the two immediately preceding paragraphs, it may be desirable that the solution of (a) occur in the presence of (b), or in the presence of (c), or in the presence from (b) and (c). Generally, in this aspect it is desirable that the solid catalyst be produced by the addition of the solution of (a), optionally containing one or both (b) and (c), to substantially dry the previously treated support material, followed by the removal of the diluent. In another alternative for the preparation of the supported catalyst, it is desirable that the support material used be a previously treated support material with a pore volume of from 0.1 to 5 cubic centimeters / gram and that in the support catalyst, the anion ( a) (2) is not chemically bound to support (b), and where the solution volume of (a), optionally in the presence of one or both (b) and (c), is greater than 200 percent by volume of the total pore volume of the support material used. In alternative aspects of this mode, it may be desirable for solution (a) to occur in the presence of (b), or in the presence of (c), or in the presence of (b) and (c). In this regard it may be desirable for the solid catalyst to be produced by adding the solution of (a), optionally containing one or both (b) and (c), to substantially dry the previously treated support material, followed by the removal of the diluent, or it can be added to a slurry of (d) in a diluent, followed by the removal of the diluent. The solid catalyst can be stored or shipped unsupported or fluidly supported under inert conditions, after the removal of the solvent. The combination of components (a) and (b) in equimolar amounts does not result in a catalyst composition having substantial activity in addition polymerization processes. After combining this composition with component (c), an active catalyst composition is surprisingly formed. Therefore, a further embodiment provides a method for activating a substantially inactive catalyst precursor to form a catalyst suitable for addition polymerization wherein a substantially inactive catalyst precursor comprising an ionic compound (a) and a metal compound of transition (b) and, optionally, component (d) is contacted with an organometal compound (c) to form an active catalyst. In one aspect, preferably, the substantially inactive catalyst precursor is in a solid form, either supported or unsupported, more preferably dispersed in a diluent, while in an alternative aspect where no support is used, they are used all the materials in solution form and the activation process produced a homogeneous solution of a catalyst suitable for solution polymerization. Preferably, in accordance with this activation method, a dispersion of a substantially inactive solid unsupported or supported catalyst precursor, comprising (a), (b) and optionally (separately), is added separately, preferably directly. d), and the organometal compound (c), in an addition polymerization reactor containing an addition polymerizable monomer or monomers, preferably under addition polymerizable conditions. The catalyst components can be added separately to the reactor or to the specific places in the reactor which allows the catalyst to be activated only in the reactor or in a specific place in the reactor, which offers a more controllable polymerization reaction. This is especially convenient where the addition polymerization reactor is operated under polymerization conditions by slurry phase or by gas phase. The relative amounts of the components that will be used in the compositions and processes of the present invention will now be described. The relative amount of the ionic compound (a) for the transition metal grammatomes in the compound (b) is not critical but is generally in the range of from 0.1 to 500 moles of (a) by grammatomes of (b). Preferably, 0.5 to 100 moles of (a) are used by grammatomes of (b), more preferably from about 1 to 3 moles of (a) by grammatomes of (b). The percentage between the organometal compound (c) and the ionic compound (a) is not critical, but is generally within the range of 0.05 to 1,000 moles of (c) per mole of (to) . Preferably, the percentage is from 0.5 to 100 moles (c) per mole (a), more preferably from about 1 to 50 moles (c) per mole (a). The amount of the optional component (d) that will be used in the present invention is also not critical, however, typical values range from 0.1 μmol to 2 μmol of the ionic compound (a) per gram of support material. Preferably, from 10 to 1,000 μmol of ionic compound (a) is used per gram of support material. The solid catalyst can be used as such or after having been subjected to prepolymerization. The prepolymerization can be performed by any known method, such as by contacting a small amount of one or more polymerizable monomers with the solid catalyst. The monomers that can be used in the prepolymerization are not particularly limited and include the olefins and diolefins mentioned hereinafter. It is preferable to use the same monomer for the prepolymerization as that used in the subsequent polymerization. The prepolymerization temperature can usually fluctuate from -20 ° C to 100 ° C, preferably from -10 ° C to 70 ° C, more preferably from 0 to 50 ° C. The prepolymerization can be carried out batchwise or continuously under atmospheric pressure or high pressures. The prepolymerization can be performed in the presence of a molecular weight controlling agent such as hydrogen. The prepolymerization is carried out in the absence or presence of a solvent or diluent. When a solvent or a diluent is used, it is preferably an inert hydrocarbon, such as those described hereinafter with respect to the polymerization process. Preferably the solvent or diluent that is used does not substantially re-dissolve the catalyst comprising the ionic compound (a). Typically prepolymerization is performed to form a prepolymerized catalyst, ie the polymer is formed on the solid catalyst particles, having from 0.1 to 100 grams of polymer per 1 gram of the solid catalyst, preferably from 1 to 10 grams of polymer per gram of solid catalyst. The typical particle sizes of the prepolymerized catalysts are in the range of 1 to 200 μm, preferably in the range of 10 to 100 μm. The solid catalysts of the present invention, optionally prepolymerized, can be used in an addition polymerization process wherein one or more of the polymerizable monomers are contacted by addition with the solid 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 8 carbon atoms and combinations of two or more of said alpha-olefins. Particularly suitable alpha-olefins include, for example, ethylene, propylene, 1-butene, 1-pentene, 4-methylpentene, 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, propylene, 1-butene, 4-methylpentene, 1-pentene, 1-hexene, 1-octene, and combinations of ethylene / or propylene with one or more of said other alpha-olefins. More preferably, ethylene or propylene is used as one of the addition polymerizable monomers. Suitable dienes include those that have 4 to 30 carbon atoms, especially those that have to 18 carbon atoms. Typical of these are the internal diamines, α-dienes, including those dienes that are typically used to prepare 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 halo- or alkyl, tetrafluoroethylene, vinyl-cyclobutene, dicyclopentadiene, and ethylidene norbornenes. Suitable addition polymerizable monomers also include any mixtures of the monomers mentioned above. The solid catalyst in itself can be formed in the polymerization mixture by introducing catalyst components (a), (b), (c), and optionally (d) into the mixture. The solid catalysts of this invention, both supported and unsupported, as well as the homogeneous catalysts can be used in different catalyst systems, either alone or with other catalyst components, wherein the catalyst of this invention is an integral part of the catalyst. catalyst system. The catalyst can be used in the polymerization reaction in 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, preferably 10 to 9x10"6 moles per liter of diluent or reaction volume.

The solid catalysts are conveniently employed in a high pressure, solution, slurry or gas phase polymerization process. For a solution polymerization process, it is desirable to dissolve the solid catalyst again or to employ homogeneous solutions of the catalyst components. Usually a high-pressure process is carried out at temperatures of 100 ° C to 400 ° C and at pressures above 500 bar. A slurry process typically uses an inert hydrocarbon diluent of from 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 from about 30 ° C, preferably from about 60 ° C to about 115 ° C, preferably up to 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. Generally, the solubility of the polymer depends on its density. For ethylene copolymers having densities of 0.86 grams / cubic centimeter, the polymerization of the solution can be achieved at temperatures as low as about 60 ° C. Preferably, the polymerization temperatures of the solution range from about 75 ° C, more preferably from about 80 ° C, and typically from about 130 ° C to about 260 ° C, more preferably up to about 170 ° C. Most preferably, the temperatures in a solution process are between about 80 ° C and 150 ° C. As inert solvents, hydrocarbons and preferably aliphatic hydrocarbons are typically used. The solution and slurry processes are usually carried out at pressures between about 1 to 100 bar. Typical operating conditions for the 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 the gas phase polymerization processes, the solid catalyst has a mean particle diameter of from about 20 to about 200 μm, more preferably from about 30 μm to about 150 μm, and more preferably from about 50 μm to about 100 μm. Preferably for use in slurry polymerization processes, the support has a mean particle diameter of from about 1 μm to about 200 μm, more preferably from about 5 μm to about 100 μm, and most preferably from about 10 μm to approximately 80 μm. Preferably for use in solution or high pressure polymerization processes, the support has a mean particle diameter of from about 1 μm to about 40 μm, more preferably from about 2 μm to about 30 μm, and greater preference from about 3 μm to about 20 μm. In the polymerization processes of the present invention, impurity cleaners can be used which serve to protect the solid catalyst from catalyst poisons such as water, oxygen, and polar compounds. These cleaners can usually be used in amounts depending on the amounts of impurities. Typical cleaners include organometallic compounds, and preferably trialkylaluminium or boron compounds and aluxomans. In addition, antistatic agents can be introduced into the reactor to prevent agglomeration or adhesion of the polymer or catalyst to the walls of the reactor. Molecular weight control agents, such as hydrogen or other chain transfer agents can also be used in the present polymerization process. The polymers prepared according to said polymerization processes can be combined with any conventional additives, such as UV stabilizers, antioxidants, 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. The solvents suitable for the different polymerization processes are inert liquids. Examples include straight and branched chain hydrocarbons such as isobutane, butane, pentane, hexane, heptane, octane, and mixtures thereof, - cyclic and alicyclic hydrocarbons such as cyclohexane, cycloheptane, methylcyclohexane, methylcycloheptane, and mixtures thereof. same; perfluorinated hydrocarbons such as perfluorinated alkanes of 4 to 10 carbon atoms, and the like; and aromatic and alkyl substituted aromatics such as benzene, toluene, xylene, ethylbenzene and the like. Suitable solvents also include olefins which can act as monomers or comonomers including ethylene, propylene, butadiene, 1-butene, cyclopentene, 1-hexene, 1-heptene, 4-vinylcyclohexene, vinyl-cyclohexene, 3-methyl-1-pentene , 4-methyl-1-pentene, 1,4-hexa-diene, 1-octene, 1-decene, styrene, divinylbenzene, allyl-benzene, vinyltoluene (including all isomers alone or in mixtures), and the like. Mixtures of the above are also suitable. The catalyst systems can be used in combination with at least one additional homogeneous or heterogeneous catalyst in separate reactors connected in series or in parallel to prepare polymer blends having desirable properties. An example of such a process is described in WO-94/00500, equivalent to United States of America Serial Number 07 / 904,770, as well as Serial Number of the United States of North America 08/10958, filed on 29 January 1993, the teachings of which are hereby incorporated herein by reference. Using the catalyst systems of the present invention, particularly for solution polymerization, copolymers having a high comonomer incorporation and a corresponding low density, and yet having a low melt index, can be easily prepared. That is, high molecular weight polymers are easily obtained by the use of the present catalyst, even at high reactor temperatures. This result is highly desirable because the molecular weight of the α-olefin copolymers can be easily reduced by the use of hydrogen or a similar chain transfer agent, however, usually the molecular weight increase of the α-olefin copolymers it can be obtained only by means of reducing the polymerization temperature of the reactor. In an inconvenient manner, the operation of a polymerization reactor at reduced temperatures significantly increases the operating cost since the heat of the reactor must be removed to maintain the reduced reaction temperature, while at the same time heat must be added to the effluent. of the reactor to vaporize the solvent. In addition, productivity is increased due to the improved solubility of the polymer, the lowered viscosity of the solution, and a higher concentration of the polymer. Using the present catalysts, α-homopolymers and copolymers having densities from 0.85 grams / cubic centimeter to 0.96 grams / cubic centimeter, and melt flow rates from 0.001 to 10.0 dg / minute, can be achieved in a process of high temperature. The solid catalysts of the present invention, when used also in a slurry process or in a gas phase process, can not only produce ethylene copolymers of typical densities for high density polyethylene, in the range of 0.980 to 0.940 grams / cubic centimeter, but surprisingly, also facilitate the production of copolymers having substantially lower densities. Copolymers of densities of less than 0.940 grams / cubic centimeter and especially less than 0.930 grams / cubic centimeter to 0.880 grams / cubic centimeter or less can be made, while providing free flowing polymers, which retain good mass density properties and while which prevent or substantially eliminate clogging in the reactor. The present invention can produce olefin polymers and copolymers having weight average molecular weights of more than 30,000, preferably more than 50,000, more preferably more than 100,000 to 1,000,000 and even higher. The typical molecular weight distributions Mw / Mn range from 1.5 to 15, or higher, preferably between 2.0 and 8.0. The catalyst systems of the present invention are particularly suitable for the production of ethylene homopolymers and ethylene / α-olefin copolymers having high levels of long chain branching, especially in solution polymerization processes and in gas phase polymerizations. . The use of the catalyst systems of the present invention in continuous polymerization processes, especially continuous solution polymerization processes, allows high reactor temperatures, which favors the formation of finished vinyl polymer chains that can be incorporated in a polymer in growth, giving by the same a long chain branching. The use of the present catalyst system conveniently allows the economical production of the ethylene / c-olefin copolymers having processability similar to high pressure, the free radical produced low density polyethylene. In another aspect of the processes of this invention, a preferred process is a high temperature solution polymerization process for the polymerization of olefins comprising contacting one or more olefins of 2 to 20 carbon atoms under polymerization conditions with a system of catalyst of this invention at a temperature of from about 100 ° C to about 250 ° C. Most preferred as a temperature range for this process is a temperature of from about 120 ° C to about 200 ° C, and even more preferred is a temperature of from about 150 ° C to about 200 ° C. The present catalyst system can be conveniently employed to prepare olefin polymers having improved processing properties by ethylene polymerization alone or mixtures of ethylene / α-olefins with low levels of an "H" branched induction diene, such as norbornadiene, 1, 7-octadiene, or 1, 9-decadiene. The unique combination of high reactor temperatures, high molecular weight (or low melt indexes) at high reactor temperatures and high comonomer reactivity conveniently allows economical production of polymers having excellent physical properties and processability. Preferably said polymers comprise an α-olefin of 3 to 20 carbon atoms, including ethylene, and a branching comonomer "H". Preferably, said polymers are produced in a process by solution, more preferably a process by continuous solution. Alternatively, said polymers can be produced in a gas phase process or a slurry process, as described in the Application of the United States of America Serial No. 08/857817, filed May 16, 1997.; Application of the United States of America Number 08/857817, filed May 16, 1997; and PCT Application Number PCT / US97 / 08466, filed May 16, 1997, all of which are incorporated herein by reference. As previously mentioned, the present catalyst system is particularly useful in the preparation of EP and EPDM copolymers in high yield and productivity. The process employed may be either a solution or a slurry process, both previously known in the art. Kaminsky, J. Poly. Sci., Volume 23, pages 2151-64 (1985) reported the use of a bis (cyclopentadienyl) zirconium dimethyl-alumoxane soluble catalyst system, for the solution polymerization of EP elastomers and EPDM. U.S. Patent No. 5,229,478 described a slurry polymerization process using similar catalyst systems based on bis (cyclopentadienyl) zirconium. In general terms, it is desirable to produce said EP and EPDM elastomers under conditions of increased reactivity of the diene monomer component. The reason for this was explained in the '478 patent identified above as follows, which is still true in spite of the advances achieved in said reference. An important factor that affects production costs and therefore the utility of an EPDM is the cost of the diene monomer. Diene is a more expensive monomer material than ethylene or propylene. In addition, the reactivity of the diene monomers with the metallocene catalysts known above is lower than that of ethylene or propylene. Consequently, in order to achieve the necessary degree of incorporation of the diene to produce an EPDM with an acceptably fast cure rate, it has been necessary to use a diene monomer concentration which, expressed as a percentage of the total monomer concentration present, is in substantial excess compared to the percentage of diene that it is desired to incorporate in the final EPDM product. Because substantial amounts of unreacted diene monomer must be recovered from the effluent polymerization reactor for recycling, the production cost is unnecessarily increased. A further addition to the cost to produce an EPDM is the fact that, generally, the exposure of an olefin polymerization catalyst to a diene, especially the high concentrations of diene monomer required to produce the necessary level of diene incorporation in the EPDM final product, generally reduces the speed or activity at which the catalyst would cause the polymerization of the ethylene and propylene monomers to proceed. Correspondingly, lower yields and longer reaction times have been required, compared to the production of an ethylene-propylene copolymer elastomer or other α-olefin copolymer elastomer. The present catalyst system conveniently allows increased diene reactivity by preparing EPDM polymers in high yield and productivity. Additionally, the catalyst system of the present invention achieves economical production of EPDM polymers with diene contents of up to 20 weight percent or more, said polymers possessing highly desirable rapid cure rates. The non-conjugated diene monomer may be a straight chain, branched chain or cyclic hydrocarbon diene having from about 6 to about 15 carbon atoms. Examples of suitable non-conjugated dienes are straight-chain acyclic dienes such as 1,4-hexadiene and 1,6-octadiene; branched chain acyclic dienes such as 5-methyl-1,4-hexadiene; 3, 7-dimethyl-l, 6-octadiene; 3, 7-dimethyl-l, 7- octadiene and mixed isomers of dihydromyricenne and dihydrocycene; single ring alicyclic dienes such as 1,3-cyclopentadiene; 1,4-cyclohexadiene; 1,5-cyclooctadiene and 1,5-cyclododecadiene; and fused multiple ring and ring alicyclic dienes such as tetrahydroindene, methyl tetrahydroindene, dicyclopentadiene; bicyclo- (2, 2, 1) -hepta-2, 5-diene, -alkenyl, alkylidene, cycloalkenyl and cycloalkylidene norbornenes such as 5-methylene-2-norbornene (MNB), -5-propenyl-2-norbornene, 5-isopropylidene-2-norbornene, 5- (4-cyclopentenyl) -2-norbornene, 5-cyclohexylidene-2-norbornene, 5-vinyl-2-norbornene and norbornadiene. Of the dienes typically used to prepare the EPDMs, the particularly preferred dienes are 1,4-hexadiene (HD), 5-ethylidene-2-norbornene (ENB), 5-vinylidene-2-norbornene (VNB), 5-methylene-2-norbornene (MNB), and dicyclopentadiene (DCPD). Especially preferred dienes are 5-ethylidene-2-norbornene (ENB) and 1,4-hexadiene (HD). Preferred EPDM elastomers may contain about 20 to about 90 weight percent ethylene, more preferably about 30 to 85 weight percent ethylene, more preferably about 35 to about 80 weight percent ethylene. Alpha-olefins suitable for use in the preparation of elastomers with ethylene and dienes are preferably alpha-olefins of 3 to 16 carbon atoms. Illustrative non-limiting examples of said alpha-olefins are propylene, 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 1-heptene, 1-octene, 1-decene, and 1-dodecene. The alpha-olefin is generally incorporated within the EPDM polymer at from about 10 to about 80 weight percent, more preferably from about 20 to about 65 weight percent. The non-conjugated dienes are generally incorporated within the EPDM at from about 0.5 to about 20 weight percent, more preferably from about 1 to about 15 weight percent, and most preferably from 3 to about 12 weight percent. weight. If desired, more than one diene can be incorporated simultaneously, for example HD and ENB, with the incorporation of total diene within the limits specified above. At all times, the individual ingredients as well as the catalyst components of the recovered, oxygen and moisture must be protected. Therefore, catalyst components and catalysts should be prepared and recovered in an atmosphere free of oxygen and moisture. Preferably, therefore, the reactions are carried out in the presence of a dry, inert gas such as, for example, nitrogen. Polymerization can be carried out as a batch or continuous polymerization process. A continuous process is preferred, in which case the catalyst components, ethylene, α-olefin, and optionally the solvent and the diene are continuously supplied to the reaction zone and the polymer product is continuously removed from the reaction zone. same. Within the scope of the terms "continuous" and "continuously" as used in this context, there are those processes in which there are intermittent additions of reagents and removal of products at small regular intervals of time, so that, over time , the total process is continuous. In a preferred mode of operation, the polymerization is conducted in a continuous solution polymerization system comprising two reactors connected in series or in parallel. A relatively high molecular weight product (Mw of 300,000 to 600,000, more preferably 400,000 to 500,000) is formed in a reactor, while a relatively low molecular weight product (Mw 50,000 to 300,000) is formed in the second reactor. The final product is a mixture of the effluents of the two reactors which are combined before devolatilization to result in a uniform mixture of the two polymer products. Said double reactor process allows the preparation of products having improved properties. In a preferred embodiment, the reactors are connected in series, that is, the effluent from the first reactor is charged to the second reactor and fresh monomer, solvent and hydrogen are added to the second reactor. The reactor conditions are adjusted so that the weight percentage of the polymer produced in the first reactor to that produced in the second reactor is from 20:80 to 80:20. In addition, the temperature of the second reactor is controlled to produce the lower molecular weight product. This system allows the production of EPDM products that have a large range of Mooney viscosities in a beneficial way, as well as excellent strength and processability. Preferably, the Mooney viscosity (ASTM D1646-94, ML1 + 4 @ 125 ° C) of the resulting product is adjusted to be within the range of 1 to 200, preferably 5 to 150 and more preferably 10 to 110. The polymerization process of the present invention can be used to benefit the gas phase copolymerization of olefins. Processes by gas phase for the polymerization of olefins, especially the homopolymerization and copolymerization of ethylene and propylene, and the copolymerization of ethylene with higher α-olefins such as, for example, 1.butene, 1-hexene, 4 -methyl-l-pentene, are well known in the art. These processes are commercially used on a large scale for the manufacture of high density polyethylene (HDPE), medium density polyethylene (MDPE), linear low density polyethylene (LLDPE) and polypropylene. The process by gas phase employed may be, for example, of the type which employs a mechanically stirred bed or a gas fluidized bed as the polymerization reaction zone. Preferred is the process in which the polymerization reaction is carried out in a vertical cylindrical polymerization reactor containing a fluidized bed of polymer particles supported or suspended on a perforated plate, the fluidization grid, by means of a flow or fluidizing gas. The gas used to fluidize the bed comprises the monomer or monomers to be polymerized, and also serves as a heat exchange medium for removing the heat of reaction from the bed. The hot gases emerge from the upper part of the reactor, usually by means of a zone of tranquility, also known as a zone of speed reduction, which has a larger diameter than the fluidized bed and where the fine particles transported in the gas stream have an opportunity to gravitate back to bed. It may also be convenient to use a cyclone to remove ultra-fine particles from the hot gas stream. Then the gas is normally recycled to the bed by means of a fan or a compressor and one or more heat exchangers to strip the gas of the heat of the polymerization. A preferred method for cooling the bed, in addition to the cooling provided by the cooled recycle gas, is to feed a volatile liquid to the bed to provide an evaporative cooling effect, often referred to as an operation in the condensation mode. The volatile liquid used in this case can be, for example, a volatile inert liquid, for example, a saturated hydrocarbon having from about 3 to about 8, preferably from 4 to 6, carbon atoms. In the event that the monomer or comonomer itself is a volatile liquid, or can be condensed to provide such a liquid, it can be suitably powered to provide an evaporative cooling effect. Examples of olefin monomers that can be used in this manner are olefins containing from about three to about eight, preferably from about three to six carbon atoms. The volatile liquid evaporates in the hot fluidized bed to form gas which is mixed with the fl uidifying gas. If the volatile liquid is a monomer or a comonomer, it will undergo some polymerization in the bed. Then the evaporated liquid emerges from the reactor as part of the hot recycle gas, and enters the compression / heat exchange part of the recycling cycle. The recycle gas is cooled in the heat exchanger and, if the temperature at which the gas is cooled is less than the dew point, the liquid will precipitate from the gas. This liquid is desirably recycled continuously to the fluidized bed. It is possible to recycle the precipitated liquid to the bed as droplets of liquid carried in the recycle gas stream. This type of process is described, for example, in EP-89691; U.S. Patent Number 4,543,399; WO 94/25495 and U.S. Patent Number 5,352,749, which are incorporated by reference herein. A particularly preferred method for recycling the liquid to the bed is to separate the liquid from the recycle gas stream and re-inject this liquid directly into the bed, preferably using a method which generates fine droplets of liquid within the bed. In WO-94/28032 of BP Chemicals this type of process is described, and is incorporated by reference herein. The polymerization reaction occurring in the gas fluidized bed is catalyzed by the continuous or semi-continuous addition of the catalyst. Such a catalyst can be supported on an inorganic or organic support material as described above. The catalyst can also be subjected to a prepolymerization step, for example, by polymerizing a small amount of olefin monomer in a liquid inert diluent, to provide a compound comprising catalyst particles embedded in the olefin polymer particles. The polymer is produced directly in the fluidized bed by the catalyzed copolymerization of the monomer and one or more comonomers in the fluidized particles of the supported catalyst, catalyst or prepolymer within the bed. The start of the polymerization reaction is achieved by using a bed of preformed polymer particles, which are preferably similar to the target polyolefin, and conditioning the bed by drying it with inert gas or nitrogen before introducing the catalyst, the monomers and any other gases that are desired in the recycle gas stream, such as a diluent gas, hydrogen chain transfer agent, or an inert condensable gas when operating in the gas phase condensation mode. The produced polymer is discharged continuously or discontinuously from the fluidized bed as desired. The gas phase processes suitable for the practice of this invention are preferably continuous processes which provide a continuous supply of reactants to the reaction zone of the reactor and the removal of products from the reaction zone of the reactor, providing by the same a stable state environment in the macro-scale in the reaction zone of the reactor. Typically, the fluidized bed of the process is operated per gas phase at temperatures greater than 50 ° C, preferably from about 60 ° C to about 110 ° C, more preferably from about 70 ° C to about 110 ° C. Typically, the molar ratio of the comonomer to the monomer used in the polymerization depends on the density desired for the composition to be produced and is about 0.5 or less. Desirably, when materials with a density range of from about 0.91 to about 0.93 are being produced, the ratio of comonomer to monomer is less than 0.2, preferably less than 0.05, even more preferred less than 0.02, and may be to less than 0.01. Typically, the ratio of hydrogen to monomer is less than about 0.2, more preferably less than 0.05, even more preferred less than 0.02 and may be up to less than 0.01. The ranges described above of variable processes are suitable for the gas phase process of this invention and may be suitable for other processes adaptable to the practice of this invention. A number of patents and patent applications describe processes by gas phase which are adaptable for use in the process of this invention, particularly US Pat. Nos. 4,588,790; 4,543,399; 5,352,749; 5,436,304; 5,405,922; 5,462,999; 5,461,123; 5,453,471; 5,032,562; 5,028,670; 5,473,028; 5,106,804; 5,556,238; 5,541,270; 5,608,019; 5,616,661; and the applications of EP 659,773; 692,500; 780,404; 697,420; 628,343; 593,083; 676,421; 683,176; 699,212; 699,212; 699,213; 721,798; 728,150; 728,151; 728,771; 728,772; 735,058; and PCT Applications WO-94/29032, WO-94/25497, WO-94/25495, WO-94/28032, WO-95/13305, WO-94/26793, WO-95/07942, WO-97 / 25355, WO-93/11171, WO-95/13305, and WO-95/13306, all of which are hereby incorporated by reference. For the preferred polyolefin polymer compositions of this invention, which can be produced by polymerization processes of this invention using the catalyst systems of this invention, the long chain branching is longer than the short chain branching resulting from the incorporation of one or more α-olefin comonomers into the base structure of the polymer. The empirical effect of the presence of long chain branches in the copolymers of this invention is manifested, as improved rheological properties which are indicated as higher flow activation energies, and I21 / I2 greater than that expected from other structural properties of The compositions . In addition, the highly preferred polyolefin copolymer compositions of this invention have an inverse molecular architecture, that is, there is a maximum molecular weight which occurs at that 50 weight percent of the composition which has the comonomer content percent in weight. higher weight. Even more preferred are the polyolefin copolymer compositions, which also have long chain branches along the base structure of the polymer, especially when produced with a catalyst system of this invention having a single metallocene complex of this invention in a single reactor, in a process for the polymerization of an α-olefin monomer with one or more olefin comonomers, more especially when the process is a continuous process.

Measurement of Comonomer Content against Record Molecular Weight by GPC / FTIR The comonomer content was measured as a function of molecular weight by coupling a Fourier Transform Infrared Spectrometer (FTIR) to a Gel Impregnation Chromatograph (GPC) ) of 150 ° C of Waters. The placement, calibration and operation of this system together with the method for data processing have been described above (LJ, Rose et al., "Characterization of Polyethylene Copolymers by Coupled GPC / FTIR" in "Characterization of Copolymers", Rapra Technology, Shawbury GB, 1995, ISBN 1-85957-048-86.). In order to characterize the degree to which the comonomer is concentrated in the high molecular weight part, the Gel Impregnation Chromatograph / Fourier Transform Infrared Spectrometer was used to calculate a parameter called the comonomer partition factor, Cpf. Mn and Mw were also determined using standard techniques from the Gel Impregnation Chromatograph data.

Comonomer Partition Factor (GPC-FTIR) The partition factor of comonomer C "f was calculated from the Gel Impregnation Chromatograph data. This characterizes the ratio of the average comonomer content of the highest molecular weight fractions to the average comonomer content of the lower molecular weight fractions. The higher and lower molecular weights are defined as being above or below the average molecular weight respectively, that is, the molecular weight distribution is divided into two parts of the same weight. The Cpf is calculated from the following equation: n S Wj-Cj i = l n S Wj i = l m S j- Cj Cpf = i = l where; c: is the content of m comonomer in mole fraction and w: is SW: i = l the normalized weight fraction as determined by the Gel Impregnation Chromatograph / Fourier transform infrared spectrometer for the data points n of the spectrometer Infrared Fourier transformation on the average molecular weight, C; is the comonomer content in mole fraction and: is the normalized weight fraction as determined by the Gel Impregnation Chromatograph / Fourier Transform Infrared Spectrometer for the data points m of the Fourier Transform infrared spectrometer below the medium molecular weight. Only those fractions of weight, w, or w = which have values of comonomer content in mole fraction associated, are used to calculate the Cpf. For a valid calculation, it is required that n and m be greater than or equal to 3. The Fourier transform infrared spectrometer data corresponding to the fractions of molecular weight below 5,000 are not included in the calculation, due to the present uncertainties. in said data. For the polyolefin copolymer compositions of this invention, Cpf is desirably equal to or greater than 1.10, more desirably equal to or greater than 1.15, still more desirably equal to or greater than 1.20, preferably equal to or greater than 1.30, more preference is equal to or greater than 1.40, even more preferred is equal to or greater than 1.50, and still more preferred is equal to or greater than 1.60.

ATREF-DV ATREF-DV has been described in U.S. Patent No. 4,798,081, which is incorporated herein by reference, and in "Determination of Short-Chain Branching Distributions of Ethylene Copolymers by Automated Analytical Temperature Rising Elution Fractionation "(Auto-ATREF), J. of Appl Pol Sci: Applied Polymer Symposium 45, 25-37 (1990). The ATREF-DV is a dual detector analytical system that can fractionate semi-crystalline polymers such as Linear Low Density Polyethylene (LLDPE) as a function of crystallization temperature while simultaneously estimating the molecular weight of the fractions. In relation to the fractionation, the ATREF-DV is analogous to the Temperature Elevation Levigation Fractionation (TREF) analysis that has been published in the open literature during the past 15 years. The main difference is that this Analytical - Temperature Raising Levigation (ATREF) technique is done on a small scale and the fractions are not really isolated. Instead, a liquid chromatographic mass (LC) detector, such as in a single infrared frequency detector, is used to quantify the distribution of crystallinity as a function of levigation temperature. This distribution can then be transformed to any number of alternative domains such as short branch frequency, comonomer distribution, or possibly density. In this way, this transformed distribution can then be interpreted according to some structural variable such as the comonomer content, although frequently the routine use of the Analytical - Temperature Raising Levigation Technique technique for comparisons of different Linear Low Density Polyethylene directly in the domain of the temperature of levigation. To obtain the ATREF-DV data, a commercially available viscometer specially adapted for LC analysis, such as Viskotek ™, is coupled to the infrared mass detector. These two detectors can be used together to calculate the intrinsic viscosity of the ATREF-DV levigator. The average viscosity molecular weight of a given fraction can then be calculated using the appropriate Mark Houwink constants, the corresponding intrinsic viscosity, and the appropriate coefficients to calculate the concentration of the fractions (dl / g) as it passes through. the detectors. In this way, a typical ATREF-DV report will provide the polymer in weight fraction and the viscosity average molecular weight as a function of levigation temperature. Then the Mpf is calculated using the given equation.

Molecular Weight Partition Factor The molecular weight partition factor pf is calculated from the TREF / DV data. This characterizes the ratio of the average molecular weight of the fractions with high comonomer content to the average molecular weight of the fractions with low comonomer content. The contents of high and low comonomer are defined as being below or above the average levigation temperature of the concentration plane of the Temperature Elevation Levigation Fractionation respectively, that is, the data of the Fractionation of Temperature Elevator Levigation are divided into two parts of the same weight. The pf is calculated from the following equation: n S Wj-Mj i = l n S Wj i = l m S Wj-Mj Mpf = i == 1, where; Mj is the average molecular weight m of viscosity and w i is S W; j-1 the normalized weight fraction as determined by the ATREF-DV for the data points n in the fractions below the average levigation temperature. M i is the viscosity average molecular weight and w i is the normalized weight fraction as determined by the ATREF-DV for data points m in the fractions above the average levigation temperature. Only those weight fractions, w¿ or w: which have average viscosity weights greater than zero associated, are used to calculate the Mpf. For a valid calculation, it is required that n and m be greater than or equal to 3. For the polyolefin copolymer compositions of this invention, the mp is desirably equal to or greater than 1.15, more desirably equal to or greater than 1.30, even more desirably is equal to or greater than 1.40, preferably equal to or greater than 1.50, more preferably equal to or greater than 1.60, even more preferred is equal to or greater than 1.70. Having described the invention, the following examples are provided as an additional illustration thereof and should not be considered limiting. Unless otherwise specified, all parts and percentages are expressed on a weight basis.

EXAMPLES The mass density of the polymers produced in the present examples was determined in accordance with the ASTM 1895. All experiments were performed under the exclusion of oxygen and water, under a nitrogen atmosphere, unless otherwise indicated.

Preparation of Kemamime hydrochloride T9701 Kemamime R T9701 (NMe (C18.22H37.45) 2 (13.4 grams, 25 mmol), available from Witco Corp. (Kemamime is a registered trademark of Witco Corp.), was dissolved in diethyl ether (300 milliliters was bubbled through the solution for 5 minutes, until the pH became acidic, as the pH paper showed, the mixture was stirred for 15 minutes and the white precipitate was collected by filtration. washed with three 50 milliliter portions of diethyl ether and dried under vacuum The production of NHCIMe (C18_22H37 ^ 5) 2 was 12.6 grams.

Preparation of f (p-HOC6H4) B (C6F5) 31 ÍNHMe (C1S 22H37 ^ s) 21 NHClMe (C23_22H37_45) 2 (4.58 grams, 8 mmol), dichloromethane (50 milliliters) was dissolved. Triethylammonium borate tris (pentafluorophenyl) (4-hydroxyphenyl) [(p-HOC6H) B (C6F5) 3] (5.66 grams, 8 mmol, prepared as described substantially in Example IB of the application for Patent of the United States of America Number 08 / 610,647, filed March 4, 1996 (corresponding to WO-96/28480), followed by 40 milliliters of distilled water. The mixture was stirred rapidly for 4 hours and then the water layer was removed by syringe. The dichloromethane layer was washed three times with portions of 40 milliliters of distilled water. The dichloromethane layer was then dried over sodium sulfate, filtered and dried under vacuum to produce an oil. The oil was extracted in toluene (200 milliliters), the resulting solution was filtered and the filtrate was vacuum dried to yield 8.84 grams of a colorless oil.

Example 1. Preparation of the catalyst 1 milliliter of a 0.031 M solution was treated [(p-HOC6H4) B (C6F5) 3] [NHMe (C18_22H37_45) 2] in toluene, with 18 milliliters of n-hexane by the addition of n-hexane producing a cloudy suspension which was stirred for 5 minutes. A solution of titanium, (Nl, 1-dimethylethyl) dimethyl (1- (1, 2, 3, 4, 5-eta) -2,3,4,5-tetramethyl-2,4-cyclopentadiene-1- was added. il) silanaminate)) (2-) N) - (? -1, 3-pentadiene) (C5Me4SiMe2NtBu) Ti (r? 4-l, 3-pentadiene) (0.33 milliliters of a 0.0925 M solution in IsoparMR E; IsoparMR E, a registered trademark of Exxon Chemical Company, is a mixture of saturated hydrocarbons with 8 carbon atoms), to generate a red-brown suspension. After 5 minutes while stirring, a 6 milliliter aliquot of this mixture was treated with 0.2 mmol of triethylaluminum (2 milliliters of a 0.1M solution in n-hexane) and the mixture was stirred for an additional 15 minutes before using it as such in a polymerization reaction.

Slurry phase polymerization A stirred 5 liter reactor was charged with 100 μmol of triisobutylaluminum, 3 liters of hexane and 0.5 standard liters of hydrogen before heating to 60 ° C. Then ethylene was added to the reactor in an amount sufficient to bring the total pressure to 10 bar. Then an aliquot of the catalyst prepared as described above containing 10 μmol of titanium was added to initiate the polymerization. The reactor pressure was maintained essentially constant by continuously feeding the ethylene in demand during the polymerization reaction. The temperature was kept substantially constant by cooling the reactor as required. After 49 minutes the fed ethylene was closed and the contents of the reactor were transferred to a sample tray. After drying, 925 grams of a free-flowing polyethylene powder were obtained. It was calculated that the efficiency was 1,931,100 grams of polyethylene PE / g Ti and the density of mass, 0.29 grams / cubic centimeter. The scanning electron micrographs of the polyethylene powder indicated the presence of spherical particles that had a smooth surface morphology.

Example 2 (comparative) The slurry polymerization process of Example 1 was repeated, but without the use of triethylaluminium in the catalyst preparation step, without adding the triisobutylaluminum to the reactor, and while using an amount of 30 μmol of titanium for the polymerization reaction. No polyethylene product was obtained.

Example 3 One milliliter of a 0.031 M solution was treated [(p-HOC6H4) B (C6F5) 3] [NHMe (C18.22H37.45) 2] in toluene, with 10 milliliters of n-hexane producing a cloudy suspension and the mixture was stirred for 5 minutes. A mixture of a solution of (C5Me4SiMe2NtBu) Ti (? 4-l, 3-pentadiene) (0.33 milliliters of a 0.0925 M solution in Isopar E) and 0.3 mmol of triethylaluminium (3 milliliters of a 0.1 M solution in n-hexane), and the mixture was stirred for 15 minutes. An aliquot of this mixture containing 10 micromol of titanium in a polymerization reaction was used as such.

The polymerization conditions were identical to those of Example 1 except that the duration was 48 minutes. After drying, 850 grams of a free-flowing polyethylene powder were obtained. It was calculated that the efficiency was 1,774,530 g PE / g Ti.

Example 4 0.5 milliliters of a 0.031 solution were treated M from [(p-HOC6H4) B (C6F5) 3] [NHMe (C18_22H37.45) 2] in toluene, with 15 milliliters of n-hexane producing a cloudy suspension and the mixture was stirred for 5 minutes. 0.075 mmol of triethylaluminum (0.75 milliliters of a 0.1M solution in n-hexane) was added, and the mixture was stirred for 5 minutes. A solution of (C5Me4SiMe2NtBu) Ti (? 4-l, 3-pentadiene) (0.16 milliliters of a solution of 0.0925 M in Isopar ^ E) was added and the mixture was stirred for 5 minutes. This mixture was used as such in a polymerization reaction. The polymerization conditions were identical to those of Example 1 except that the duration was 30 minutes. After drying, 630 grams of a free-flowing polyethylene powder were obtained. It was calculated that the efficiency was 888.675 g PE / g Ti.

Example 5 40 grams of silica SP12 (Grace Davidson) were made slurry which had been heated at 250 ° C for 3 hours under vacuum, in toluene (400 milliliters) and then treated with 40 milliliters of triethylaluminum in 250 milliliters of toluene. The mixture was stirred for 1 hour, the treated silica (100 milliliters, approximately 100 ° C) was filtered and washed with toluene and dried under high vacuum. 10 milliliters of a 0.031 M solution of [(p-HOC6H4) B (C6F5) 3] [NHMe (C18.22H37.45) 2] in toluene was treated with 40 milliliters of n-hexane producing a cloudy suspension. The mixture was stirred for 5 minutes. 3.1 mmol of triethylaluminum (15.5 milliliters of a 0.2 M solution in n-hexane) was added, and the mixture was stirred for 5 minutes. An aliquot of this suspension containing 40 μmol of borate was treated with 40 μmol of a solution of (C5Me4SiMe2NtBu) Ti (IT4-1, 3-pentadiene) (0.43 milliliters of a 0.0925M solution in IsoparMK-E). The resulting suspension was added to a slurry of 1 gram of silica treated as described above, in 20 milliliters of hexane. The mixture was stirred for 5 minutes and then an aliquot of the mixture containing μmol of titanium as such in a slurry polymerization. The polymerization conditions were identical to those of Example 1 except that the duration was 30 minutes. 600 grams of a free-flowing polyethylene powder of a mass density of 0.31 grams / cubic centimeter were obtained. The efficiency was calculated to be 835.070 g PE / g Ti.

Example 6 Two grams of silica treated with triethylaluminium (prepared as in Example 5) were placed in a 20 milliliter flask. In a separate vessel, 1.23 milliliters of a solution of [(p-HOC6H4) B (C6F5) 3] [NHMe (C18_22H37.45) 2] (0.065 M) in toluene containing 80 micromol of borate was diluted with an additional 1 milliliter. of toluene. 0.13 milliliters of a 0.6 M solution of triethylaluminum in hexane was added and the mixture was stirred for 10 minutes. The borate / triethylaluminum solution, the volume of which corresponded to the pore volume of the support material, was added to the treated support material and the mixture was stirred. 8 milliliters of hexane were added to the dry powder to give a slurry, followed by a solution of (C5Me4SiMe2 N (Bu) Ti (β-1,3-pentadiene) (0.86 milliliters of a 0.0925M solution in Isopar® E) producing a green supported catalyst The polymerization conditions were identical to those of Example 1 except that the polymerization time was 36 minutes and an aliquot of the catalyst containing 15 micromole Ti was used, 260 grams of a powder were obtained of free-flowing polyethylene with a mass density of 0.25 grams / cubic centimeter.The efficiency was 361.860 g PE / g Ti.

Example 7 10 milliliters of a 0.031 solution were treated M from [(p-HOC6H4) B (C6F5) 3] [NHMe (C18.22H37.45) 2] in toluene, with 10 milliliters of n-hexane producing a cloudy suspension. In a separate vessel, 0.33 milliliters of a 0.08 M solution of (n-BuCp) 2ZrCl2 were treated in toluene with 3 milliliters of a 0.1 M solution of triethylaluminum in n-hexane followed by 2 milliliters of n-hexane. The zirconocene solution was added to the borate suspension and the mixture was stirred for a few minutes. An aliquot of the catalyst prepared as above containing 10 μmol of zirconium was used in a polymerization reaction. After 55 minutes, 580 grams of a free-flowing polyethylene powder were obtained. The efficiency was calculated to be 317.912 g PE / g Ti.

Example 8 0.43 milliliters of a 0.092 M solution of [(p-HOC6H4) B (C6F5) 3] [NHMe (C18.22H37.45) 2] in toluene was treated with 40 milliliters of a 0.1 M solution of triethylaluminum in toluene. 10 milliliters of n-hexane was added to produce a fine precipitate. 0.31 milliliters of a 0.13 M solution of (C5MeSiMe2NtBu) Ti (γ4-l, 3-pentadiene) in Isopar® was added and the mixture was stirred for a few minutes. An aliquot of the catalyst containing 20 μmol of titanium was used in a polymerization reaction. No alkylaluminium cleaner was used and 0.3 liters of hydrogen were added. After 30 minutes, 420 grams of a free-flowing polyethylene powder were obtained. The density of the mass was 0.22 grams / cubic centimeter and the efficiency was calculated to be 438.413 g PE / g Ti.

Example 9 0.43 milliliters of a 0.092 M solution of [(p-HOC6H4) B (C6F5) 3] [NHMe (C18.22H37.45) 2] in toluene was treated with 10 milliliters of n-hexane to give a suspension cloudy 0.31 milliliters of a 0.13 M solution was added (C5Me4SiMe2NtBu) Ti (? 4-1,3 -pentadiene) in Isopar1 ^ E to produce an orange-brown suspension. An aliquot of this suspension containing 20 μmol of titanium was used in a polymerization reaction. 500 μmol of triethylaluminum was added as a preload to the reactor. After 15 minutes, 120 grams of a free-flowing polyethylene powder were obtained. The efficiency was calculated to be 125,260 g PE / g Ti.

Example 10 1 gram of silica treated with triethylaluminum (prepared as in Example 5 but using 45 micron silica gel, Grace Davidson) was placed in a 20 milliliter flask. In a separate vessel, 0.43 milliliters of a solution of [(p-HOC6H) B (C6F5) 3] [NHMe (C18.22H37_45)] in toluene was treated with 0.40 milliliters of a 0.1 M solution of triethylaluminum in toluene. The resulting solution was added to the treated support material and the mixture was stirred. 10 milliliters of n-hexane were added to make the support slurry followed by a solution of 0.031 grams of rac-Me2Si (2-methyl-4-phenyl-indenyl) 2Zr (1,4-diphenyl-l, 3-butdiene), in 10 milliliters of n-hexane. A stirred 5 liter reactor was charged with 1.6 liters of n-hexane and 1.4 liters of propylene and the mixture was maintained at a temperature of 10 ° C. An aliquot of the catalyst prepared above containing 20 μmol of Zr was injected into the reactor together with 400 milliliters of n-hexane. The contents of the reactor were heated to 70 ° C and after holding at 70 ° C for ten minutes, the reaction was stopped by transferring the contents to a sample vessel. After drying, 585 grams of free-flowing polypropylene powder with a mass density of 0.34 grams / cubic centimeter was obtained. The efficiency was calculated to be 320.723 g PE / g Zr.

Example 11 20 grams of silica treated with triethylaluminium (prepared as in Example 5) was charged to a vessel. 17.2 milliliters of a 0.0465 M solution of [(p-HOC6H4) B (C6F5) 3] [NHMe (C18.22H37.45) 2] in toluene was treated with 8 milliliters of a 0.1 M solution of triethylaluminum in toluene and the mixture was stirred briefly. An additional 10 milliliters of toluene was added to give a total volume of 36 milliliters. This solution was added to the silica treated with dry triethylaluminum and the mixture was stirred rapidly. 400 milliliters of n-hexane was added and the resulting slurry was stirred for 10 minutes. A solution of 0.13 M of (C5Me SiMe2NtBu) Ti (γ4-l, 3-pentadiene) in Isopar1 ^ 11 E was added and the mixture was stirred for 1 hour. This resulted in the formation of a supported dark green catalyst. Isopentane, ethylene, 1-butene (if required), hydrogen and supported catalyst were continuously fed to a continuously stirred tank reactor, covered with 10 liters, and the slurry product was continuously removed. The total pressure was 15 bar and the temperature was maintained at 70 ° C. The slurry was fed to a flask tank to remove the diluent and the free flowing dry polymer powder was collected. At the first run, the following feed rates were used: Isopentane (2500 grams / hour), ethylene (760 grams / hour), hydrogen (1 Nl / hour) and supported catalyst, 0.368 grams / hour. efficiency of 823,000 g PE / g Ti and with the following properties: I2 2.41, density 0.9638 grams / cubic centimeter In a second run, the following feed rates were used: Isopentane (2500 grams / hour), ethylene (1120 grams / hour) ), 1-butene ( 37 grams / hour), hydrogen (1 Nl / hour) and supported catalyst, (0.325 grams / hour). The polymer powder was produced at an efficiency of 1,569,000 g PE / g Ti and with the following properties. I2 1.02, density 0.9303 grams / cubic centimeter, 1-butene, 1.72 percent.

Example 12 15 grams of silica treated with triethylaluminium (prepared as in Example 5 but using 45 micron silica gel, Grace Davidson) was charged in a container, treated with 2 milliliters of a 0.298 M solution of [(p- HOC6H4) B (C6F5) 3] [NH e (C18_22H37_45) 2] in toluene, with 6 milliliters of a 0.1 M solution of triethylaluminum in toluene and the mixture was stirred briefly. An additional 8.5 milliliters of toluene was added to give a total volume of 16.5 milliliters. This solution was added to the silica treated with dry triethylaluminum and the mixture was stirred rapidly. 400 milliliters of n-hexane was added and the resulting slurry was stirred for 10 minutes. 4.61 milliliters of a 0.13 M solution of (C5Me4SiMe2N £ Bu) Ti (γ4-l, 3-pentadiene) in Isopair® E were added and the mixture was stirred for 1 hour. This resulted in the formation of a supported dark green catalyst. The n-hexane (2500 grams / hour), the ethylene (1025 grams / hour), the hydrogen (3.5 Nl / hour) and the supported catalyst (0.5875 grams / hour) were continuously fed to a stirred tank reactor. continuously, covered with 10 liters, and the slurry product formed was continuously removed. The total pressure was 12 bar and the temperature was maintained at 65 ° C. The slurry that was withdrawn was fed to a second identical reactor together with n-hexane (2500 grams / hour), ethylene (950 grams / hour), 1-butene (4.7 grams / hour) and supported catalyst (0.5875 grams / hour) . The total pressure in the second reactor was 11 bar and the temperature 75 ° C. The slurry was withdrawn to a flash tank to remove the diluent and the free flowing, dry polymer powder was collected. It was calculated that the total efficiency was 750,000 g PE / g Ti. The polymer powder had the following properties, I2 0.47, density, 0.9679 grams / cubic centimeter and mass density, 0.373 grams / cubic centimeter. Scanning Electron Micrographs: The samples of polyethylene produced by slurry (HDPE), of Example 1, which had been coated with gold, were examined by scanning electron micrograph using a Philips model SEM505 operating at an acceleration voltage of 6. kV, which results in what is shown in Figure 1A and in Figure IB at a 50-fold amplification, in Figure 2A and Figure 2B at 200 times, and in Figure 3A and Figure 3B at 1000 times. The photomicrographs indicate that the surface morphology is very smooth and that it seems that there are particles of mainly two size ranges. The largest particles are in the size range of approximately 50 microns in diameter and the smallest particles are in the size range of approximately 5 microns in diameter.

Gas Phase Example The following polymerization examples were carried out in a 13-liter gas phase reactor having a fluidization zone of four inches in diameter and thirty inches in length and a speed reduction zone of eight inches in diameter. diameter and ten inches in length, which are connected by a transition section having tapered walls. The typical operating ranges were from 40 to 100 ° C, total pressure from 6 to 25 bar and up to 8 hours of reaction time. Ethylene, comonomer, hydrogen and nitrogen entered the bottom of the reactor where they passed through the gas distributor plate. The gas flow was 2 to 8 times the minimum particle fluidization rate. See Fluidization Engineering, 2a. edition, D. Kunii and 0. Levenspiel, 1991, Butterworth-Heinemann. Most of the suspended solids were separated in the velocity reduction zone. The reactive gases left the top of the velocity reduction zone and passed through a dust filter to remove any fines. Then the gases passed through a gas booster pump. The polymer was allowed to accumulate in the reactor during the course of the reaction. The total system pressure during the reaction was maintained constant by regulating the monomer flow within the reactor. The polymer was removed from the reactor to a recovery vessel by opening a valve located at the bottom of the fluidization zone. The polymer recovery vessel was maintained at a lower pressure than that of the reactor. The pressures of ethylene, the comonomer and hydrogen reported, refer to partial pressures. Reference is made to the mode of operation of the reactor that was used as a semilote. The catalyst was prepared and charged into a catalyst injector in an inert atmosphere cover box. The appropriate amounts of ethylene, 1-butene, hydrogen and nitrogen were introduced into the reactor to bring the total pressure to the desired reaction temperature. The catalyst was then injected and the polymer was usually allowed to form for 30 to 90 minutes. The total system pressure was maintained constant during the reaction, by means of regulating the monomer flow inside the reactor. Upon completion of the run, the reactor was emptied and the polymer powder was collected.

Example 13 Catalyst / support preparation 15.9 grams of ES70Y Crosfield type silica (surface area = 315 square meters / gram and a Malvern particle size of [D50] = 106.8 microns) were heated at 500 ° C for 4 hours in a stream inert nitrogen The silica was allowed to cool to room temperature in an inert stream of nitrogen. The silica calcination tube was then sealed at both ends and carried inside an inert atmosphere cover box. The silica was removed from the calcination tube, then slurry was made with 80 milliliters of hexane at a ratio of 5 milliliters of hexane / gram of silica. To the silica in the form of slurry, 2.93 grams of a solution of 93 percent by weight of triethylaluminium (TEA) was added, which corresponded to a treatment of 1.5 mmol triethylaluminum / gram of silica. The slurry was allowed to stand for 2 hours with gentle shaking by hand every 15 to 20 minutes. After 2 hours the silica was filtered and washed twice with a total of 100 milliliters of hexane to remove any soluble aluminum compounds that may have resulted during the triethylaluminium treatment step. The silica was then dried at room temperature under vacuum to give a free-flowing powder. To 100 milliliters of a 0.036 M solution of [(p-HOC6H4) B (CgF5) 3] [NHMe (Ci8-22 7-45) 2] in toluene, 0.0036 mol (0.383 grams) of triethylaluminium was added. The mixture was stirred at room temperature for 18 1/2 hours. 0.278 milliliters of the above solution were added dropwise to 1.0 gram of silica ES70Y treated with triethylaluminum described above followed by vigorous stirring for 15 minutes. Then 0.0427 milliliters of a 0.234 M solution of (i75-C5Me4SiMe2NtBu) Ti (γ4,1, 3-pentadiene) were added dropwise to the silica followed by vigorous stirring for 15 minutes. The catalyst loading was 10 micromol / gram of silica. 10 milliliters of hexane was added to the formulated catalyst followed by vigorous stirring of the resulting slurry for 20 minutes. The slurry was then filtered and washed twice with a total of 10 milliliters of hexane. The formulated catalyst was then dried at room temperature under vacuum to give a free flowing powder.

Polymerization 0.1 grams of the above-described formulated catalyst was added to the semilote gas phase reactor which was under an ethylene pressure of 6.5 bar, a pressure of 1-butene of 0.14 bar, a hydrogen pressure of 0.04 bar and a pressure of nitrogen of 2.8 bar. The polymerization temperature throughout the run was 70 ° C. An exotherm of 6 ° C was measured on the catalyst injection. After 30 minutes, 16.0 grams of polymer was recovered.

Example 14 0.075 grams of the formulated catalyst described above in Example 13 was added to a semilote gas phase reactor which was under an ethylene pressure of 6.5 bar, a pressure of 1-butene of 0.14 bar, a pressure of hydrogen 0.04 bar and a nitrogen pressure of 2.8 bar. The polymerization temperature throughout the run was 70 ° C. An exotherm of 6 ° C was measured on the catalyst injection. After 30 minutes, 15.9 grams of polymer was recovered.

Example 15 0.05 grams of the formulated catalyst described above in Example 13 was mixed with 0.415 grams of the triethylaluminum-treated silica described in Example 13. The mixture was added to the semilote gas phase reactor which was under an ethylene pressure. of 6.5 bar, a pressure of 1-butene of 0.14 bar, a pressure of hydrogen of 0.04 bar and a pressure of nitrogen of 2.8 bar. The polymerization temperature throughout the run was 69 ° C. An exotherm of 5 ° C was measured on the catalyst injection. After 18 minutes, 5.4 grams of polymer was recovered.

Example 16 0.05 grams of the formulated catalyst described above in Example 13 was mixed with 0.4 grams of the triethylaluminum treated silica described in Example 13. The mixture was added to the semilote gas phase reactor, which was under an ethylene pressure of 6.5 bar, a pressure of l-butene of 0.14 bar, a hydrogen pressure of 0.04 bar and a nitrogen pressure of 13.7 bar. The catalyst was injected at a reactor temperature of 70 ° C. An exotherm of 4 ° C was measured on the catalyst injection. After injection of the catalyst, the temperature in the reactor increased to 75 ° C over the course of 90 minutes. After 90 minutes, 24.3 grams of polymer was recovered.

Example 17 Preparation of the catalyst To 100 milliliters of a solution of 0. 036 M [(p-HOC6H) B (C6F5) 3] [NHMe (C18.22H37.45) 2] in toluene, 0.0036 mol (0.383 grams) of triethylaluminum was added. The mixture was allowed to stir at room temperature for 18 1/2 hours. 0.417 milliliters of the above solution were added dropwise to 1.0 gram of silica ES70Y treated with triethylaluminum described above followed by vigorous stirring for 15 minutes. Then 0.0641 milliliters of a 0.234 M solution of (j75C5MeSiMe2NtBu) Ti (? -1,3-pentadiene) was added dropwise to the silica followed by vigorous stirring for 15 minutes. The catalyst loading was 15 micromol / gram of silica. 10 milliliters of hexane was added to the formulated catalyst followed by vigorous stirring of the resulting slurry for 20 minutes. The slurry was then filtered and washed twice with a total of 10 milliliters of hexane. The formulated catalyst was then dried at room temperature under vacuum to give a free flowing powder.

Polymerization 0.033 grams of the above-described formulated catalyst was mixed with 0.35 grams of the triethylaluminum treated silica described in Example 13. The mixture was added to the semilote gas phase reactor which was under an ethylene pressure of 6.5 bar, a n-butene pressure of 0.14 bar and a nitrogen pressure of 13.7 bar. The temperature of the polymerization throughout the run was 72 ° C. No exotherm was measured on the catalyst injection. After 15 minutes, 5.8 grams of polymer was recovered.

Example 18 0.017 grams of the formulated catalyst described in Example 5 was mixed with 0.35 grams of the triethylaluminum treated silica described in Example 1. The mixture was added to the semilote gas phase reactor which was under an ethylene pressure of 6.5 bar, a n-butene pressure of 0.14 bar, a hydrogen pressure of 0.04 bar and a nitrogen pressure of 13.7 bar. The temperature of the polymerization throughout the run was 71 ° C. No exotherm was measured on the catalyst injection. After 90 minutes, 12.5 grams of polymer were recovered.

Example 19 Preparation of the catalyst To 100 milliliters of a 0.036 M solution of [(p-HOC6H) B (C6F5) 3] [NHMe (C18.22H37.45) 2] in toluene, 0.0036 mol (0.383 grams) of triethylaluminium. The mixture was allowed to stir at room temperature for 18 1/2 hours. 0.278 milliliters of the above solution were added dropwise to 1.0 gram of silica ES70 type Crosfield, treated with triethylaluminum (surface area = 289 square meters / gram and a Malvern particle size of [D50] = 35.2 microns), followed by agitation vigorous for 15 minutes. The silica ES70 type Crosfield and treated with triethylaluminum had been calcined in a manner analogous to the procedure described in Example 1. Then 0.0427 milliliters of a 0.234 M solution of (t? 5C5Me4SiMe2 tBu) Ti (r? -1) were added dropwise. , 3 -pentadiene) to the silica followed by vigorous agitation for 15 minutes. The catalyst loading was 10 micromol / gram of silica. 10 milliliters of hexane was added to the formulated catalyst followed by vigorous stirring of the resulting slurry for 20 minutes. The slurry was then filtered and washed twice with a total of 10 milliliters of hexane. The formulated catalyst was then dried at room temperature under vacuum to give a free flowing powder.

Polymerization 0.05 grams of the above-described formulated catalyst was mixed with 0.35 grams of the triethylaluminum treated silica described in Example 13. The mixture was added to the semilote gas phase reactor which was under an ethylene pressure of 6.5 bar, a n-butene pressure of 0.14 bar, a hydrogen pressure of 0.04 bar and a nitrogen pressure of 13.7 bar. The temperature of the polymerization throughout the run was 72 ° C. An exotherm of 3 ° C was measured on the catalyst injection. After 90 minutes, 26.3 grams of polymer was recovered.

III. Examples of Polypropylene Example 20 Preparation of the catalyst In relation to different aspects of the preparation of the transition metal compound, see Organomet 13, (1994), 954 on page 962; also see the Patent of the United States of America Number 5,278,264 which is hereby incorporated by reference: 24Dn Me2Si bis (2-Me-4-Ph-Indenyl) Zr diphenyl butadiene The rac-Me2Si (2-methyl-4-phenyl-indenyl) 2 zrCl2 (4.00 grams, 6.36 mmol) and the diene (1.313 grams, 6.36 mmol) in a 250 milliliter flask and slurry was made in 150 milliliters of octane, 8.9 milliliters of nBuLi were added. (1.6 M, 14.31 mmol) by syringe. The reaction mixture was stirred at room temperature throughout the weekend. The reaction was then held at 80-85 ° C for about 6 hours followed by 2 hours at reflux, then cooled to room temperature. The octane solution was filtered after cooling and the insolubles were washed with hexane until it is colorless. The solvent was removed in vacuo. The product was slurried in 10 milliliters of fresh hexane and placed in the freezer at -30 ° F for 1 hour. The cold slurry was filtered and the solid product was dried in vacuo to give rac-Me2Si (2-methyl-4-phenyl-indenyl) 2 Zr (1,4-diphenyl-1,3-butadiene) as a red solid ( yield = 2182 grams, 45 percent, 82.3 percent by weight 24DN, 17.7 percent by weight of free diene). ÍH NMR (CgDg, ppm): 7.8 - 6.5 (multiplets, aromatic protons, and free diene protons), 5.6 (s, 2H, indenyl proton), 3. 45 (multiplet, 2H, PhC4H4Ph), 1.7 (multiplet of singlet superposition, s, indenylmethyl; m, PLtu ^^ Ph, total 8H), 0.9 (s, SiMe2, 6H). Previous treatment of the silica: To 5.00 grams of 50μm silica (Grace Davidson XPO-2402, which was previously calcined at 500 ° C) were added 50 milliliters of toluene. To the mixture was added 5 milliliters of clean triethylaluminium (TEA), and the mixture was stirred for one hour. The mixture was filtered over a medium frit, and the silica was washed twice with 50 milliliters of boiling toluene, followed by 50 milliliters of hexane. The silica was then pumped dry by closing the top of the frit with a plug. After 3 hours 45 minutes in vacuo, 5.48 grams of treated silica was recovered (SiO2 / triethylaluminum). A 0.91 milliliter 0.1M solution of [(p-HOC6H4) B (C6F5) 3] [NHMe (C18.22H37.45) 2] in toluene (91 mmol) was combined with 2.7 milliliters of toluene and 0.91 milliliters of 0.1 M triethylaluminum (91 mmol) and the solution was stirred with a total volume of 4.5 milliliters for 10 minutes. This mixture was added in three portions to 2.28 grams of the previously treated Si02, prepared above, in a 50 milliliter flask. The mixture was gently stirred for several minutes with a spatula to evenly distribute the liquid over the solid until a free-flowing powder was obtained. 20 milliliters of hexane was added to the solid, mixing the new mixture with a spatula for 2 minutes. The previously treated silica was filtered and pumped to dry for one hour. 2.33 grams of solid product were obtained and placed in a 100 milliliter container. A solution of 85 milligrams of the transition metal compound 24Dn prepared above, was dissolved in 3.6 milliliters of toluene (91 μmol) and added to the vessel in 3 portions of approximately 1.2 milliliters each, by gently mixing thoroughly with a spatula after which each portion was added, to ensure the homogeneous distribution of the catalyst solution in the solid. The solid material was rinsed four times with 40 milliliters of hexane. The gray-blue solid was dried for one hour in vacuo. A sample of 127 milligrams of this finished material was subjected to a Zr analysis by neutron activation. The analysis showed that the loading was 23 μmol Zr / gram of silica.

Example 21 Preparation of previously treated support. Silicone ES70 from Crosfield was calcined at 250 ° C for four hours with nitrogen flow through a fluidized bed. After cooling, 50 milliliters of clean triethylaluminum was added to 5 grams of the calcined silica in a 4 ounce bottle. The bottle was closed and balanced for one hour on a mixer type oscillator. The sample was dried under vacuum for one hour to give 5.3 grams of the silica treated with finished triethylaluminium. A 0.91 milliliter 0.1M solution of [(p-HOC6H4) B (C6F5) 3] [NHMe (C18.22H37_45) 2] in toluene (60 mmol) was combined with 0.3 milliliters of toluene and 0.06 milliliters of 0.1M of triethylaluminum (60 mmol) and the solution was stirred with a total volume of 4.5 milliliters for 10 minutes. This solution was added in three portions to 1.0 gram of the previously treated Si02, prepared above, in a 100 milliliter bottle. The mixture was stirred gently for several minutes with a spatula to evenly distribute the liquid over the solid until a free flowing powder was obtained, and at that time it was washed three times with 20 milliliter portions of hexane. The previously treated silica was filtered and pumped to dry for one hour. The solid product was placed in a 100 milliliter container. A solution of 1.5 milliliters containing 60 μmol of 24Dn of the transition metal compound was added to the vessel, mixing thoroughly with a spatula to ensure a homogeneous distribution of the catalyst solution on the solid.

General Polymerization Procedure Propylene, Isopar ^ E, hydrogen and nitrogen were purified by passing them through packed columns of activated Q-5 and alumina. The 24Dn catalyst supported on the cover box was made with approximately 20 milliliters of hexane.

Polypropylene prepared with the Supported Catalyst of Example 20 A two liter stainless steel reactor was dried by vigorously stirring 1 milliliter of 0.1 M aluminum tri-isobutyl in toluene solution, added to 1 liter of Isopar® for one hour. at 70 ° C. The reactor was washed with isopaiX ^ at 70 ° C. It was then charged with a mixture consisting of 351 grams of propylene, 40 grams of hexane, and 26 delta psi hydrogen by differential pressure expansion from a 75 milliliter tank. The mixture was heated to 70 ° C and then a slurry was prepared with 100 milligrams (2 μmol 24Dn catalyst as Zr), 10 μmol of triethylaluminum and 5 milliliters of hexane were added to the reactor. The reaction was allowed to proceed for 30 minutes. The contents of the reactor were then collected in a stainless steel container purged with nitrogen. The polymers were dried overnight in a vacuum oven at 130 ° C. Performance 48 grams. The standard 13C techniques showed that the polymer was 96 percent isometric triad [mm], with 0.95 percent inverse inserts. The polymer had an Mw / Mn = 320,000 / 82,000 = 3.9, as determined by standard GPC techniques.

Polypropylene prepared with the Supported Catalyst of Example 21 The same procedure as described above was repeated, using 351 grams of propylene, 40 grams of hexane, and 26 delta psi hydrogen by differential pressure expansion from a 75 milliliter tank. After 35 minutes of reaction time, the polymer was collected and dried as described above. The yield of polypropylene was 45 grams.

Solubility of Ionic Compounds 1) The influence of the long chain hydrocarbon ammonium cation on the solubility of toluene is evident, by comparing 1 and 2. 2) The solubility to hexane of [(p-HOC6H4) B (C6F5) 3] [NHMe (C18.22H37.45) 2] is much smaller than the solubility of toluene (compare 1 and 3). 15 The influence of the hydroxy substituent on the solubilities of the long chain ammonium salts is evident, by means of comparing 3 and 4. 4) The influence of the solvent on the solubilities of the product of [(p-HOC6H4) becomes evident. B (C6F5) 3] [NHMe (C18.22H37.45) 2] and triethylaluminum, by comparing 5 and 6. Note that 6 is even more insoluble than 3.

The solubilities were determined as follows. A known amount of the material was weighed into a flask, followed by a known amount of hexane or toluene. The mixture was stirred rapidly for at least a period of 16 hours at 22 ° C. If the material was not dissolved under these test conditions, then it was considered to be insoluble at that concentration and temperature. The total dissolution gave a minimum solubility at that temperature. A sign greater than (>) indicates a minimum solubility. A sign less than (<) indicates that the maximum solubility was less than the given number.

Claims (13)

1. CLAIMS 1. A compound that is the reaction product of: (a) an ionic compound comprising (a) (1) a cation and (a) (2) an anion having up to 100 non-hydrogen atoms and contains at least one substituent comprising a fraction having an active hydrogen, wherein the cation (a) (1) is represented by the following general formula: [L * -H] +, wherein: L is a nitrogen, oxygen , sulfur or phosphorus containing Lewis base, containing from one to three alkyl groups of 10 to 40 carbon atoms, with a total of from 12 to 100 carbons, and the anion (a) (2) corresponds to the Formula ( II): [M'm + Qn (Gq (TH) r) z] d "(II) where: M 'is a metal or metalloid selected from Groups 5 to 15 of the Periodic Table of the Elements; Q is independently selected in each presentation, from the group consisting of hydride, dihydrocarbylamido, halide, hydrocarbyloxide, hydrocarbyl, and hydrocarbyl radicals. The hydrocarbyl radicals substituted by halogen, and organo-metalloid radicals substituted by hydrocarbyl and halohydrocarbyl, preferably having the hydrocarbyl portion in each of these groups of 1 to 20 carbons, with the proviso that in no more than one presentation Q is halide; G is a polyvalent hydrocarbon radical having valences of r + 1 linked to the groups M 'and r (T-H); the group (TH) is a radical wherein T comprises 0, S, NR, or PR, whose 0, S, N, or P atom is linked to the hydrogen atom H, wherein R is a hydrocarbyl radical, a radical of trihydrocarbylsilyl, a trihydrocarbylgermyl radical or hydrogen; m is an integer from 1 to 7, n is an integer from 0 to 7, q is an integer from 0 to 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, and (c) an organometal or metalloid compound corresponding to the formula: M ° Rc? Xay, where M ° is a metal or metalloid selected from Groups 2, 12, 13, or 14 of the Periodic Table of the Elements, Rc independently in each presentation is hydrogen, or a group having from 1 to 80 non-hydrogen atoms, which is hydrocarbyl, hydrocarbylsilyl, trihydrocarbylsilyl, trihydrocarbylgermyl, or hydrocarbylsilylhydrocarbyl; Xa is a non-interfering group having from 1 to 100 non-hydrogen atoms, which is hydrocarbyl substituted by halogen, hydrocarbyl substituted by hydrocarbylamino, hydrocarbyl substituted by hydrocarbyloxy, hydrocarbylamino, di (hydrocarbyl) amino, hydrocarbyloxy or halide; x is an integer that is not zero, which can vary from 1 to an integer equal to the valence of M °; and is zero or an integer that is not zero, which can vary from 1 to an integer equal to 1 less than the valence of M °; and x + y is equal to the valence of M °.
2. 2. A compound of claim 1, corresponding to the formula: [L * -H] + [(CgF5) 3BC6H4-0-M ° Rc? _1Xay] ~.
3. 3. The compound of claim 2, corresponding to the formula: [L * -H] + [(C5F5) 3BC6H4-0-AIREc2] "4. A composition of matter comprising the compound of any of claims 1 a 3, and (b) a transition metal compound 5. A composition of matter, which comprises: (a) a compound according to any of claims 1 to 3, and (d) a support material which is a porous resinous material or a solid inorganic oxide, where: (i) the support material is pretreated to remove the binding groups, and the anion (a) (2) is not chemically bonded thereto. composition according to claim 5, wherein: the cation (a) (1) is selected from the group consisting of Bronsted acid cations, carbonium cations, silylium cations, oxonium cations, organometallic cations, and agents cationic oxidants 7. A composition according to claim 6, wherein the cation (a) (1) of the ionic compound (a) is represented by the following general formula: [L * -H] +, wherein: L is a nitrogen, oxygen, sulfur or phosphorus containing Lewis base, containing from one to three alkyl groups of 10 to 40 carbon atoms, with a total of from 12 to 100 carbons. 8. A composition of matter, which comprises: (a) a compound according to claim 4, and (d) a support which is a porous resinous material or a solid inorganic oxide, wherein: (i) the support material is pre-treat to remove binding groups, and anion (a) (2) is not chemically bonded to it. 9. A composition according to claim 8, wherein: the cation (a) (1) is selected from the group consisting of Bronsted acid cations, carbonium cations, silylium cations, oxonium cations, organometallic cations , and cationic oxidizing agents. 10. A composition according to claim 9, wherein the cation (a) (1) of the ionic compound (a) is represented by the following general formula: [L -H] +, wherein: L is a nitrogen, oxygen, sulfur or phosphorus containing Lewis base, containing from one to three alkyl groups of 10 to 40 carbon atoms, with a total of from 12 to 100 carbons. 11. A composition according to claim 4, in the form of a dispersion in a diluent. 12. A composition according to claim 5, in the form of a dispersion in a diluent. 13. A composition according to claim 8, in the form of a dispersion in a diluent.