MXPA98005406A - Catalyzer of fosfinimina-ciclopentadienilo sport - Google Patents

Abstract

A catalyst component which is especially useful in the so-called "gas phase" or "slurry" olefin polymerizations and which comprises an organometallic complex of a group 4 metal (having a ligand of the cyclopentadienyl type and a ligand of phosphinimine) and a particulate support. The catalyst component forms a catalyst system, excellent when combined with an activated such as an aluminoxane or a so-called "substantially non-coordinating anion". In a preferred embodiment, the organometallic complex and the activator both are deposited on the particulate support

Description

CATAL I ZADORE S DE FOS END IMINA-CICLOPENTADIENILO SUPPORTED FIELD OF THE INVENTION This invention relates to a supported phosphinimine-cyclopentadienyl catalyst component which is useful in the polymerization of olefins. The catalyst component is particularly useful in the gaseous phase or slurry polymerization processes.

BACKGROUND OF THE INVENTION The use of olefin polymerization catalysts, based on bis (cyclopentadienyl) complexes of transition metals (metallocenes) and related mono-5-cyclopentadienyl complexes (which are also frequently referred to as metallocenes) in the polymerization of olefins is now widely known. These complexes can be activated by aluminum alkyls and / or aluminum alkyl halides which are conventionally used with the so-called "Ziegler Natta" polymerization catalysts, although the use of REF: 027768 such conventional activators usually do not provide a highly active catalyst. Professors Kaminsky and Sinn discovered that alu oxanes are excellent activators for zirconocenes in homogeneous polymerizations. However, the catalyst systems reported by Kaminsky and Sinn typically contained a very large excess of alumoxane (as much as 10,000 / 1 excess of aluminum to the transition metal on a molar basis). It has not been found commercially practical to use such a large excess of aluminum for supported catalysts. Most notably, it is difficult to efficiently support large amounts of the alumoxane. The lower amount of supported aluminoxane used in the supported form of these catalysts has the effect of increasing the aluminum / transition metal ("Al / M") ratios of such catalysts. Simply put, the concentration of metal would need to approach impractically low levels to maintain the Al / M ratio, given the limited amount of alumoxane which can be supported. Elborn and Turner reveal various forms of supported Kaminsky / Sinn catalysts which have low Al / M ratios (see, for example, the US patent ("USP" for its acronym in English) No. 4,897,455 and USP No. 5,077,255). Hlatky and Turner subsequently fabricated the highly refined invention which refers to the use of the so-called "substantially non-coordinating anions" to activate the bis-Cp metallocenes (as published in USP No. 5,153,157 and USP No. 5, 198, 401). The present invention relates to a catalyst component which contains an organometallic complex of a group 4 metal having a cyclopentadienyl type ligand and a phosphinimine ligand ("phosphinimine complex"). References in the literature describing similar phosphinimine complexes include: Cyclopentadienyl Titanium Complexes with aryldiasenido or phosphiniminate-Ligands by J.R. Dilworth, Journal of Organometallic Chemistry, 159 (1978) 47-52; Syntheses und Reaktionen von (? 5_ Pentamethylcyclopentadienyl) -und (? 5 Ethyltetramethylcyclopentadienyl) titantri fluorid by S. Manshoeh et al., Chem. Ber. , 1993 136, 913-919; Neue Komplexe des Titans mit silylierten Aminoiminophosphoran - und Sulfodiimidliganden by R. Hasselbring et al., Zei tschrift für anorganische und a llgemeine Chemie, 619 (1993) 1543-1550; Phosphaniminato-Ko plese des Titans, Syntheses und Kristallstrukturen von CpTiCl2 (NPMe3), [TiCl3 (NPMe3)] 2, Ti2Cl5 (NPMe2Ph) 3 und [Ti3Cl6 (NPMe3) 5] [BPh] by T. Rubenstahl et al., Zei tschrift für anorganische und al lgemeine Chemi e, 620 (1994) 1741-1749; and Syntheses and reactivity of Aminobis (diorganylamino) phosphanes by G. Shick et al., Chem. Ber. , 1969, 129, 911-917. While the prior art describes some of the complexes published per se, and in one example, the complex in conjunction with an activator, the technique does not publish the polymerization of olefins, and in particular the polymerization of olefins using a supported form of the complex.

An announcement presentation by J.C. Stewart and D. Stephan, Department of Chemistry and Biochemistry at the University of Windsor, at the ID conference at McGill University in November 1996, publishes the polymerization of ethylene using certain cyclopentadienyl-phosphinimine catalysts. The change in terms of polyethylene grams / mmol / hr (e.g., productivity or activity) is several classes of lower magnitude than that obtained with the catalyst components of the present invention. The advertisement presentation does not disclose the use of supported catalyst components of the present invention, or polymerization above ambient temperature, or productivity / activity results which approximate a commercial utility. USP No. 5,625,016, issued April 29, 1997, assigned to Exxon Chemical Patents Inc. publishes the polymerization of olefins and in particular the preparation of ethylene-propylene rubbers or copolymers of ethylene-propylene diene monomers, in the presence of a system catalysts prepared from a group 4 metal without bridge, a monocyclopentadienyl ligand voluminous (substituted), a ligand of group 15, bulky, uninegative and two reactive activation ligands, uninegative. The patent publication teaches that the group 15 ligand is an amido ligand. The '016 patent does not teach or suggest the use of a phosphinimine ligand.

BRIEF DESCRIPTION OF THE INVENTION The invention provides a catalyst component for the polymerization of olefins comprising: (a) An organometallic complex comprising (i) a group 4 metal selected from Ti, Hf, and Zr; (ii) a ligand of the cyclopentadienyl type; (iii) a phosphinimine ligand; (iv) two univalent ligands; and (b) a particulate support.

DETAILED DESCRIPTION The organometallic complex of this invention includes a cyclopentadienyl ligand.

As used in this specification, the term "cyclopentadienyl" refers to a 5-membered carbon ring having a delocalized bond within the ring and typically being attached to the group 4 (M) metal through the bonds? covalent An unsubstituted cyclopentadienyl ligand has a hydrogen attached to each carbon in the ring. ("Cyclopentadienyl type" ligands also include substituted and hydrogenated cyclopentadienyls, as discussed in, detailed later in the specification.) More specifically, the metal complexes of group 4 of the present invention (also referred to herein as "Group 4 metal complex" or "Group 4 OMC") comprise a complex of the formula: Cp [(R1) 3-P = N] n- M - (L1) 3-n wherein M is selected from the group consisting of Ti, Zr, and Hf; n is 1 or 2; Cp is a ligand of the cyclopentadienyl type which is unsubstituted or substituted by up to 5 substituents independently selected from the group consisting of a hydrocarbyl radical of 1 to 10 carbon atoms or two hydrocarbyl radicals taken together can form a ring which Hydrocarbyl substituents or the cyclopentadienyl radical are unsubstituted or additionally substituted by a halogen atom, an alkyl radical of 1 to 8 carbon atoms, an alkoxy radical of 1 to 8 carbon atoms, an aryl or aryloxy radical of 6 to 10. carbon atoms; an amido radical which is unsubstituted or substituted by up to two alkyl radicals of 1 to 8 carbon atoms; a phosphide radical which is unsubstituted or substituted by up to two alkyl radicals of 1 to 8 carbon atoms; the silyl radicals of the formula -Si- (R2) 3 wherein each R2 is independently selected from the group consisting of hydrogen, an alkyl or alkoxy radical of 1 to 8 carbon atoms, aryl or aryloxy radicals of 6 to 10 carbon atoms; germanyl radicals of the formula Ge- (R2) 3 wherein R2 is as defined above; each R1 is independently selected from the group consisting of a hydrogen atom, a halogen atom, hydrocarbyl radicals of 1 to 10 carbon atoms which are unsubstituted or further substituted by a halogen atom, an alkyl radical of 1 to 8 carbon atoms, an alkoxy radical of 1 to 8 carbon atoms, an aryl or aryloxy radical of 6 to 10 carbon atoms, a silyl radical of the formula -Si- (R2) 3 wherein each R2 is independently selected from the group which consists of hydrogen, an alkyl or alkoxy radical of 1 to 8 carbon atoms, aryl or aryloxy radicals of 6 to 10 carbon atoms, a germanyl radical of the formula Ge- (R2) 3 wherein R2 is as defined above or two radicals R1 taken together can form a hydrocarbyl radical of 1 to 10 carbon atoms, bidentate, which is unsubstituted by or additionally substituted by a halogen atom, an alkyl radical of 1 to 8 carbon atoms, a alkoxy radical of 1 to 8 carbon atoms, an aryl or aryloxy radical of 6 to 10 carbon atoms, a silyl radical of the formula -Si- (R2) 3 wherein each R2 is selected independently of the group consisting of hydrogen, an alkyl or alkoxy radical of 1 to 8 carbon atoms, aryl or aryloxy radicals of 6 to 10 carbon atoms, germanyl radicals of the formula Ge- (R 2) 3 wherein R 2 is as defined above, with the proviso that radicals R1 individually or two radicals R1 taken together can not form a ligand Cp as defined above; each L1 is independently selected from the group consisting of a hydrogen atom, a halogen atom, a hydrocarbyl radical of 1 to 10 carbon atoms, an alkoxy radical of 1 to 10 carbon atoms, an aryl oxide radical of 5 to 10 carbon atoms, each of the alkoxy, hydrocarbyl and aryl oxide radicals can be unsubstituted or additionally substituted by a halogen atom, an alkyl radical of 1 to 8 carbon atoms, an alkoxy radical of 1 to 8 carbon atoms, an aryl or aryloxy radical of 6 to 10 carbon atoms, an amido radical which is unsubstituted or substituted by up to two alkyl radicals of 1 to 8 carbon atoms; a phosphide radical which is unsubstituted or substituted by up to two alkyl radicals of 1 to 8 carbon atoms, with the proviso that L1 can not be a radical Cp as defined above. With reference to the above formula, the fragment [(R1) 3-P = N] is the phosphinimine ligand. The ligand is characterized in that (a) it has a double band of nitrogen phosphorus; (b) has only one substituent on the N atom (i.e., the P atom is the sole substituent on the N atom); and (c) the presence of three substituents on the P atom. It is preferred that each of the three substituents R1 is tertiary butyl (or "t-butyl"), ie, the preferred phosphinimine is tri (tertiary butyl) phosphinimine . For cost reasons, the Cp ligand in the group 4 metal complex is preferably unsubstituted. However, if the Cp is replaced, then preferred substituents include a fluorine atom, a chlorine atom, a hydrocarbyl radical of 1 to 6 carbon atoms, or two hydrocarbyl radicals taken together can form a bridging ring, a radical amido which is substituted or unsubstituted by up to two alkyl radicals of 1 to 4 carbon atoms, a phosphide radical which is unsubstituted or substituted by up to two alkyl radicals of 1 to 4 carbon atoms, a silyl radical of the formula -Si- (R2) 3 wherein each R2 is independently selected from the group consisting of a hydrogen atom and an alkyl radical of 1 to 4 carbon atoms; a germanyl radical of the formula -Ge (R2) 3 wherein each R2 is independently selected from the group consisting of a hydrogen atom and an alkyl radical of 1 to 4 carbon atoms. In the metal complex of group 4, preferably, each R1 is selected from the group consisting of a hydrogen atom, a halide, preferably a chlorine or fluorine atom, an alkyl radical of 1 to 4 carbon atom , an alkoxy radical of 1 to 4 carbon atoms, a silyl radical of the formula -Si (R2) 3 wherein each R2 is independently selected from the group consisting of a hydrogen atom and an alkyl radical of 1 to 4 carbon atoms; carbon; and a germanyl radical of the formula -Ge (R2) 3 wherein each R2 is independently selected from the group consisting of a hydrogen atom and an alkyl radical of 1 to 4 carbon atoms. Particularly it is preferred that each R1 is a tertiary butyl radical.

Each L1 is a univalent ligand. The primary performance criterion for each L1 is that it does not interfere with the activity of the catalyst system. As a general guideline, any of the non-interfering univalent ligands which can be employed in analogous metallocene compounds (for example, halides, especially chlorine groups, alkyls, alkoxy, amido groups, phosphide groups, etc.) can be used. in this invention. Preferably, in the metal complex of group 4 each L1 is independently selected from the group consisting of a hydrogen atom, a halogen, preferably a chlorine or fluorine atom an alkyl radical of 1 to 6 carbon atoms, an alkoxy radical from 1 to 6 carbon atoms and an aryl oxide radical of 6 to 10 carbon atoms. The supported catalyst components of this invention are particularly suitable for use in a thick slurry polymerization process or a gas phase polymerization process. A typical, thick slurry polymerization process uses total reactor pressures of up to about 50 bar and temperatures of reactor up to approximately 200 ° C. The process employs a liquid medium (for example, an aromatic one such as toluene or an alkane such as hexane, propane or isobutane) in which the polymerization takes place. This results in a suspension of polymer particles, solid in the medium. Loop reactors are widely used in thick slurry processes. Detailed descriptions of the slurry polymerization processes are widely reported in the open and patent literature. The gas phase process is preferably started in a fluidized bed reactor. Such fluidized bed reactors are widely described in the literature. Follow a concise description of the processes. In general, a fluidized bed gas phase polymerization reactor employs a "bed" of the polymer and catalyst which is fluidized by a flow of the monomer which is at least partially gaseous. The heat is generated by the polymerization enthalpy of the monomer flowing through the bed. The unreacted monomer exits the fluidized bed and is brought into contact with a cooling system to remove this heat. He The cooled monomer is then circulated again through the polymerization zone, together with the "replacement" monomer to replace that which was polymerized in the previous step. As will be appreciated by those skilled in the art, the "fluidized" nature of the polymerization bed helps to equally distribute / mix the heat of the reaction and thereby minimize the formation of localized temperature gradients (or "heat spots"). ). However, it is essential that the heat of the reaction is adequately removed in order to avoid softening or melting of the polymer (and the resulting "highly undesirable" "steam exhaust or reactor explosions"). The obvious way to maintain good mixing and cooling is to have a very high monomer flow through the bed. However, the extremely high monomer flow causes undesirable drag of the polymer. An alternative (and preferable) approach to high monomer flow is the use of an inert, condensable fluid which will boil in the fluidized bed (when exposed to the enthalpy of polymerization), then leave the fluidized bed as a gas, then he will get in touch with a cooling element which will condense the inert fluid. The cooled, condensed fluid will then be returned to the polymerization zone and the boiling / condensing cycle will be repeated. The above-described use of a condensable fluid additive in a gas phase polymerization is often referred to by those skilled in the art as "condensed mode operation" and is described in further detail in USP No. 4,543,399 and USP No. 5,352,749. As noted in reference? 399, it is permissible to use alkanes such as butane, pentanes or hexanes as the condensable fluid and the amount of such condensed fluid should not exceed about 20 weight percent of the gas phase. Other reaction conditions for the polymerization of ethylene which are reported in reference? 399 are: Preferred polymerization temperatures: about 75 ° C to about 115 ° C (with the lower temperatures that are preferred for lower melt copolymers - especially those that have densities less than 0.915 g / cc - and the higher temperatures that are preferred for higher density copolymers and homopolymers); and Pressure: up to about 70,216 kg / cm2 (1000 psi) (with a preferred range of about 7.0216 kg / cm2 to 24.5756 kg / cm2 (100 to 350 psi) for the polymerization of olefins). Reference 399 teaches that the fluidized bed process is well suited for the preparation of polyethylene but also notes that other monomers can also be used. The present invention is similar with respect to the choice of monomers. Preferred monomers include ethylene and alpha olefins of 3 to 12 carbon atoms which are unsubstituted or substituted by up to two alkyl radicals of 1 to 6 carbon atoms, aromatic vinyl monomers of 8 to 12 carbon atoms which are unsubstituted or substituted by up to two substituents selected from the group consisting of alkyl radicals of 1 to 4 carbon atoms, cyclic or straight-chain diolefins of 1 to 12 atoms of carbon which are unsubstituted or substituted by an alkyl radical of 1 to 4 carbon atoms. Illustrative, non-limiting examples of such alpha olefins are one or more of propylene, 1-butene, 1-pentene, 1-hexene, 1-octene, and 1-decene, styrene, alpha methyl styrene, p-t-butyl styrene , and cyclic ring or restricted ring olefins such as cyclobutene, cyclopentene, dicyclopentadiene norbornene, alkyl-substituted norbornenes, alkenyl-substituted norbornenes and the like (e.g., 5-methylene-2-norbornene and 5-ethylidene-2-norbornene, bicyclo- (2,2, l) -hepta-2, 5-diene). The polyethylene polymers, which can be prepared according to the present invention, typically comprise not less than 60, preferably not less than 70% by weight of the ethylene and the remainder one or more alpha olefins of 4 to 10 carbon atoms. carbon, preferably selected from the group consisting of 1-butene, 1-hexene and 1-octene. The polyethylene prepared according to the present invention can be linear low density polyethylene having a density of about 0.910 to 0.935 g / cc or high density polyethylene having a density above 0.935 g / cc. The present invention could also be useful for preparing polyethylene having a density below 0. 910 g / cc - the so-called polyethylenes of very low and ultra low density. The present invention can also be used to prepare co- and ter-polymers of ethylene, propylene and optionally one or more diene monomers. In general, such polymers will contain from about 50 to about 75% by weight of ethylene, preferably from about 50 to 60% by weight of ethylene and correspondingly from 50 to 25% by weight of propylene. A portion of the monomers, typically the propylene monomer, can be replaced by a conjugated diolefin. The diolefin may be present in amounts of up to 10% by weight of the polymer although typically it is present in amounts of about 3 to 5% by weight. The resulting polymer can have a composition comprising from 40 to 75% by weight of ethylene, from 50 to 15% by weight of ethylene and up to 10% by weight of a diene monomer to provide 100% by weight of the polymer. Preferred but non-limiting examples of the dienes are dicyclopentanediene, 1,4-hexadiene, 5-methylene-2-norbornene, 5-ethylidene-2-norbornene and 5-vinyl-2-norbornene. The dienes particularly preferred are 5-ethylidene-2-norbornene and 1,4-hexadiene. The present invention unequivocally requires the use of a support. An exemplary list of support materials includes metal oxides (such as silica, alumina, silica-alumina, titania and zirconia); metal chlorides (such as magnesium chloride); talc, polymers (including polyolefins); partially prepolymerized mixtures of a group 4 metal complex, activator and polymer; dry, powdered mixtures of the group 4 metal complex, activator and fine, "inert" particles (as published, for example, in the patent application of European Patent No. 668,295 (for Union Carbide)). The preferred support material is silica.

In a particularly preferred embodiment, the silica has been treated with an alumoxane (especially methylalumoxane or "MAO") before the deposition of the group 4 metal complex. The process for preparing the "MAO supported" which is described in USP No. 5,534,474 (to Witco) is preferred for reasons of economy. It will be recognized by those skilled in the art that silica can be characterized by parameters such as size of particle, pore volume and concentration of residual silanol. The pore size and silanol concentration can be altered by heat treatment or calcination. The residual silanol groups provide a potential reaction site between the alumoxane and the silica (and, in fact, some production of malodorous gases is observed when the alumoxane is reacted with silica having residual silanol groups). This reaction can help "fix" the alumoxane to the silica (which, in turn, can help re reactor fouling). The preferred particle size, the preferred pore volume and the preferred residual silanol concentration can be influenced by reactor conditions. Typical silicas are dry powders having a particle size of 1 to 200 microns (with an average particle size of 30 to 100 which is especially suitable); the pore size from 50 to 500 Angstroms; and pore volumes of 0.5 to 5.0 cubic centimeters per gram. As a general guideline, the use of commercially available silicas, such as those sold by W.R. Grace under the trademarks Davison 948 or Davison 955, are suitable.

The activator can be selected from the group consisting of: (i) An aluminoxane; and (ii) A combination of an alkylating activator and an activator capable of ionizing the metal complex of group 4. The aluminoxane activator can be of the formula (R4) 2A10 (R4A10) mAl (R4) 2 wherein each R4 it is independently selected from the group consisting of hydrocarbyl radicals of 1 to 20 carbon atoms, and m is 0 to 50, preferably R4 is an alkyl radical of 1 to 4 carbon atoms, and m is 5 to 30. The activator of aluminoxane may be used prior to the reaction but preferably alkylation in itself is preferred (eg alkyl groups replacing L1, hydrogen or halide groups). The activator of the present invention can be a combination of an alkylating agent (which can also serve as a scavenger) in combination with an activator capable of ionizing the group 4 metal complex. The alkylating agent can be selected from the group which consists of (R3) pMgX2-p in where X is a halide and each R3 is independently selected from the group consisting of alkyl radicals of 1 to 10 carbon atoms, and p is 1 or 2; R3Li wherein in R3 is as defined above, (R3) qZnX2-q wherein R3 is as defined above, X is halogen and q is 1 or 2; (R3) SA1X3_S wherein R3 is as defined above, X is halogen and s is an integer from 1 to 3. Preferably in the above compounds, R3 is an alkyl radical of 1 to 4 carbon atoms and X is chloro . Commercially available compounds include triethylaluminum (TEAL), diethylaluminum chloride (DEAC), dibutyl magnesium ((Bu) 2Mg), and butyl ethyl magnesium (BuEtMg or BuMgEt). The activator capable of ionizing the metal complex of group 4 can be selected from the group consisting of: (i) compounds of the formula [R5] + [B (R7) 4] "wherein B is a boron atom, R5 is an aromatic cation of 5 to 7 carbon atoms, cyclic or a triphenyl methyl cation and each R7 is independently selected from the group consisting of phenyl radicals which are substituting or substituted with 3 to 5 substituents selected from the group consisting of a fluorine atom, an alkoxy radical or alkyl of 1 to 4 carbon atoms which is unsubstituted or substituted by a fluorine atom; and a silyl radical of the formula -Si- (R9) 3; wherein each R9 is independently selected from the group consisting of a hydrogen atom and an alkyl radical of 1 to 4 carbon atoms; and (ü) compounds of the formula [(R8) tZH] + [B (R7)] "wherein B is a boron atom, H is a hydrogen atom, Z is a nitrogen atom or a phosphorus atom, t is 2 or 3 and R8 is selected from the group consisting of alkyl radicals of 1 to 8 carbon atoms, a phenyl radical which is unsubstituted or substituted by up to three alkyl radicals of 1 to 4 carbon atoms, or an R8 taken together with the nitrogen atom can form an anilinium radical and R7 is as defined above; (iii) compounds of the formula B (R7) 3 wherein R7 is as defined above. In the above compounds R7 is preferably a pentafluorophenyl radical, and R5 is a triphenylmethion cation, Z is a nitrogen atom and R8 is an alkyl radical of 1 to 4 carbon atoms, or R8 taken together with the nitrogen atom it forms an anilinio radical which is substituted by two alkyl radicals of 1 to 4 carbon atoms. While not wishing to be bound by theory, it is generally believed that the activator capable of ionizing the group 4 metal complex extracts one or more ligands L1 in order to ionize the center of the group 4 metal in a cation (but not for a covalent bond with the metal of group 4), and provide a sufficient distance between the metal of the ionized group 4 and the ionization activator to allow a polymerizable olefin to enter the resulting active site. In summary, the activator capable of ionizing the metal complex of group 4 keeps the metal of group 4 in a state of valence +1, while being sufficiently exposed to allow its displacement by an olefinic monomer during polymerization. In the catalytically active form, those activators are frequently referred to by those skilled in the art as substantially non-coordinating anions ("SNCA"). Examples of the compounds capable of ionizing the metal complex of group 4 include the following compounds: triethylammonium tetra (phenyl) boron, tripropylammonium tetra (phenyl) boron, tetra (phenyl) boron of tri (n-butyl) ammonium, tetra (p-tolyl) boron of trimethylammonium, tetra (o-tolyl) boron of trimethylammonium, tetra (pentafluorophenyl) boron of tributylammonium, tetra (o, p-dimethylphenyl) boron of tripropylammonium, tetra (m, m-dimethylphenyl) boron of tributylammonium, tributylammonium tetra (p-trifluoromethylphenyl) boron, tributylammonium tetra (pentafluorophenyl) boron, tetra (o-tolyl) gold of tri (n-butyl) ammonium, tetra (phenyl) boron of N, N-dimethylanilinium, tetra ( phenyl) boron of N, -diethylanilinium, tetra (phenyl) n-butyl boron of N, N-diethylanilinium, tetra (phenyl) boron of N, N-2,4,6-pentamethylanilinium, tetra (pentafluorophenyl) boron of di- (isopropyl) ammonium, tetra (phenyl) boron of dicyclohexylammonium, tetra) phenyl) boron of triphenylphosphonium, tetra (phenyl) boron Tri (methylphenyl) phosphonium, tetra (phenyl) boron tri (dimethylphenyl) phosphonium, tetracispentafluorophenyl borate tropylium, tetracispentafluorophenyl borate triphenylmethylium, tetracispentafluorophenyl benzene borate (diazonium), phenyltris-pentafluorophenyl borate triphenyl, triphenylmethyl phenyltrisfentafluorophenyl borate, phenyltrispentafluorophenyl benzene borate (diazonium), tetracis (2, 3, 5, 6-tetrafluorophenyl) borate of tropilium, tetracis (2, 3, 5, 6-tetrafluorophenyl) borate of triphenylmethylium, tetracis (3,4,5-trifluorophenyl) borate of benzene (diazonium), tetrac (3, 4, 5-trifluorophenyl) borate of tropylium, tetracis (3,4,5-trifluorophenyl) borate of benzene (diazonium), tetracis (1,2,2-trifluoroethenyl) borate of tropylium, tetracis (1, 2, 2-trifluoroethenyl) borate of triphenylmethylium, tetracis (1,2,2-trifluoroethenyl) borate of benzene (diazonium), tetracis (2, 3, 4, 5-tetrafluorophenyl) borate of tropylium, tetracis (2, 3, 4, 5 -tetrafluorophenyl) triphenylmethylium borate, and benzene (diazonium) tetracis (2, 3, 4, 5-tetrafluorophenyl) borate. Commercial and readily available activators, which are capable of ionizing group 4 metal complexes, include: tetracispentafluorophenyl N, N-dimethylaniline borate ("[Me2NHPh] [B (C6F5) 4]"); tetracispentafluorophenyl triphenylmethyl borate ("[Ph3C] [B (C6F5)"); and trispentafluorophenyl boron. If the metal complex of group 4 is activated with a combination of an alkylating agent (different from aluminoxane) and a compound capable of ionizing the metal complex of group 4, then the molar ratios of the metal of group 4: metal in the alkylating agent; the metalloid (ie, boron or phosphorus) in the activator capable of ionizing the group 4 metal complex (for example, boron) can vary from 1: 1: 1 to 1: 10: 5. Preferably, the alkylation activator is pre-mixed / reacted with the group 4 metal complex and the resulting alkylated species, then reacted with the activator capable of ionizing the group 4 metal complex. The term "Catalyst component" as used herein refers to a combination of: (1) the organometallic complex of group 4 defined above having a ligand of the cyclopentadienyl type and a phosphine ligand ("OMC of the group 4") and (2) a particulate support material (in a form in which the OMC of group 4 is" supported ".) This catalyst component is used in conjunction with an activator such as the aluminoxanes described above and / or SNCA to form an active catalyst system The activator can be added to the polymerization reactor separately from the catalyst component or, alternatively, the activator can be co-supported with the OMC of group 4. It is preferred to use an activator which is co-supports with the OMC of group 4. The OMC of group 4, co-supported and the activating system can be prepared using one of the three general techniques: Technique 1: First deposit the OMC of group 4 on the support (then support the activator); Technique 2: First deposit the activator on the support (then support the OMC of group 4); o Technique 3: Support a mixture (solution or slurry) of the OMC of group 4 and the activator at the same time.

The second technique (ie, first support the activator, then support the OMC of group 4) is generally preferred if the objective is to achieve maximum catalytic activity on a WTO basis of group 4. (This may be necessary if the WTO of group 4 which is being used has a comparatively low activity). Especially, high activity can be obtained through the use of gel-free aluminoxanes having specific particle sizes (as described in PCT patent applications No. 95/18809 and 95/18836). However, as will be recognized by those skilled in the art, there is often some correlation between very high catalytic activity and undesirable dirt in the reactor. On the other hand (although it is not desired to be joined by any particular theory), it has been assumed that some dirt from the reactor is caused by the productivity gradients within the supported catalysts (or "heat spots" of the catalysts located from the high activity) and that these "heat spots" are in turn caused by an unequal distribution of the catalytic metal in the support.

Therefore, if the primary objective is to prepare a catalyst system which causes minimal reactor fouling, then the use of low concentrations of OMC of group 4 and / or pre-mix the activator and OMC of group 4 is preferred. in a solvent or diluent, then deposit this mixture / solution on the support. The use of "incipient moisture" techniques to deposit an activator and OMC mixture of group 4 is described in USP No. 5,473,028 (to Mobil) as a means to produce catalyst systems having "low dirt" characteristics. It is preferred to use low concentrations of OMC of group 4 (particularly when using a highly active group 4 OMC, such as the (t-butyl) 3-phosphinimine system described in the examples). When an alumoxane is used as the activator, the low concentration of OMC of group 4 results in a relatively high Al / transition metal ratio (for a supported catalyst). When preparing the "low dirt" catalysts it is especially preferred to use an Al / transition metal ratio of 75/1 to 200/1, especially 100/1 to 200/1, and preferably 110/1 to 150/1. Those relationships are produced by using small amounts of OMC of group 4. However, the very low concentration of OMC of group 4 in these catalysts can cause problems in the "shelf life" for the catalyst (ie, catalyst systems that have concentrations low transition metal may be more susceptible to deterioration of activity by exposure to oxygen, light or similar catalytic systems that have a high level of transition metal). The use of a thin coating of a mineral oil is desirable to alleviate this problem. In this way, the highly preferred catalyst samples of this invention use the OMC of the co-supported group 4 and the activator; the support is particulate silica; the activator is metaluminoxane; Group 4 WTO is highly active but used at a low concentration (in order to provide a ratio of Al / transition metal from 100/1 to 200/1) and the catalyst system (consisting of the OMC of group 4). supported and alumoxane in particulate silica) is coated with a thin layer of mineral oil. The use of the SNCA as an activator can also be used in combination with a component catalyst according to this invention. Silica is also the preferred support when the SNCA is used. It is recommended to initially treat the silica with a lower amount of aluminum alkyl before depositing the SNCA. The amount of aluminum alkyl should be less than the amount of the residual silanol groups on a molar basis. The additional details are illustrated in the following non-limiting examples.

EXAMPLES Polymer Analysis The gel permeation chromatography ("GPC") analysis was carried out using commercially available chromatography (sold under the name of Waters 150 GCP) using 1,2,4-trichlorobenzene as the mobile phase at 140 ° C. The samples were prepared by dissolving the polymer in the solvent of the mobile phase in an external oven at 0.1% (weight / volume) and running without filtration. Molecular weights were expressed as polyethylene equivalents with a normal, relative deviation of 2.9% and 5.0% for the number average molecular weight Mn and weight average molecular weight Mw, respectively. The melt index (MI) dimensions were conducted according to the method of ASTM D-1238-82. The polymer densities were measured using compressed plates (ASTM D-1928-90) with a densitometer. The polymer composition was determined using the FTIR where the content of 1-butene or 1-hexene was measured.

Catalyst Preparation and Polymerization Test Using a Semi-Lase Gas Phase Reactor The catalyst preparation methods, described below, employ typical techniques for the synthesis and handling of air-sensitive materials. The standard Schlenk and dewatering box techniques were used in the preparation of ligands, metal complexes, support substrates and supported catalyst systems. Solvents were purchased as anhydrous materials and further treated to remove oxygen and polar impurities by contact with a combination of activated alumina, molecular sieves and copper oxide in silica / alumina Where the elemental, appropriate compositions of the supported catalysts were measured by a Neutron Activation analysis with a reported accuracy of ± 1% (basis weight). All supported catalyst components according to the invention were coated with a thin layer of mineral oil subsequent to the deposition of the OMC of group 4. This was done by preparing a slurry of the catalyst component supported on mineral oil. All the polymerization experiments described below were conducted using a gas phase polymerization reactor, of half batches of total internal volume of 2.2 L. The reaction gas mixtures, including separately ethylene or ethylene / butene mixtures, were measured for the reactor on a continuous basis using a thermal, calibrated mass flowmeter, following the passage through the purification means as described above. A predetermined mass of the catalytic sample was added to the reactor under the flow of the admission gas without prior contacting the catalyst with any reagent, such as a catalyst activator. The catalyst activated in si tu (in the polymerization reactor) at the reaction temperature in the presence of the monomers, using a metal alkyl complex which has been previously added to the reactor to remove the foreign impurities. The rigorously anhydrous and purified sodium chloride was used as a catalyst dispersing agent. The internal temperature of the reactor is monitored by a thermocouple in the polymerization medium and can be controlled at the required reference point at +/- 1.0 ° C. The duration of the polymerization experiment was one hour. After completion of the polymerization experiment, the polymer was separated from the sodium chloride and the product was determined. Example 1: Preparation and Copolymerization with Ethylene / 1-Butene of titanium [(tri (t-butyl) phosphinimine)] - (2,6-di (isopropyl) phenoxy) Cyclopentadienyl chloride Supported in MAO / Silice Catalyst synthesis Commercial "polymethylaluminoxane" or "metalumoxane" (MAO) in granular silica (1.65 g, Witco TA) 02794 / HL / 04, 23% by weight of Al) was suspended in anhydrous toluene (40 mL). A solution of titanium [(tri (t-butyl) -phosphinimine)] (2) was prepared, 6-di (isopropyl) phenoxy) cyclopentadienyl chloride (0.098 g, 0.18 mmol) in anhydrous toluene and the total volume was added dropwise to a stirred suspension of the MAO on silica. The slurry was allowed to stir overnight and subsequently heated at 45 ° C for a period of 2.0 hours. The resulting solid was collected by filtration and washed first with toluene (2 x 15 L) and then with hexane (2 x 20 mL). After drying in vacuo, 1.55 grams of a flowing yellow powder were obtained. The compositional analysis of the catalyst supported by the Neutron Activation showed that the catalyst contains aluminum and titanium in a ratio of 97: 1 (base in mol).

Polymerization Gas-phase ethylene homopolymerization of the supported catalyst was conducted by introducing the supported catalyst (25 mg) in a 2L pressure vessel, continuously stirred, under operating conditions of 14,043 kg / cm2 (200 psig) of 1-butene in ethylene (Airgas, degree of polymerization, 3.9% by moles) and at a constant temperature of 90 ° C for a period of 1 hour. A bed of NaCl seed (70 g, oven-dried at 175 ° C for 48 hours), treated in-situ with a solution of tri-isobutylaluminum-heptane (TIBA1, 1 mL of a 25% by weight solution, Akzo Nobel), was added to the reactor before the introduction of the catalyst as a contaminant scavenger. Upon termination of the reaction and isolation of the polymer, a flowing product was obtained in a yield of 25 g, which represents a catalytic activity of 125,000 g of PE / g of Ti. The polymer, characterized by the GPC, showed a molecular weight of 362,000 (Mw) and a polydispersity of 3.4 (where the polydispersity = Mw / Mn). The polymer was found to contain 3.0% mol of 1-butene.

Example Preparation and Copolymerization with Ethyl / 1-Butene of titanium [(tri (t-butyl) osphinimine)] (2,6-di (isopropyl) phenoxy) chloride Cyclopentadienyl supported on MAO / Silica Polymerization Using the same catalyst as described in Example 1, and identical polymerization conditions as described in Example 1, with the exception that the duration of the polymerization experiment was two hours and 13 mg of the supported catalyst was used, obtained a flowing product in a yield of 40 g, which represents a catalytic activity of 398,000 g of PE / g of Ti. The polymer, characterized by gel permeation chromatography (GPC), showed a molecular weight of 452,000 (Mw) and a polydispersity of 2.3. The polymer was found to contain 2.9% mol of 1-butene.

Example Preparation and Copolymerization with Ethylene / 1-Butene of titanium [(tri (t-butyl) phosphinimine)] Cyclopentadienyl dichloride supported on MAO / Silice Catalyst synthesis The same procedure was used as described in Example 1, except that the one of titanium (cyclopentadienyl tri (t-butyl) phosphiniminadichloride (0.065 g, 0.18 mmol) was used instead of titanium [(tri (t-butyl) phosphinimine )] (2,6-di (isopropyl) phenoxy) cyclopentadienyl chloride and 1.47 g of a flowing brown powder was obtained The compositional analysis of the catalyst supported by Neutron Activation showed that the catalyst contains aluminum and titanium in a ratio 90: 1 (base in mol).

Polymerization Using the same procedure as that described in Example 1, except that 50 mg of the supported catalyst was used, 49 g of polyethylene was obtained, which represents a catalytic productivity of 113,000 g / g Ti. The polymer, characterized by the GPC, showed a molecular weight of 533,000 (Mw) and a polydispersity of 4.5. It was found that the polymer contains 2.8 mol% of 1-butene.

Example Preparation and Copolymerization with Ethylene / 1-Butene of titanium [(tri (t-butyl) phosphinimine)] Cyclopentadienyl dichloride supported on MAO / Silice Using the same catalyst as that described in Example 3, and the identical polymerization conditions as those described in Example 3, with the exception that the duration of the polymerization experiment was 2 hours, 149 g of polyethylene were obtained, which represents a catalytic productivity of 344,000 g / g Ti. The polymer, characterized by GPC, showed a molecular weight of 512,000 (Mw) and a polydispersity of 2.3. The polymer was found to contain 3.1% mol of 1-butene.

Example 5: Preparation and Copolymerization with Ethylene / 1-Butene of titanium [(tri (t-butyl) phosphinimine)] Cyclopentadienyl dichloride supported on MAO / Silica Synthesis of the catalyst The same procedure as described in Example 3 was used, except that a smaller amount of the titanium (tri (t-butyl) phosphinimine) cyclopentadienyl dichloride was used (0.032 g, 0.089 mmol) in combination with the Witco MAO in Si02 (1.07 g) to give a catalyst having aluminum to titanium in a ratio of 113: 1 (base in mol).

Polymerization Using the same procedure as described in Example 1, except that 26 mg of the supported catalyst was used, 38 g of polyethylene was obtained, which represents a catalytic productivity of 201,000 g / g Ti. The polymer, characterized by the GPC, showed a molecular weight of 546,000 (Mw) and a polydispersity of 3.7. It was found that the polymer contains 3.1 mol% of 1-butene.

Example 6: Preparation and Copolymerization with Ethylene / 1-Butene of titanium [(tri (t-butyl) phosphinimine)] dichloride of Cislopentadienyl supported on MAO / Silica Catalyst Synthesis The same procedure was used as described in Example 3, except that a larger amount of the titanium (tri (t-butyl) phosphinimine) cyclopentadienyl dichloride was used (0.076 g, 0.211 mmol) in combination with the MAO Witco in Si02 (1.07 g) to give a catalyst having aluminum to titanium in a ratio of 47: 1 (base in mol).

Polymerization Using the same procedure as described in Example 1, except that 13 mg of the supported catalyst was used, 25 g of polyethylene was obtained, which represents a catalytic productivity of 109,000 g / g Ti. The polymer, characterized by the GPC, showed a molecular weight of 588,000 (Pm) and a polydispersity of 4.2. The polymer was found to contain 2.9% mol of 1-butene.

Example Preparation and Copolymerization with Ethylene / 1-Butene of Titanium [(tri (t-butyl) phosphonimine)] Cyclopentadienyl dichloride supported on MAO / Modified silica Catalyst synthesis The supported MAO was prepared according to the following instructions: To a sample of partially dehydroxylated silica (5.01 g, Grace Davison 948) was added, by dropwise addition, a solution of MAO in toluene (100.95). g, 10% by weight, Akzo Nobel) with stirring. The resulting slurry was allowed to stir slowly overnight at room temperature, after which the toluene was removed in vacuo and the solid was dried overnight in vacuo. Subsequently, the solid was heated to 170 ° C in vacuo for three hours, then a thick slurry in toluene (150 mL) was made and further heated for one hour at 90 ° C. The white solid was filtered, washed with hot toluene (2 x 30 mL) and hexane (2 x 20 mL). The solid was then dried in vacuo during a time at 120 ° C after which 11.7 g of a flowing, white powder was recovered. The modified MAO on silica (0.898 g) was suspended in anhydrous hexane (40 mL) and allowed to stir for 30 minutes. A slurry of titanium [(tri (t-butyl) phosphinimine)] cyclopentadienyl dichloride (0.018 g, 0.051 mmol) in anhydrous hexane was prepared and the total volume was added dropwise to the stirred suspension of the MAO on silica. The slurry was allowed to stir for 30 minutes, then filtered, washed with hexane (2 x 20 L) and dried in vacuo. The catalyst was isolated as a white powder in a yield of 0.80 g.

Polymerization Using the same procedure as described in Example 1, except that 25 mg of the supported catalyst was used, 36 g of polyethylene was obtained, which represents a catalytic productivity of 145,000 g / g Ti. The polymer, characterized by the GPC, showed a molecular weight of 472,000 (Mw) and a polydispersity of 3.3. The polymer was found to contain 2.9% mol of 1-butene.

Example 8: Preparation and Copolymerization with Ethylene / 1-Butene of Cyclopentadienyl [(tri (t-butyl) phosphinimine)] dimethyl] Supported in MAO / Silica Preparation of the Catalyst A sample of titanium [(tri (t-butyl) phosphinimine)] cyclopentadienyl dichloride (0.186 g, 0.52 mmol) was dissolved in anhydrous diethyl ether (40 mL) and the temperature was reduced to -78 ° C.

A solution of 15 mL containing 1.4 mmoL of MeMgBr was slowly added thereto and the resulting solution was allowed to warm to room temperature. Removal of the solvent in vacuo, followed by washing with hexane yielded a green solid. This was dissolved in toluene, filtered and precipitated using hexane to give a pale yellow / green solid. The existence of the dimethyl adduct was confirmed by 1 H NMR. The commercial polymethylaluminoxane (MAO) in granular silica (0.62 g, Witco TA 02794 / HL / 04, 23% by weight Al) was suspended in anhydrous hexane (40 mL) and a toluene solution was added thereto. titanium [(tri (t-butyl) phosphinimine)] dimethyl cyclopentadienyl (0.062 mmoL, 0.019 g in 3.6 mL) and the resulting suspension was allowed to stir for 30 minutes. The solid was filtered, washed with hexane and dried in vacuo to give 0.49 g of a flowing yellow powder. The compositional analysis of the catalyst supported by Neutron Activation showed that the catalyst contains aluminum and titanium in a ratio of 93 (base in mol) Polymerization Using the same procedure as described in Example 1, except that 13 mg of the supported catalyst was used, 20 g of polyethylene was obtained, which represents a catalytic productivity of 178,000 g / g Ti. The polymer, characterized by the GPC, showed a molecular weight of 557,000 (Mw) and a polydispersity of 3.1. The polymer was found to contain 3.8% mol of 1-butene.

Example 9: Preparation and Copolymerization with Ethylene / 1-Butene of titanium [(tri (t-butyl) phosphinimine)] dimethyl of Cyclopentadienyl Supported in MAO / Modified Silice Catalyst Preparation A sample of the titanium [tri (t-butyl) phosphinimine)] cyclopentadienyl dichloride (0.186 g, 0.52 mmoL) was dissolved in anhydrous diethyl ether (40 mL) and reduced to a temperature of -78 ° C. A solution of 15 mL containing 1.4 mmoL of MeMgBr was slowly added thereto and the resulting solution was allowed to warm to room temperature. Removal of the solvent in vacuo, followed by washing with hexane yielded a green solid. This was dissolved in toluene, filtered and precipitated using hexane to give a pale yellow / green solid. The existence of the dimethyl adduct was confirmed by 1 H NMR. A sample of the MAO on silica (0.56 g) as described in Example 3 was suspended in 30 mL of hexane and a toluene solution of the titanium [tri (t-butyl) phosphinimine)] dimethyl cyclopentadienyl (0.056 mmoL) was added thereto. , 0.017 g in 3.3 mL) and the resulting suspension was allowed to stir for 30 minutes. The solid was filtered, washed with hexane and dried in vacuo to give 0.46 g of a flowing yellow powder.

Polymerization Using the same procedure as described in Example 1, except that 13 mg of the supported catalyst was used, 24 g of polyethylene was obtained, which represents a catalytic productivity of 209,000 g / g Ti. The polymer, characterized by GPC, showed a molecular weight of 622,000 (Mw) and a polydispersity of 2.3. It was found that the polymer contains 2.5% mol of 1-butene.

Example 10 Preparation and Copolymerization with Ethylene / 1-Butene of Cyclopentadienyl [tri (t-butyl) phosphinimine)] dimethyl and [Ph3C] [B (C6F5) 4] Supported on Triethylaluminum-treated silica Preparation of the catalyst A sample of silica (10 g, Davison 948) was calcined by heating to a temperature of 600 ° C under a fixed gas stream. of nitrogen during a period of 8 hours. After cooling to room temperature, the sample was made a slurry in dry n-hexane (100 mL), cooled to 0 ° C and a solution of triethyl aluminum in n-hexane (50 mL of a solution of 25% by weight, Akzo Nobel) by means of a dropping funnel. The resulting suspension was allowed to warm slowly to room temperature with intermittent stirring and the solid was isolated by filtration. After repeated washing with n-hexane and drying in vacuo, a white powder was obtained. To a solution of the cyclopentadienyl [tri (t-butyl) -phosphinimine)] dimethyl in toluene (0.110 mmoL, prepared as described in Example 5) was added a toluene solution of [Ph3C] [B ((C6F5) 4] (0.11 mmoL) The dark yellow solution was allowed to stir for fifteen minutes and then slowly added to a toluene suspension of triethylaluminium-treated silica.

("TEAL") (1.07 g in 30 mL). The suspension was allowed to stir for 30 minutes and the toluene was removed in vacuo at a temperature of 40 ° C. The addition of dry hexane gave a suspension which was filtered and, after repeated washing with hexane and drying Subsequently in vacuo, gave 0.62 g of a bright yellow solid.

Polymerization Using the same procedure as described in Example 1, except that 13 mg of the supported catalyst was used, 25 g of polyethylene was obtained, which represents a catalytic productivity of 68,000 g / g Ti. The polymer, characterized by the GPC, showed a molecular weight of 519,000 (Mw) and a polydispersity of 3.5. The polymer was found to contain 1.8% mol of 1-butene.

Example 11: Preparation and Copolymerization with Ethylene / 1-Butene of Titanium [tri (t- (butyl) phosphinimine)] Cyclopentadienyl dichloride and MAO Supported on Silica treated with Trisobutylaluminium Catalyst Preparation The silica-supported triisobutylaluminium was prepared in a manner similar to that used for the preparation of the silica-supported triethylaluminum described in Example 7, except that the triisobutylaluminum on silica was heated at 150 ° C (in vacuo) for three hours. To a solution of the titanium [tri (t-butyl) phosphinimine)] dimethyl cyclopentadienyl in toluene (0.085 mmoL, prepared as described in Example 5) was added a toluene solution of PMAO (0.574 g of a toluene solution of 10% by weight, Akzo Nobel). The solution was allowed to stir for 30 minutes and then slowly added to a toluene suspension of silica treated with triisobutylaluminum (0.934 g in 15 mL). The suspension was allowed to stir for 30 minutes and the toluene was removed in vacuo at a temperature of 40 ° C. The addition of dry hexane gave a suspension which was filtered and, after repeated washing with hexane and subsequent drying in vacuo, gave 0.71 g of a light yellow powder.

Polymerization Using the same procedure as described in Example 1, except that 52 mg of the supported catalyst was used, 15 g of polyethylene was obtained, which represents a catalytic productivity of 33,800 g / g Ti. The polymer, characterized by GPC, showed a molecular weight of 688,000 (Mw) and a polydispersity of 3.5. It was found that the polymer contains 2.8 mol% of 1-butene.

Example 12: Preparation and Copolymerization with Ethylene / 1-Butene of Titanium [(tri (t-butyl) phosphinimine)] Cyclopentadienyl dichloride Supported in MAO / Silica Using the same catalyst as described in Example 3 in an amount of 50 mg, and identical polymerization conditions as described in Example 3, with the exception that hydrogen gas was added to give a molar ratio of hydrogen to ethylene of 2.5%, 26 g of polyethylene was obtained, which represents a catalytic productivity of 60,000 g / g Ti. The polymer, characterized by the GPC, showed a molecular weight of 80,000 (Mw) and a polydispersity of 3.6. The polymer was found to contain 3.1% mol of 1-butene.

Comparative example 1: Preparation and Copolymerization with Ethylene / 1-Butene of titanium (2,6-di (isopropyl) phenoxy) Cyclopentadienyl dichloride Supported in MAO / Silica [Note: the organometallic complex in this comparative example does not contain a phosphinimine ligand. ] Synthesis of the Catalyst The same procedure was used as described in Example 1, except that titanium (2,6-di (iso-propyl) phenoxy) cyclopentadienyl dichloride (0.051 g, 0.14 mmol) was used instead of titanium [tri (t-butyl) phosphinimine)] (2,6-di (isopropyl) phenoxy) cyclopentadienyl chloride and 1.2 g of the catalyst was obtained.

Polymerization Using the same procedure as described in Example 1, except that 50 mg of the supported catalyst was used, 0.7 g of polyethylene was obtained, which represents a catalytic productivity of 2,000 g PE / g of Ti. The polymer, characterized by GPC, showed a molec weight of 233,000 (Mw) and a polydispersity of 7.7.

Comparative Example 2: Preparation and Polymerization with Ethylene / 1-Butene of Cyclopentadienyl zirconiotrichloride Supported on Silica treated with MAO Preparation of the Catalyst To 3 g of Witco MAO in Si02 (product TA-02794, 25% by weight of Al), 30 mL of dry toluene were added and the slurry was heated to 60 ° C. Separately, a solution of CpZrCl3 (146 mg, 0.56 mmol) in 75 mL of dry toluene was prepared (note that the CpZrCl3 solution was heated to about 50 ° C to stime solubilization). The solution of CpZrCl3 was then added to the slurry of MA0 / Si02 with constant stirring. After the addition, the thick suspension was allowed to settle at 60 ° C for two hours with frequent agitation, but not constant. After two hours the heat was removed and the slurry allowed to settle for two additional hours after which the solvent was removed. decanted and the product was dried in vacuo. The resulting dry powder was washed with dry pentane (2 x 30 mL) and dried in vacuo at room temperature for two hours.

Polymerization Using the same procedure as described in Example 1, except that 60 mg of the supported catalyst was used, 2.5 g of polyethylene was obtained, which represents a catalytic activity of 27,800 g / g of Zr. The polymer, characterized by the GPC, showed a molec weight of 136,000 (Mw) and a polydispersity of 4.6. It was found that the polymer contains 3.5% mol of 1-butene.

Comparative Example 3: Preparation and polymerization with ethylene of cyclopentadienyl zirconiotrichloride and MAO supported on silica treated with MAO Catalyst Preparation To a 3 g sample of Grace Davison MAO on silica (XPO-2409) was silica D948 (dehydrated at 200 ° C for 10 hours) 30 mL of dry toluene was added. In a separate flask, CpZrCl3 (61 mg, 0.23 mmoL) was dissolved in 50 mL of dry toluene and to this was added 2.5 mL (5.5 mmoL) of MAO solution (Akzo PAMO / tol-236, 6.7% by weight of Al ), and the resulting solution was allowed to stir at room temperature for fifteen minutes. The MAO / CpZrCl3 solution was transferred to the silica slurry and the resulting mixture was stirred occasionally for a period of two hours at room temperature. The solvent was decanted and the solids were repeatedly washed with dry pentane (4 x 30 mL) and dried in vacuo at room temperature for two hours to give 2.9 g of a pale yellow solid.

Polymerization Using the same procedure as described in Example 1, except that 67 mg of catalyst was used and ethylene was used in place of ethylene / 1-butene, 1.3 g of polyethylene was obtained, which represents a catalytic productivity of 3, 900 g / g of Zr.

Comparative Example 4: Preparation and polymerization with ethylene of cyclopentadienyl zirconiotrimethyl and [Me2NHPh] [B (C6F5) 4] supported on Silica treated with Triethylaluminum A usable MeLi solution (0.14 mmol / mL, 10 mL total volume) was prepared by diluting the stock solution (1.4 M in Et20) using dry Et20. CpZrCl3 (26 mg, 0.0926 mmol) was slurried in dry toluene (15 mL), and then treated with MeLi (2 eq., 0.185 mmol, 1.3 mL of usable solution) and allowed to stir for 10 minutes at room temperature. ambient. The solvent was removed in vacuo and the solids were dried for 60 minutes at room temperature. This product was taken up in dry toluene and to this was added a solution of ([Me2NHPh] [B (C6F5) 4] in toluene (0.20 mmoL, 10 mL) and the resulting solution was allowed to stir for 30 minutes. triethylaluminium supported on silica (1 g, prepared as described in Example 7) was suspended in dry toluene (20 mL) and the solution of CpZrMe2Cl / [Me2NHPh] [B (C6F5) 4] was added slowly during 15 minutes. After stirring for 15 minutes, the solvent was removed in vacuo, the solid was dried in vacuo for 60 minutes and washed repeatedly with dry hexane. The resulting solid was dried in vacuo overnight to give a flowing powder (1.0 g).

Polymerization Using the same procedure as described in Example 1, except that 75 mg of catalyst and ethylene were used in place of ethylene / 1-butene, 4.6 g of polyethylene was obtained, which represents a catalytic productivity of 5,100 g / kg. g of Zr.

Comparative Example 5: Preparation and Polymerization with? Tylene / 1-Butene of zirconium bis-cyclopentadienyl dichloride Supported in Silica Preparation of the Catalyst The same procedure was used as described in Example 1, except that 2.0 g of the MAO / SI02 Witco were used, and zirconium was used bis-cyclopentadienyl dichloride (0.056 g, 0.20 mmol) in place of titanium [tri (t-butyl) phosphinimine)] (2,6-di- (isopropyl) phenoxy) cyclopentadienyl chloride and 1.78 g of a powder was obtained flowing The compositional analysis of the catalysts supported by the Neutron Activation showed that the catalyst contains aluminum and zirconium in a ratio of 106: 1 (base in mol).

Polymerization Using the same procedure as described in Example 1, except that 58 mg of the supported catalyst was used, 37 g of polyethylene was obtained, which represents a catalytic productivity of 81,000 g / g of Zr. The polymer, characterized by the GPC, showed a molecular weight of 107,000 (Mw) and a polydispersity of 2.9. It was found that the polymer contains 1.5% mol of 1-butene.

Comparative Example 6: Preparation and Polymerization with Ethylene of titanium cyclopentadienyl trichloride supported on silica treated with MAO Preparation of the Catalyst Commercial polymethylaluminoxane (MAO) in granular silica (2.0 g, Witco TA 02794 / HL / 04, 23% by weight Al) was suspended in anhydrous toluene (40 mL). A solution of cyclopentadienyl titanotrichloride (0.020 g, 0.11 mmol) in anhydrous toluene was prepared and the total volume was added dropwise to a stirred suspension of MAO on silica. The slurry was allowed to stir overnight and subsequently heated at 45 ° C for a period of 2.0 hours. The resulting solid was collected by filtration and washed first with toluene (2 x 15 mL) and then with hexane (2 x 20 mL). After drying in vacuo, 1.55 grams of a flowing solid was obtained. The compositional analysis of the catalyst supported by Neutron Activation showed that the catalyst contains aluminum and titanium in a ratio of 173: 1 (base in mol).

Polymerization Using the same procedure as described in Example 1, except that they were used 46 mg of the catalyst and ethylene was used instead of ethylene / 1-butene. They only recovered small amounts of the polymer of this experiment, which gives an estimated catalytic productivity that is less than 10 g / g Ti.

Polymerization data for Examples 1-12 and Comparative Examples 1 - 6 • fc- unmeasured data Catalyst Preparation and Polymerization Test using a Thickness, Semi-Batch Suspension Phase Reactor All the polymerization experiments described below were conducted using a slurry phase polymerization reactor, of semi-batch-s of total internal volume of 2.2 L. Ethylene, at a fixed reactor pressure of 14,043 km / cm2 (200 psig), was calculated for the reactor on a continuous basis using a calibrated, thermal mass flow meter, which tracks the passage through the purification means as described above. A predetermined mass of the catalyst sample, such as a slurry slurry in purified Nujol, was added to the reactor under the flow of the exhaust gas without the prior contact of the catalyst with any reagent, such as a catalyst activator. The polymerization solvent was n-hexane (600 mL) which was also purified in the manner previously described. The copolymerization experiments used 1-hexene as the comonomer at an initial concentration of 0.41 mol / L in the liquid phase. Purification methods were used similar for 1-hexene. The catalyst is activated in itself (in the polymerization reactor) at the reaction temperature in the presence of the monomers, using a metal alkyl compound (triisobutylaluminum) which has previously been added to the reactor to remove foreign impurities. The internal temperature of the reactor is monitored by a thermocouple in the polymerization medium and can be controlled to the required reference point at +/- 2.0 ° C. The duration of the polymerization experiment was one hour. After completion of the polymerization experiment, the polymerization solvent was allowed to evaporate and the polymer was dried under ambient conditions after which the yield was determined.

Example 14 Preparation and Copolymerization with Ethylene / 1-Hexene of Titanium [(tri (t-butyl) phosphinimine)] (2,6-di (isopropyl) phenoxy) Cyclopentadienyl chloride Supported in MAO / Silica The polymerization experiment was conducted using 3 mg of the same catalyst used in Example 1. In the isolation and drying of the polymer, a yield of 25 g was obtained, which represents a catalytic productivity of 1,200,000 g of PE / g of Ti . The polymer, characterized by the GPC, showed a molecular weight of 887,000 (Mw) and a polydispersity of 2.1. The polymer was found to contain 1.5% mol of 1-hexene.

Example 15 Preparation and Copolymerization with Ethylene / 1-Hexene of Titanium [(tri (t-butyl) phosphinimine)] Cyclopentadienyl dichloride Supported in MAO / Silica The polymerization experiment was conducted using 3 mg of the same catalyst used in Example 2. In the isolation and drying of the polymer, a yield of 21 g was obtained, which represents a catalytic productivity of 970,000 g of PE / g of You. The polymer, characterized by the GPC, showed a molecular weight of 994,000 (Mw) and a polydispersity of 2.1. It was found that the polymer contains 1.6 mol% 1-hexene.

Example 16 Preparation and Copolymerization with Ethylene / 1-Hexene of Cyclopentadienyl [tri (t-butyl) phosphinimine)] dimethyl and [Ph3C] [B (C6Fs) 4] Supported on Silica treated with Triethylaluminium The polymerization experiment was conducted using 8 mg of the same catalyst used in Example 7. In the isolation and drying of the polymer, a yield of 27 g was obtained, which represents a catalytic productivity of 500,000 g of PE / g of Ti. The polymer, characterized by the GCP, showed a molecular weight of 700,000 (Mw) and a polydispersity of 2.1. The polymer was found to contain 1.2% mol of 1-hexene.

Polymerization Data for Examples 13-15 ^ 1 o It is noted that in relation to this date, the best method known to the applicant to carry out the aforementioned invention, is that which is clear from the present description of the invention.

Having described the invention as above, the content of the following claims is claimed as property.

Claims (20)

1. . A catalyst component for the polymerization of olefins characterized in that it comprises: (a) an organometallic complex comprising (i) a group 4 metal selected from Ti, Hf and Zr; (ii) a ligand of the cyclopentadienyl type; (iii) a phosphinimine ligand; (iv) two univalent ligands; and (b) a support of particulate material.

2. The catalyst component according to claim 1, characterized in that the organometallic complex comprises a complex of the formula: Cp [(R1) 3-P = N] p- M - (L1) 3-n wherein M is selected from the group consisting of Ti, Zr and Hf; n is 1 or 2; Cp is a ligand of the type of cyclopentadienyl which is unsubstituted or substituted by up to five substituents independently selected from the group consisting of a hydrocarbyl radical of 1 to 10 carbon atoms or two hydrocarbyl radicals taken together can form a ring that the hydrocarbyl substituents or the cyclopentadienyl radicals are without substituting or additionally substituted by a halogen atom, an alkyl radical of 1 to 8 carbon atoms, an alkoxy radical of 1 to 8 carbon atoms, an aryloxy or aryl radical of 6 to 10 carbon atoms; an amido radical which is unsubstituted or substituted by up to two alkyl radicals of 1 to 8 carbon atoms; a phosphide radical which is unsubstituted or substituted by up to two alkyl radicals of 1 to 8 carbon atoms; silyl radicals of the formula -Si (R2) 3 wherein each R2 is independently selected from the group consisting of hydrogen, an alkoxy or alkyl radical of 1 to 8 carbon atoms, aryloxy or aryl radicals of 6 to 10 carbon atoms; germanyl radicals of the formula Ge- (R2) 3 wherein R2 is as defined above; each R1 is independently selected from the group consisting of one hydrogen atom, a halogen atom, hydrocarbyl radicals of 1 to 10 carbon atoms which are unsubstituted by or further substituted by a halogen atom, an alkyl radical of 1 to 8 carbon atoms, an alkoxy radical of 1 to 8 carbon atoms, an aryloxy or aryl radical of 6 to 10 carbon atoms, a silyl radical of the formula -Si- (R2) 3 wherein each R2 is independently selected from the group consisting of hydrogen, an alkoxy or alkyl radical from 1 to 8 carbon atoms, aryloxy or aryl radicals of 6 to 10 carbon atoms, a germanyl radical of the formula Ge- (R2) 3 wherein R2 is as defined above or two R1 radicals taken together can form a radical hydrocarbyl of 1 to 10 carbon atoms, bidentate, which is unsubstituted by or further substituted by a halogen atom, an alkyl radical of 1 to 8 carbon atoms, a radical alkoxy of 1 to 8 carbon atoms, an aryloxy radical or ari from 6 to 10 carbon atoms, a silyl radical of the formula -Si (R2) 3 wherein each R2 is independently selected from the group consisting of hydrogen, an alkoxy radical or alkyl of 1 to 8 carbon atoms, aryloxy radicals or aryl of 6 to 10 carbon atoms, germanyl radicals of the formula Ge- (R2) 3 wherein R2 is as defined above, with the proviso that Ri individually or two Ri radicals taken together can not form a Cp ligand as defined above; each L1 is independently selected from the group consisting of a hydrogen atom, a halogen atom, a hydrocarbyl radical of 1 to 10 carbon atoms, an alkoxy radical of 1 to 10 carbon atoms, an aryl oxide radical of 5 to 10 carbon atoms, each of which hydrocarbyl, alkoxy and aryl oxide radicals may be unsubstituted by or further substituted by a halogen atom, an alkyl radical of 1 to 8 carbon atoms, an alkoxy radical of 1 at 8 carbon atoms, an aryloxy or aryl radical of 6 to 10 carbon atoms, an amido radical which is unsubstituted or substituted by up to two alkyl radicals of 1 to 8 carbon atoms; a phosphide radical which is unsubstituted or substituted by up to two alkyl radicals of 1 to 8 carbon atoms, with the proviso that L1 can not be a Cp radical as defined above.

3. The catalyst component according to claim 1, characterized in that the particulate support is selected from metal oxide, metal chloride, talc and polymer.

4. The catalyst component according to claim 3, characterized in that the particulate support is a metal oxide selected from silica and silica-alumina.

5. The catalyst component according to claim 1, characterized in that it contains a supported activator.

6. The catalyst component according to claim 5, characterized in that the activator is selected from an alumoxane and a substantially non-coordinating anion.

7. The catalyst component according to claim 6, characterized in that the activator is a substantially non-coordinating anion described by the formula: B (R7) 3 or 4 wherein each R7 is a phenyl ligand treated with fluorine and B is boron.

8. The catalyst component according to claim 5, characterized in that the supported activator is an alumoxane.

9. The catalyst component according to claim 8, with the additional proviso that the molar ratio of Al / M is from 100: 1 to 200: 1, characterized in that Al is aluminum contained in the aluminoxane and M is the transition metal.

10. The catalyst component according to claim 9, characterized in that: (a) the alumoxane is initially deposited in the support; (b) the organometallic complex is subsequently deposited; and (c) the molar ratio of Al / M is from 110: 1 to 150: 1.

11. The catalyst component according to claim 1, characterized in that it is prepared by the co-pulverization / drying of the organometallic complex and the particulate support.

12. The catalyst component according to claim 5, characterized in that: 12 (1) the organometallic complex and the activator are initially provided in the form of a volume of activator / catalyst solution; 12 (2) the particulate support has a pore volume which is greater than the volume of the activator / catalyst solution; 12 (3) The catalyst component is prepared by mixing the volume of the activator / catalyst solution of 12 (1) and the particulate support of 12 (2) until the volume of the activator / catalyst solution is contained substantially within the pore volume.

13. A process for the polymerization of olefins, characterized in that it comprises the polymerization of ethylene, optionally with at least one addition of alpha olefin, in the presence of a catalyst component according to claim 1.

14. The process according to claim 13, characterized in that it is conducted in a gas phase reactor.

15. The process according to claim 13, characterized in that it is conducted in a slurry reactor.

16. The process according to claim 14, characterized in that a trialkyl aluminum is added as a contaminant scavenger.

17. The process according to claim 16, characterized in that it is conducted a temperature of 75 to 115 ° C and a pressure of 7,022 to 10,532 kilograms per square centimeter (100 to 350 pounds per square inch).

18. The process according to claim 17, characterized in that it is conducted in a condensation mode in the presence of an alkane or isoalkane which is condensable at the polymerization pressure by contact with a cooling coil.

19. The catalyst component according to claim 1, characterized in that the phosphinimine ligand is tri (tertiary butyl) phosphinimine.

20. The catalyst component according to claim 10, characterized in that it contains a coating of mineral oil, wherein the mineral oil is coated subsequent to the deposition of the organometallic complex.