MXPA00009379A

MXPA00009379A - Ion exchanged aluminium-magnesium or fluorinated magnesium silicate aerogels and catalyst supports therefrom

Info

Publication number: MXPA00009379A
Application number: MXPA/A/2000/009379A
Authority: MX
Inventors: R Wilson David; Tao Sun; Juan M Garces
Original assignee: The Dow Chemical Company
Priority date: 1998-03-26
Filing date: 2000-09-25
Publication date: 2001-07-09

Abstract

Aluminum-magnesium silicate- or fluorinated magnesium silicate- aerogels which may be calcined, chemically modified, ion-exchanged, agglomerated, used as a component of a catalyst composition for an addition polymerization;supported versions thereof;and processes for polymerization are disclosed.

Description

ALUMINUM-MAGNESIUM OR SILICATE SILICATE AEROGELS OF MAGNESIUM FLUORATED WITH IONS EXCHANGED AND SUPPORTS OF CATALYSTS OF THEMSELVES This invention relates to novel aerogels materials of aluminum-magnesium silicate or fluorinated magnesium silicate which are useful, inter alia, as supports for Group 3-10 metal complexes used in the polymerization by the addition of monomers such as olefins to form high molecular weight homopolymers and copolymers. The materials are also useful as thickeners or thixotropic agents for paints or greases, viscosity modifiers for oils and lubricants, ion exchange media, vehicles for pigments and supports for hydrogenation catalysts. It is widely known that addition polymerization processes using metallocene catalysts have been used to produce a large scale of novel polymers for use in a variety of applications and products. The supported olefin polymerization catalysts are widely known and used in the gas phase and slurry polymerization of said olefins. Suitable support materials have silica, alumina, aluminosilicates, clays and other metal oxides included. In US-A-5,529,965 and related patents, a type of supported metallocene catalyst was prepared by contacting a support material containing water with an aluminum trialkyl compound to prepare a support material containing alumoxane suitable for use in combination with metallocenes as olefin polymerization catalysts. In US-A-5,362,825, stacked clays are used to provide supports for transition metal catalysts. The stacked clay is preferably prepared by reacting smectite clay with an aqueous solution of a complex of polymeric cationic hydroxy metals, drying the solid product produced and then calcining the product. The preparation of stacked clays, also known as interleaved clays, was described in detail in US-A-4,248,739, US-A-4,666,887, US-A-4,367,163, US-A-4,271,043, US-A-4,248,739, US. -A-4,238,364, US-A-4,216, 188 and US-A-4, 176,090, among other references. Catalysts for olefin polymerization comprising a metallocene, an ion exchange compound, especially a clay, and an organic aluminum compound, such as a trialkyl aluminum compound, were described in US-A-5, 308,811. More recently, EP-A-658,576 described the formation of modified clay containing supported catalysts containing a metallocene, wherein an ionic compound, especially a salt of Bronsted acid, such as dimethylanilinium chloride, was included in the clay. Delaminated clays, that is, clay materials that lack the X-ray diffraction pattern in the first order and have a random orientation of platelets, are a known class of materials. Another technique for preparing such delaminated clay materials is the freezing of an aqueous dispersion of the clay material and subsequently removing the water, such as by freeze drying. Said preparation methods using non-stacked clays are described in JP-A-01/103908 and JP-A-63/230581. T.J. Pinnavaia, "Preparation and Properties of Pillared and Delaminated Clay Catalysts", Heterogeneous Catalvsts. B.L. Shapiro, ed., Texas A &M University Press, College Station, Texas, (1984), described a similar method using clay starting materials. A second technique for preparing such delaminated clays using air drying instead of freeze drying was described in US-A-4,761,391. Ion-exchange techniques of conventional, unexpanded, hydrated metal oxide gels, including aluminum-magnesium silicate gels, were previously known in the art. Examples include FR 1.090, 868-A, in which an ion exchange resin is used in the ion exchange, and US-A-2,688,002, where the conventional treatment with metal salt solutions used for the change process was used. US-A-3,404,097 disclosed unexpanded silicate and magnesium and its fluorinated derivatives. All the above materials were used as catalyst supports, for catalytic cracking catalysts. EP-A-669,346 discloses particulate magnesium and aluminosilicates, but not their derivatives with changed form. It was said that said compositions were useful as supports for olefin polymerization catalysts.

Despite the advancement in the art resulting from the use of the above inventions and discoveries, it remains desirable to provide catalyst supports and catalyst components that have improved physical and chemical properties. In particular, a catalyst support or catalyst component is desired for olefin polymerizations lacking cocatalyst substances, especially alumoxane materials, or the alumoxane type, or Bronsted acid salts contained in uncoordinated anions, for the purpose of reduce costs of the catalyst material. Especially, the use of extremely low density substances lacking harmful polar groups or intercalated substances which can detrimentally react with the active metal complexes used in the catalyst formulation is desired. According to one embodiment of the present invention, an aluminum-magnesium silicate airgel or fluorinated magnesium silicate airgel having exchanged ions is provided. The airgel material of the present invention can also be calcined, chemically modified or functionalized, in addition to having exchanged ions, impregnated, coated with any chemical coating, formed into particles or modified in some manner according to techniques known in the prior art. , or not previously known in the techniques to adapt them to particular end uses. It is understood that one or more of the above steps may be carried out on the airgel and the same procedure may be repeated one or more times in the same or varied manner without departing from the scope of the present invention. In a preferred embodiment, the airgel is calcined, contacted with a functionalizing agent, treated with a catalyst activating material capable of forming active polymerization catalysts of the metal complexes of group 3-10 or of contacting a complex or compound of metals of group 3-10 to produce a composition of addition polymerization catalysts. If desired, the airgel, before or after the modification in the above form, can be treated with a reinforcing agent and / or formed into agglomerated particles in order to provide substrates of the size of substantially uniform particles. When used in a gas phase or slurry polymerization, the catalyst compositions are heterogeneous and can be referred to as a supported polymerization catalyst composition. In another embodiment of the invention, a support material is provided for use in order to prepare supported catalysts for addition polymerizations comprising an aluminum-magnesium silicate airgel or fluorinated magnesium silicate airgel. In a preferred embodiment, the airgel has the form of agglomerated particles. More preferably, the airgel also has exchanged ions. Accordingly, the present invention also includes a supported addition polymerization catalyst, comprising the aluminum-magnesium silicate airgel with exchanged ions previously described or fluorinated magnesium silicate airgel, which has been optionally calcined, has been contacted with a functionalizing agent, it has been treated with a catalyst activating material as previously described, treated with a reinforcing agent and / or agglomerated and optionally, additionally, treated with one or more metal complexes of the group 3-10 so that it deposits the complex on the airgel, said metal complex being deposited in an amount of 0.00001 to 1,000 mg / g of the support. Finally, according to the present invention, there is provided a process for polymerizing an addition polymerizable monomer, comprising contacting the monomer or a mixture comprising the monomer, with a composition comprising one or more of the addition polymerization catalysts. described above. The use of such supported catalysts results in highly efficient production of high molecular weight polymers over a wide range of polymerization conditions., especially at elevated temperatures. The present compositions are especially useful for catalyzing the phase homopolymerization in solution, gaseous or slurry phase of ethylene or propylene or the phase copolymerization in solution, gas phase or ethylene / propylene slurry (EP polymers), ethylene / octene (EO polymers), ethylene / styrene (ES polymers) and ethylene / propylene / diene (EPDM polymers) wherein the diene is ethylideneorbornene, 1,4-hexadiene, or a similar unconjugated diene. The above polymeric materials are useful in the preparation of films for packaging or other uses, foamed structures for cushioning or insulating applications and the preparation of fibers and solid molded objects. As used herein, the term "airgel" refers to an aluminum-magnesium silicate material or fluorinated magnesium silicate material that has been expanded in a manner that reduces the volume density thereof to 1.0 g / cm 3 or more. less. Preferably, the material retains at least a partial laminar structure. That is, at least in portions of the composition, alternating layers of aluminum silicate and magnesium silicate are found to exist in at least two dimensions, however, the separation between the layers thereof can be expanded from 2 to 100,000. times more than the separation of a non-expanded clay material. Therefore, in the present, the materials are alternatively referred to as "layered aerogels". Preferred aerogels of aluminum-magnesium silicate or fluorinated magnesium silicate according to the present invention have a volume density of 0.5 to 0.0001 g / cm3, more preferably 0.1 to 0.001 g / cm3. Although very conveniently prepared from natural or artificial clays, it is understood that the present aerogels materials can be prepared from individual aluminum silicate and magnesium silicate compounds or mixtures of silicate compounds or by any technique adequate If prepared from a clay, the type of clay used in the preparation of aluminum-magnesium silicate airgel may be any of the 5 recognized classes, classified by the amount of negative charge in silicate layers of the clay. These are: 1) clays of biofilite, kaolinite, dicalite or talc, 2) smectite clays 3) vermiculite clays 4) mica, and 5) brittle mica. Preferred clays are those that have good proton transfer properties. The above clay materials exist in nature and can also be synthesized, generally, with a purity higher than that of the natural material. Any of the naturally occurring or synthetic clay materials can be used to form the aerogels used in the present invention. The preferred clay materials are smectite clays, including montmorillonite, bidelite, saponite and hectorite or fluoromagnesium silicate. A more preferred clay is montmorillonite clay. Mixtures of the above clays can also be used with inorganic silicates, such as sodium silicate. The expansion of the silicate layers of the clay or other material can be achieved by any suitable technique. Preferably, the silicate material is formed in a relatively homogeneous aqueous dispersion, and subsequently dried in a form that retains the delaminated or partially delaminated, expanded structure, more preferably, freeze drying thereof. Any other technique that allows the operator to prepare a stable expanded, similar, dismembered or partially delaminated structure, including calcination, may also be used. The silicate material conveniently has exchanged ions, either before or after the previous expansion process, in order to replace at least a portion of the natural alkali metal cations or alkaline earth metal cations, especially sodium or magnesium cations, with a cation selected from the group consisting of H +, conjugated acids of Lewis bases, reduced cations of Lewis acid, and reduced metal cations. Examples of conjugated acids of Lewis bases include ammonium, phosphonium, sulfonium and ozonium cations, containing at least one proton. Preferred conjugated acids of Lewis bases are protonated ammonium cations, especially NH 4 +. Examples of reducible Lewis acid cations include quaternary ammonium cations, ferrocenium cations, carbonium and silylium. Examples of reducible metal cations include Ag +, Pb + 2 and FeA Any suitable anion, especially halide, nitrate, sulfate or phosphate anions, can be used as a counter-anion for the above cations in the exchange process. After recovering the airgel (i.e. after freeze drying), the residual water and organic contaminants are conveniently removed and the beneficial properties are imparted to the resulting aerosol by calcining them. Calcination can be achieved by heating the airgel, optionally in the presence of an inert gaseous medium, especially nitrogen or argon, for a time, preferably 10 minutes to 48 hours. Conveniently, the calcination is carried out at a temperature of 200 to 800 ° C, preferably 400 to 800 ° C. Conveniently, the water content of the airgel after calcination is less than 0.5 percent by weight, more preferably less than 0.1 percent by weight. The residual hydroxyl or other reactive functionality is also conveniently removed, generally by plugging or reacting said groups with a chemical modifying agent or functionalizing agent, especially a Lewis acid. Conveniently, the residual surface hydroxyl or other reactive functionality content of aluminum magnesium silicate airgel is reduced to a level of less than 1 weight percent, preferably less than 0.1 weight percent. Suitable chemical modifying agents include trihydrocarbylaluminum compounds, trihydrocarbylchlorosilane compounds, and hydrocarbylsiloxane compounds containing from 3 to 20 atoms without counting hydrogen. The preferred reactive materials are those lacking labile protons. The most preferred chemical modifying agents include trialkyl aluminum compounds of 1 to 10 carbons in each alkyl group and hydrocarbylsilanes or siloxanes wherein the hydrocarbyl substituents contain from 1 to 20 carbon atoms, such as trimethylchlorosilane. The use of chemical silane or siloxane modification agents additionally provides a material that is extremely stable at elevated temperatures. For optimal catalytic activity, it is convenient to treat the airgel material with the chemical modifying agent containing silane or siloxane and trihydrocarbyl aluminum compound, preferably an aluminum trial having 1 to 10 carbons in each alkyl group. Preferably, the amount of chemical modifying agent that is reacted with the airgel material is 0.001 to 100 g / g of the airgel, preferably 0.005 to 0.1 g / g of the airgel. The chemical modifying agent can be added to the airgel at any time during the synthesis and still be added to the catalyst formulation at the time when the metal complex catalyst and the airgel are combined. While not wishing to be bound by any particular theory of operation, it is thought that the aluminum-magnesium silicate airgel or fluorinated magnesium silicate materials of the present invention provide superior catalyst activity due to the increased distance between the silicate layers. of them compared to other supports, thus increasing the available surface area of the material for the bonding of the catalyst. In addition, airgel materials are conveniently finally impregnated with Bronsted acid salts containing an organic ligand group, especially protonated ammonium salts, preferably tri (hydrocarbyl) ammonium salts, more preferably N, N-dialkylanilinium salts, which may play a role in causing the airgel to retain its expanded form. In addition, the present aerogels are highly oleophilic and exhibit a remarkable ability to absorb or imbibe hydrocarbons up to 50 times the weight of the airgel itself or higher. This property may also benefit access to the active catalytic sites contained within the airgel by hydrocarbon reagents including the monomers. For use in the gas phase polymerization of olefin monomers, aerogels can be formed into particles by any suitable technique in order to provide a highly porous particle sized uniformly. Suitable techniques for forming airgel particles include agglomerating the aluminum-magnesium silicate airgel by adding an inorganic binder while the clay is dispersed in the water or by partially compacting and grinding the resulting airgel material. Agglomerates with uniform particle size can be formed by dispersing them in the form of an oil-in-water emulsion with uniform particle size and optionally agglomerating to form larger particles before removing the water phase. Inorganic binders suitable for the above process include the reaction product in bound form with a water-soluble silicate such as sodium or potassium silicate. Said particulate form of the airgel generally has a higher density than the non-particulate product. Additionally, a particulate form of the supported catalyst can be produced by prepolymerizing one or more olefins using the catalyst and then shaping the resulting prepolymerized catalyst into the desired particle size. To form the airgel particles, it may also be convenient to include one or more reinforcing agents in the formulation to avoid excessive loss of pore volume. Suitable reinforcing agents include silicon dioxide and inorganic silicate materials. A preferred reinforcing agent is finely divided silica, such as fumed silica. The size and porosity of the agglomerated airgel particles can be controlled by the amount of the inorganic binder and the reinforcing agent, the rate of agitation, temperature, use of a coagulant and other known techniques. When used as catalyst supports, the aerogels of the invention do not beneficially require the use of metallocene catalyst activators containing inert non-coordinated anions, especially those containing tetrakis (pentafluorophenyl) borate anions, which are relatively expensive. However, the use of said activators is not necessarily outlawed and can be used by the skilled person without departing from the scope of the present invention. After preparation of the airgel, a complex or compound of metals of group 3-10 is added to form the finished supported polymerization catalyst. The complexes or compounds of metals of group 3-10 suitable for use in combination with the above supports, include any compound or complex of a metal of Groups 3-10 of the Periodic Table of the Elements capable of being activated to polymerize the compounds ethylenically unsaturated in combination with the present supports. In a preferred embodiment, the above steps for preparing the present ion exchange airgel can be summarized as: 1) dispersing a fluorinated magnesium clay or silicate in water, 2) exchanging ions from the fluorinated magnesium clay or silicate dispersed with a cationic material or cation formation material, and 3) drying the dispersion, to provide an aluminum-magnesium silicate airgel or fluorinated magnesium silicate. In the previous step 2), a preferred ion exchange material is a strong Bronsted acid, such as hydrochloric acid or a protonated cationic salt, such as ammonium salt, especially NH4CI or NH4NO3. In addition, steps 2) and 3) can be carried out in reverse order without adversely affecting.

In the preparation of aluminum-magnesium silicate airgel or fluorinated magnesium silicate airgel to be used as a support for catalysts, the following additional steps are preferably carried out: 4) optionally calcining the airgel with ion exchange, ) redispersing the ion exchange airgel in an organic liquid, 6) contacting the airgel with exchanged ions, redispersed, with one or more chemical modification agents capable of removing the hydroxyl or other surface functionality of reagents that could interfere with the catalytic properties of the resulting substance. In a further preferred embodiment for preparing catalyst compositions including supported catalyst compositions used for addition polymerizations, the following additional steps are conveniently carried out: 7) optionally forming the airgel into particles of relatively uniform particle size. 8) contacting the airgel with ion exchange with a complex or compound of metals of group 3-10 capable of forming a polymerization catalyst, and 9) recovering the resulting supported catalyst. While the above steps have been enumerated for purposes of differentiation, the skilled person will appreciate that it is not necessary for the operation of the invention, that said steps are carried out chronologically in the order in which they have been listed. Examples of suitable metal complexes or compounds for use herein include Group 10 diimine derivatives corresponding to the formula: r * M ** is Ni (ll) or Pd (ll); X 'is halo, hydrocarbyl or hydrocarbyloxy; Ar * is an aryl group, especially 2,6-di-isopropylphenyl or aniline group; and CT-CT is 1, 2-ethanedi-yl, 2,3-butanedi-yl, or forms a fused ring system wherein the two T groups together are a 1,8-naphthanedi-yl group. Compounds similar to the above are also described by M. Brookhart, et al., In J. Am. Chem. Soc, 188, 267-68 (1996) and J ^ Am. Chem. Soc, 117, 6414-6415 (1995). , being polymerization catalysts of α-olefins, either alone or in combination with polar comonomers such as vinyl chloride, alkyl acrylates or alkyl methacrylates. Additional complexes or compounds include derivatives of Group 3, 4 metals, or lanthanides that are in the formal oxidation state +2, +3 or +4. Preferred are those containing from 1 to 3 groups of anionic or neutral p-linked ligands, which may be groups of anionic or neutral p-linked cycloalkyl or non-cyclic ligands. Illustrative of said p-linked groups are cyclic or non-cyclic, conjugated or non-conjugated diene and dienyl groups, allyl groups, boratabenzene groups, phosphols and arene groups. By the term "p-linked" is meant that the group of ligands is attached to the transition metal by an electron shearing stress from a partially delocalized p-bond. Each atom in the independently delocalized p-linked group can be substituted with a radical selected from the group consisting of hydrogen, halogen, hydrocarbyl, halohydrocarbyl, hydrocarbyl substituted heteroatoms wherein the heteroatom is selected from Group 14-16 of the Periodic Table of the Elements and said radicals of hydrocarbyl substituted heteroatoms are further substituted with a Group 15 or 16 heteroatom containing portion. In addition, two or more of said radicals can together form a system of fused rings, including, partially or completely, ring systems fused hydrogenated, or can form a metallocycle with the metal. Within the term "hydrocarbyl" are branched and straight-chain alkyl radicals of C 1-20, aromatic C 6-2o radicals, aromatic radicals substituted with C 7-20 alkyl and alkyl radicals substituted with C 7 aryl. twenty. Suitable hydrocarbyl substituted heteroatom radicals include mono-, di- and tri-substituted boron, silicon, germanium, nitrogen, phosphorus or oxygen, wherein each of the hydrocarbyl groups contains from 1 to 20 carbon atoms. Examples include N, N-dimethylamino, pyrrolidinyl, trimethylsilyl, triethylsilyl, t-butyldimethylsilyl, methyldi (t-butyl) silyl, triphenylgermyl and trimethylgermyl groups. Examples of the heteroatom containing portions of Group 15 or 16 include amino, phosphino, alkoxy, or alkyl portions or divalent derivatives thereof, e.g., amide, phosphide, alkyleneoxy or alkylenethio groups attached to the transition metal or metal of Lanthanides and attached to the hydrocarbyl group, p-linked group or hydrocarbyl substituted heteroatom. Examples of groups delocalized p-bonded cyclopentadienyl groups include suitable anionic, indenyl, fluorenyl, tetrahydroindenyl, tetrahydrofluorenyl, octahydrofluorenyl, pentadienyl, cyclohexadienyl, dihydroanthracenyl, hexahydroanthracenyl, decahydroanthracenyl groups, and boratabenzene, and substituted derivatives of C 1-10 hydrocarbyl or derivatives silyl substituted with C? -10 hydrocarbyl. Preferred delocalized anionic p-linked groups are cyclopentadienyl, pentamethylcyclopentadienyl, tetramethylcyclopentadienyl, tetramethylsilylcyclopentadienyl, indenyl, 2,3-dimethylindenyl, fluorenyl, 2-methylindenium, 2-methyl-4-phenylindenyl, tetrahydrofluorenyl, octahydrofluorenyl, 1-indacenyl. , 3-pyrrolidinoinden-1-yl, 3,4- (cyclopenta (/) phenanthren-1-yl and tetrahydroindenyl) Boratabenzenes are anionic ligands that are boron-containing analogs for benzene, previously known in the art being described by G. Herberich et al., In Orqanometallics, 14, 1, 471-480 (1995) The boratabenzenes Preferred correspond to the formula: wherein R "is selected from the group consisting of hydrogen, hydrocarbyl, silyl or germyl, said R" having up to 20 non-hydrogen atoms. In complexes involving divalent derivatives of said delocalized p-linked groups, one atom thereof is bound by means of a covalent bond or a divalent group covalently linked to another atom of the complex thereby forming a bridged system.

The phospholes are anionic ligands that are phosphorus-containing analogs for a cyclopentadienyl group. Previously they were known in the art having been described in WO 98/50392 and elsewhere. Preferred phosphole ligands correspond to the formula: wherein R "is as previously defined The phosphinimine / ciopentadienyl complexes were described in EP-A-890581 and correspond to the formula [(R **) 3 = P = N] bM ** (Cp) (L1 ) 3-b, wherein: R ** is a monovalent ligand, illustrated by hydrogen, halogen or hydrocarbyl, or two R ** groups together form a divalent ligand, M ** is a Group 4 metal, Cp is cyclopentadienyl or a similar delocalized p-linked group, L1 is a monovalent ligand group, illustrated by hydrogen, halogen or hydrocarbyl, and b is 1 or 2. An additional suitable class of the transition metal complexes for use herein correspond to the formula : K'kMZ'mL | Xp, or a dimer thereof, wherein: K 'is an anionic group containing delocalised p-electrons through which K' is attached to M, said group of K 'containing up to 50 atoms without counting hydrogen atoms, optionally two K 'groups can be attached forming a bridged structure and optionally and in addition a K 'can join Z'; M is a metal of Group 4 of the Periodic Table of the Elements in the formal oxidation state +2, +3 or +4; Z 'is an optional divalent substituent of up to 50 non-hydrogen atoms that together with K form a metallocycle with M, L is an optional neutral ligand having up to 20 non-hydrogen atoms; X, each time it is presented, is a monovalent anionic portion that has up to 40 atoms that are not hydrogen, optionally two X groups can be covalently linked to form a divalent dianionic portion having both valences attached to M, u, optionally two X groups can be covalently linked to form a conjugated or non-conjugated diene that binds to M by means of delocalized p-electrons (whereby M is in the oxidation state +2), or optionally additionally one or more of the groups X and one or more of the L groups can be linked thereby forming a portion that is covalently linked to M and coordinated thereto via Lewis base functionality; K is 0, 1 or 2; m is 0 or 1; I is a number from 0 to 3; p is an integer from 0 to 3; and the sum, k + m + p, is equal to the formal oxidation state of M, except when 2 groups X together form a conjugated or neutral non-conjugated diene that is attached to M via the delocalized p-electrons, in which case the sum of k + m is equal to the formal oxidation state of M. Preferred complexes include those containing one or two K 'groups. The last complexes include those that contain the bridging group that unites the two K 'groups. Preferred bridging groups are those corresponding to the formula (ER'2) X wherein E is silicon, germanium, tin or carbon, R ', independently whenever it occurs, is hydrogen or a selected group of silyl, hydrocarbyl , hydrocarbyloxy and combinations thereof, said R 'having up to 30 carbon or silicon atoms and x is from 1 to 8. Preferably, R' independently each time it occurs, is methyl, ethyl, propyl, benzyl, tert-butyl, phenyl, methoxy, ethoxy or phenoxy. Examples of the complexes containing two K 'groups are the compounds corresponding to the formula: wherein: M is titanium, zirconium or hafnium, preferably zirconium or hafnium, in the formal oxidation state +2 or +4. R3 independently each time it occurs is selected from the group consisting of hydrogen, hydrocarbyl, silyl, germyl, cyano, halo, and combinations thereof, R3 having up to 20 non-hydrogen atoms, or adjacent R3 groups together a divalent derivative (ie, a hydrocarbyl-ilo, siladi-yl or germadi-yl group) thus forming a fused ring system, and X "independently whenever it occurs, is an anionic ligand group of up to 40 atoms that does not are hydrogen, or two X groups "together form a divalent anionic ligand group of up to 40 non-hydrogen atoms or together are a conjugated diene having from 4 to 30 non-hydrogen atoms attached by means of delocalized p-electrons to M , so that M is in the formal oxidation state +2, and R ', E, and x are as previously defined. The above metal complexes are especially suitable for the preparation of polymers having stereoregular molecular structure. In such a capacity, it is preferred that the complex have Cs symmetry or have a chiral stereorigid structure. Examples of the first type are compounds having different groups of delocalised p-linked ligands, such as a cyclopentadienyl group and a fluorenyl group. Similar systems based on Ti (IV) or Zr (IV) were described for the preparation of syndiotactic olefin polymers in Ewen, et al., J. Am. Chem. Soc. 110, 6255-6256 (1980). Examples of chiral structures include complexes of bis-indenyl rae. Similar systems based on Ti (IV) or Zr (IV), were described for the preparation of isotactic olefin polymers in Wild et al., J. Organomet. Chem. 232, 233-47, (1982). Exemplary bridged ligands containing two p-linked groups are: dimethylbis (cyclopentadienyl) silane, dimethylbis (tetramethylcyclopentadienyl) silane, dimethylbis (2-ethylcyclopentadien-1-yl) silane, dimethylbis (2-t-butylcyclopentadiene-1-) il) Si, 2,2, -bis (tetramethylcyclopentadienyl) propane, dimethylbis- (inden-1-yl) silane, dimethylbis (tetrahydroinden-1-yl) silane, dimetyl Ib i s- (fluoren-1-yl) if tin, dimet ilbis (tetrah id rof luoren-1 -i I) if tin, dimethyl-bis (2-methyl-4-f in -linden-1-yl) - if not, dimethylbis (2-methylinden- 1-yl) silane, dimethyl (cyclopentadienyl) (fluoren-1-yl) silane, dimethyl- (cyclopentadienyl) (octahydrofluoren-1-yl) silane, dimethyl (cyclopentadienyl) (tetrahydrofluoren-1-yl) silane, (1,1,2,2-tetramethyl) -1,2-bis (cyclopentadienyl) disilane, (1,2-bis (cyclopentadienyl) ethane and dimethyl (cyclopentadienyl) -1- (fluoren-1-yl) methane. Preferred "X" groups are selected from the groups of hydride, hydrocarbyl, silyl, germyl, halohydrocarbyl, halosilyl, silyl idrocarbyl and aminohydrocarbyl, or two X groups "together form a divalent derivative of a conjugated diene or together form a conjugated diene p-linked neutral. The most preferred "X" groups are C 1-20 hydrocarbyl groups A further class of metal complexes used in the present invention corresponds to the preceding formula K'kMZ'mLnXp, or a dimer thereof, wherein Z 'is a substituent divalent of up to 50 non-hydrogen atoms that together with K 'form a metallocycle with M. Preferred divalent Z' 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 attached directly to K ', and a different atom, selected from the group consisting of nitrogen, phosphorus, oxygen or a sulfur that is covalently bound to M. Another preferred class of Group metal complexes 4 used according to the present invention, corresponds to the formula: R3 wherein: M is titanium or zirconium, preferably titanium in the formal oxidation state +2, +3 or +4; R3 independently each time it occurs is selected from the group consisting of hydrogen, hydrocarbyl, silyl, germyl, cyano, halo, and combinations thereof, R3 having up to 20 non-hydrogen atoms, or adjacent R3 groups together forming a divalent derivative (i.e., a hydrocarbyl-ilo, siladi-yl or germadi-yl group) thus forming a fused ring system, each X is a halo, hydrocarbyl, hydrocarbyloxy or silyl group, said group having up to 20 atoms that are not hydrogen, or two X groups together form a neutral C5-30 conjugated diene or a divalent derivative thereof; And it is -O-, -S-, -NR'-, -PR'-; and Z is SiR'z, CR'2, SiR'2SIR'2l CR'2CR'2, CR '= CR', CR'2SiR'2 or GeR'2, where R 'is as previously defined. Illustrative Group 4 metal complexes that may be employed in the practice of the present invention include: cyclopentadienyltitaniotrim ethyl cyclopentadienyltitaniotri ethyl, cyclopentadienyltitaniotriisopropyl, cyclopentadienyltitaniotyphenyl, cyclopentadienyltitaniotribenzyl, cyclopentadienyltitanium-2,4-dimethylpentadienyl, cyclopentadienyltitanium-2,4-dimethylpentadienyl »triethylphosphine, cyclopentadienyltitanium-2,4-dimetiipentadienil methoxide "trim ethyl phosphine ciclopentadieniltitaniodimetilo of ciclopentadieniltitaniodimetilo chloride, methyl pentametilciclopentadieniltitaniotri, indeniltitaniotrietilo indeniltitaniotrimetilo, indeniltítaniotripropilo, indeniltitaniotrifenilo, tetrahidroindeniltitaniotri benzyl, pentametilciclopentadieniltitaniotriisopropilo, pe nt ametilciclopentad i eni Ititaniotri benzyl, methoxide pentametilciclopentadieniltitaniodimetilo of pentametilciclopentadieniltitaniodimetilo chloride, bis (? 5-2,4-dimethylpentadienyl) titanium bi s (? 5-2,4-d.methylpentadyl) thiolium »trimethylphosphine, bis (? 5-2,4-dimethylpentadienyl) titanium» triethyl phosphine, octahydrofluorenylthrityltrimethyl, tetrahydro-indenyltitanitrimethyl, tetrahydroforenylthiothiotrimethyl, (ter- butylamido (1,1-dimethyl, 2,3,4,9,10 -? - 1,4,5,6,7,8-hexahydronaphthaleni) dimethylsilanetitaniodimethyl, (tert-butylamido) (1,1,2,3- tetramethyl-2,3,4,9 -? - 1,4,5,6,7,8-hexahydronaftaleniI) dimethylsilanetitaniodimethyl, (tet-butylamido) (tetramethyl- (? 5-cyclopentadienyl) dimethylsilanetitanium dibenzyl, (tert-butylamido) (tetramethyl- (? 5-cyclopentadienyl) dimethylsilanetitanium dimethyl, (tert-butylamido) (tetramethyl- (? 5-cyclopentadienyl) -1,3-ethanediiltitanium dimethyl, (tert-butylamido) (tetra met il - (? 5-in of nil) d imet ilsilanotitanio di methyl, (tert-butylamido) (tetramethyl - (? 5-cyclopentadienyl) dimethylsilane titanium (III) 2- (dimethylamino) benzyl; (tert-butylamido) (tetramethyl - (? 5-cyclopentadienyl) dimethylsilanetitanium (III) allyl, (tert-butylamido) (tetramethyl - (? 5-cyclopentadienyl) dimethylsilanetitanium (III) 2,4-dimethylpentadienyl, (tert-butylamido) (tetramethyl- (? 5-cyclopentadienyl) dimethylsilanetitanium (II) 1,4-diphenyl-1,3-butadiene, (tert-butylamido) (tetramethyl- (? 5-cyclopentadienyl) dimethylsilanetitanium (ll) 1,3-pentadiene, (te r -butylamido) (2, methylindenyl) dimet ilsilanotitanium ( II) 1, 4-d ifenyi-1,3-butadiene, (tert-butylamido) (2-methylindenyl) dimethylsilanetitanium (II) 2,4-hexadiene, (te r-butylamido) (2-methylindenyl) dimethylsilanetitanium (IV) 2,3-dimethyl-1,3-butadiene, (tert-butylamido) (2-methylindenyl) dimethylsilanetitanium (IV) isoprene, (tert-butylamido) (2-methylindenii) dimethylsilanetitanium (IV) 1,3-butadiene, (tert-butylamido) (2,3-dimethylindenyl) dimethylsilanetitanium (IV) 2,3-dimethyl-1,3-butadiene (tert-butylamido) (2,3-dimethylindenyl) dimethylsilanetitanium (IV) isoprene (tert-butylamido) (2,3-dimethylindenyl) dimethylsilanetitanium (IV) dimethyl (tert-butylamido) (2,3-dimethylindenyl) dimethylsilanetitanium (IV) dibenzyl (tert-butylamido) (2,3-dimethylindenyl) dimethylsilanetitanium (IV) 1,3-butadiene, (te r -butylamido) (2,3-dimethylindenyl) dimethylsilanetitanium (II) 1,3-pentadiene, (tert-butylamido) ) (2,3-dimethylindenyl) dimethylsilanetitanium (II) 1,4-dif eni I-1,3-butadiene, (tert-butylamido) (2-methylindenyl) dimethylsilanetitanium (II) 1,3-pentadiene, (tert-butylamido) (2-methylindenyl) dimethylsilanetitanium (IV) dimethyl, (tert-butylamido) (2-methylindenyl) dimethylsilanetitanium (IV) dibenzyl, (tert-butylamido) (2-methyl-4-phenylindenyl) dimethylsilanetitanium (II) 1,4-d if enyl-1,3-butadiene, (tert-butylamido) (2-methyl-4-phenyl) -dimethylsilanetitanium (II) 1,3-pentadiene, (tert-butylamido) (2-methyl-4-phenylindenyl) dimethylsilanetitanium (II) 2,4-hexadiene, (tert-butylamido) (tetramethyl-? 5-cyclopentadienyl) dimethyl-silanetitanium (IV) 1,3-butadiene, (tert-butylamido) (tetramethyl-? 5-cyclopentadienyl) dimethyl-silanetitanium (IV) 2,3-dimethyl-1,3-butadiene, (tert-butylamido) (tetramethyl-? 5-cyclopentadienyl) dimethylsilanetitanium (IV) isoprene, (tert-butylamido) (tetramethyl-? 5-cyclopentadienyl) dimethylsilanetitanium (II) ) 1,4-dibenzyl-1,3-butadiene, (tert-butylamido) (tetramethyl-? 5-cyclopentadienyl) dimethylsilanetitanium (II) 2,4-hexadiene, (tert-butylamido) (tetramethyl-? 5-cyclopentadienyl) dimethylsilanetitanium (II) 3-methyl-1,3-pentadiene, (tert-butylamido) (2,4-dimethylpentadien-3-yl) dimethylsilaneditaniodimethyl, (tert-butylamido) (6,6-dimethylcyclohexadienyl) dimethylsilanetitanium-dimethyl, (tert-butylamido) (1,1-di-methyl-2, 3,4, 9,10 -? - 1, 4, 5,6 , 7, 8-hexah id ro-naphthalen-4-yl) dimethylsilanetitaniodimethyl, (tert-butylamido) (1,1,2,3-tetramethyl-2,3,4,9,10 -? - 1,4,5 , 6,7,8-hexahydronaphthalen-4-yl) dimethylsilanetitaniodimethyl, (tert-butylamido) (tetramethyl-? 5-cyclopentadienyl) methylphenylsilanetitanium (IV) dimethyl, (tert-butylamido) (tetramethyl-? 5-cyclopentadienyl) methylphenylsilanetitanium (II) 1,4-diphenyl-1,3-butadiene, 1- (tert-butylamido) -2- (tetramethyl-? 5-cyclopentadienyl) methyl-f-nylsilane-titanium (II) 1,4-diphenyl-1, 3-butadiene, 1- (tert-butylamido) -2- (tetramethyl-? 5-cyclopentadienyl) ethanediiltitanium (IV) dimethyl, and 1- (tert-butylamido) -2- (tetramethyl-? 5-cyclopentadiene I) ethanodii I-titanium (II) 1,4-diphenyl-1,3-butadiene.

Complexes containing two K 'groups including bridged complexes suitable for use in the present invention include: bis (cyclopentadienyl) zirconium ethyl bis (cyclopentadienyl) zirconium dibenzyl, bis (cyclopentadienyl) zirconium methyl benzyl, bis (cyclopentadienyl) zirconium methyl phenyl, bis (cyclopentadienyl) zirconiodiphenyl, bis (cyclopentadienyl) titanium-allyl, bis (cyclopentadienyl) cyconiomethyl methoxide, bis (cyclopentadienyl) zirconiomethyl chloride, bis (pentamethylcyclopentadienyl) zirconiodimethyl, bis (pentamethylcyclopentadienyl) titaniodimethyl, bis (indenyl) circoniodimetilo, indenilfluorenilcirconiodimetilo, bis (indenyl) circoniometil (2- (dimethylamino) benzyl), bis (indenyl) circoniometiltrimetilsililo, bis (tetrahydroindenyl) circoniometiltrimetilsililo, bis (pentamethylcyclopentadienyl) circoniometilbencilo, bis (pentamethylcyclopentadienyl) circoniodibencilo methoxide, bis (pentamethylcyclopentadienyl) circoniometilo, bis (pentamethylcyclopentadienyl) zirconium chloride linden, bis (metiletilciclopentadienil) circoniod¡metilo, bis (butylcyclopentadienyl) circoniodibencilo, bis (t-butilciclopentadieni) circoniodim acetate, bis (ethyltetramethylcyclopentadienyl) circoniodimetilo, bis (metilpropilciclopentadienil) circoniodibencilo, bis (trimethylsilylcyclopentadienyl) criconiodibencilo, dimeth ilisilil-bis (Cj clopentadienyl) zirconiodimethyl, dimethylsilyl-bis (tetramethylcyclopentadienyl) thiranium (III) allyl, dimethylsilyl-bis (t-butylcyclopentadienyl) zirconium dichloride, dimethylsilyl-b is (n-butylcyclopentadienyl) zirconium dichloride, (methylene-bis (tetramethylcyclopentadienyl) titanium (III) 2- (dimethylamino) benzyl, (methylene-bis (n-butylcyclopentadienyl) titanium (III) 2- (dimethylamino) benzyl, dimethylsilyl-bis (indenyl) zirconiobenzyl chloride, dimethylsilyl-bis (2-methylindenyl) zirconiodimethyl, dimethylsilyl-bis (2-methyl-4-phenylindenyl) zirconiodimethyl, dimethylsilyl-bis (2-methylindenyl) zirconium (II 1,4-diphenyl-1,3-buta-diene, dimethylsilyl-bis (2-methyl-4-phenylindenyl) zirconium (II) 1,4-diphenyl-1,3-butadiene, dimethylsilyl-bis (tetrahydroindenyl) zirconium ( ll) 1,4-diphenyl-1,3-butadiene, dimethylsilyl-bis (fluorenyl) zirconiomethyl, dimethylsilyl-bis (tetrahydrofluorenyl) zirconium bis (trimethylsilyl), (isopropylidene) (cyclopentadienyl) (fluorenyl) zirconium dibenzyl, and dimethylsilyl (tetramethyl and clopentadienyl) (fl uo re nyl) circoldium dimethyl. Other complexes, especially those containing other Group 4 metals, will of course be apparent to those skilled in the art.

The complexes are combined with the airgel by any suitable technique. Ideally, they are deposited from the solution in an aliphatic, cycloaliphatic or aromatic liquid, putting them in contact with a solution of the metal complexes and removing the solvent. They can be submerged in the solution of metal complexes or the solution can be coated or sprayed on the surface of the support. Preferably, the liquid is then removed or substantially removed. Although not preferred, it is also within the scope of the present invention to include a known cocatalyst in the catalyst formulation. Suitable cocatalysts for use herein include oligomeric alumoxanes, especially methylalumoxane, methylalumoxane modified by triisobutyl aluminum or isobutylalumoxane, which may be generated in situ by reaction of, for example, a trialkylaluminum compound with water contained in the clay if desired. Additional suitable activating cocatalysts include Lewis acids, such as Group 13 compounds substituted with C1.30 hydrocarbyl, especially tri (hydrocarbyl) aluminum or tri (hydrocarbyl) boron compounds and halogenated (including perhalogenated) derivatives thereof , having from 1 to 20 carbons in each hydrocarbyl or halogenated hydrocarbyl group, more especially, perfluorinated tri (aryl) boron compounds and more especially tris (pentafluorophenyl) borane; non-polymeric, compatible, non-coordinated ion formation compounds (including the use of compounds under oxidation conditions), especially the use of ammonium, phosphonium, ozone, carbonium, silyl, sulfonium or ferrocenium salts of uncoordinated compatible anions; and combinations of activating cocatalysts and prior techniques. Activation cocatalysts and activation techniques above have previously been taught with respect to different metal complexes in the following references: US-A-5,132,380, US-A-5,153,157, US-A-5,064,802, US-A-5,321, 106, US-A-5,721,185, US-A-5,350,723 and WO-97/04234. Combinations of the neutral Lewis acids, especially the combination of a trialkyl aluminum compound having 1 to 4 carbon atoms in each alkyl group and a halogenated borane tri (hydrocarbyl) compound having from 1 to 20 carbons in each hydrocarbyl group, especially tris (pentafluorophenyl) borane, additional combinations of neutral Lewis acid mixtures with a polymeric or oligomeric alumoxane and combinations of a single neutral Lewis acid, especially tris (pentafluorophenyl) borane with a polymeric or oligomeric alumoxane they are especially convenient activation cocatalysts. Preferred molar ratios of the Group 4 metal complex: tris (pentafluorophenylborane: alumoxane) are from 1: 1: 1 to 1: 5: 5, more preferably from 1: 1: 1.5 to 1: 5: 3. of suitable ions useful as cocatalysts in one embodiment of the present invention (but not a preferred embodiment), comprise a cation which is a Bronsted acid capable of donating a proton and an anion which is not of compatible coordination, A *. used herein, the term "non-coordinating" means an anion or substance which does not coordinate the precursor complex containing the Group 4 metal and the catalytic derivative derived therefrom, or chronically is weakly coordinated to the complexes thus remaining labile enough to be displaced by a Lewis base such as olefin monomer.An anion that is not coordinating, especially refers to an anion which when functioning as a valence anion of charges and A complex of cationic metals does not transfer an anionic substituent or fragment thereof from the cation thus forming neutral complexes. "Compatible anions" are anions that do not degrade to neutrality when the initially formed complex decomposes and does not interfere with the desired subsequent polymerization or other uses of the complex. The non-coordinating anions preferred are those that contain a single or multiple coordination complex, said anion is capable of balancing the charge of the active catalyst species (the metal cation) that can be formed when the two components are combined. Also, said anion must be sufficiently labile to displace olefinic, diolefinic and acetylenically unsaturated compounds or other neutral Lewis bases such as ethers or nitriles. Suitable metals include, but are not limited to, aluminum, gold and platinum. Suitable metalloids include, but are not limited to, boron, phosphorus and silicon. Compounds containing anions comprising coordination complexes containing a single metal or metalloid atom are, of course, well known and many, particularly such compounds containing a single atom in the anion portion, are commercially available. The preferable cocatalysts can be represented by the following general formula: (L * H) d + (A ') d-wherein L * is a neutral Lewis base; (L * -H) + is a Bronsted acid; Ad is a non-coordinating compatible anion that has a charge of d- and d is an integer from 1 to 3. More preferably Ad corresponds to the formula: [M * Q4]; wherein: M * is boron or aluminum in the formal oxidation state +3; and Q independently each time it occurs is selected from hydride, dialkylamido, halide, hydrocarbyl, halohydrocarbyl, halocarbyl, hydrocarbyloxy, hydrocarbyl substituted hydrocarbyl, hydrocarbyl substituted with organometal, hydrocarbyl substituted with organometalloid, hydrocarbyloxy, hydrocarbyl substituted with halohydrocarbyloxy, hydrocarbyl substituted with halocarbyl and halo substituted silylohydrocarbyl radicals (including perhalogenated hydrocarbyl radicals, perhalogenated hydrocarbyloxy and perhalogenated silylohydrocarbyl), said Q having up to 20 carbon atoms as long as no more than one Q is present is halide. Examples of suitable hydrocarbyloxy Q groups are described in US-A-5,296,433. In a more preferred embodiment, d is one, that is, the counter ion has a single negative charge and is A "Activation cocatalysts comprising boron which are particularly useful in the preparation of catalysts of this invention can be represented by the following general formula: (L * -H) + (BQ4) "; where: L * is as previously defined; B is boron in a formal oxidation state of 3; and Q is a hydrocarbyl, hydrocarbyloxy, fluorinated hydrocarbyl, fluorinated hydrocarbyloxy or fluorinated silylohydrocarbyl group up to atoms that are not hydrogen, as long as in no more than one occasion Q is hydrocarbyl. Most preferably, Q each time it occurs is a fluorinated aryl group, especially a pentafluorophenyl group. Illustrative, but not limiting, examples of the boron compounds that can be used as an activating cocatalyst in the preparation of the improved catalysts of this invention are the tri-substituted ammonium salts such as: trimethylammonium tetraphenyl borate, methyldioctadecylammonium tetraphenyl borate. , triethylammonium etraphenylborate, tripropylammonium etraphenylborate, tri (n-butyl) ammonium etraphenylborate, methyltetradecyclooctadecylammonium tetraphenyl borate, N, N-dimethylanilinium tetraphenyl borate, NN-diethylanilinium epfenylborate, N, N-dimethyl etraphenylborate (2,4,6 -trimethylanilinium), etrakis (pentafluoropheni lo) borate trimethylammonium, ethacry (pentafluoropheni) borate methylditetradecylammonium, etraquis (pentafluorofeni lo) borate methyldioctadecylammonium, etraquis (pentafluorofeni lo) triethylammonium borate, etraquis (pentafluorofeni lo) borate tripropilamonio, etraquis (pentafluorofeni lo) tri (n-butyl) ammonium borate, etraquis (pentafluorophen o) tri (sec-butyl) ammonium borate, N, N-dimethylanilinium (N-N-dimethyl) ethacrylate (pentafluorophene) borate, N, N-diethylanilinium (N-N-dimethyl) ethacrylate (pentafluorophene) borate, N, N-dimethyl ether (pentafluorophene) borate (2,4,6-dimethylamilinium), tetrathra (2,3,4,6-tetrafluorophenyl) borate trimethylammonium, tetrathra (2,3,4,6-tetrafluorophenyl) borate of triethylammonium, ethaquim (2,3, 4,6-tetrafluoropheni l) tripropylammonium borate, ethacry (2,3,4,6-tetrafluorophenol) tri (n-butyl) ammonium borate, tetrahydrofuran (2,3,4,6-tetrafluorophenyl) borate dimethyI (t-butyl) ammonium, ethacry (2,3,4,6-tetrafluorophenyl) borate of N, N-dimethylanilinium, ethacry (2,3,4,6-tetrafluorophenyl) borate of N, N-diethylanilinium, and N, N-dimethyl-2- (2,4,6-trimethylanilinium) tetrakis (2,3,4,6-tetrafluorophenyl) borate. Dialkylammonium salts such as: tetrakis (pentafluorophenyl) borate dioctadecylammonium, tetrakis (pentafluorophenyl) borate ditetradecylammonium, and tetrakis (pentafluorophenyl) borate dicyclohexylammonium. Tri-substituted phosphonium salts such as triphenylphosphonium tetrakis (pentafluorophenyl) borate, methyldioctadecylphosphonium tetrakis (pentafluorophenyl) borate, and tri (2,6-dimethylphenol) phosphonium tetrakis (pentafluorophenyl) borate. Preferred are the tetrakis (pentafluorophenyl) borate salts of mono- and disubstituted ammonium complexes of long-chain alkyl, and especially C 14 -C 20 alkyl ammonium complexes. especially methyl (octadecyl) ammonium tetrakis (pentafluorophenyl) borate and methyl (tetradecyl) -ammonium tetrakis (pentafluorophenyl) borate or mixtures including the same. Such mixtures include protonated ammonium cations derived from amine comprising two C14, C16 or C18 alkyl groups and a methyl group. Said amines are available from Witco Copr., Under the tradename Kemamine ™ T9701 and from Akzo-Nobel under the trade name Armeen ™ M2HT. Another suitable ammonium salt, especially for use in heterogeneous catalyst systems, is formed by reaction of an organometal compound, especially a tri (C 1-6 alkyloxy) aluminum compound with an ammonium salt of a hydroxyaryltris compound (fluoroaryl) )borate. The resulting compound is an organometaloxyaryltris (fluoroaryl) borate compound which is generally insoluble in aliphatic liquids. Typically, said compounds are advantageously precipitated in the present airgel materials to form a supported cocatalyst mixture. Examples of suitable compounds include the reaction product of a tri (C 1 .6) aluminum compound with the ammonium salt of hydroxyapltris (apl) borate. Borates of hydroxyaryltris (aryl) include ammonium salts, especially the above long chain alkyl ammonium salts of: (4-dimethylaluminumoxy-1-phenyl) tris (pentafluorophenyl) borate, (4-dimetilaluminumoxi-3,5-di (trimethylsilyl) -1-phen yl) tps (pentaf luorof in i I) borate, (4-dimetilaluminumoxi-3,5-di (t-butyl) -1-phenyl) tris (pentafluorophenyl) borate, (4-dimetilaluminumoxi-1-benzyl) tris (pentafluorophenyl) borate, (4-dimetilaluminumoxi-3-methyl-1-phenyl) tris (pentaf luorofenil) borate, (4-tetrafluoro-1- dimetilaluminumoxi- phenyl) tris (pentafluorophenyl) borate, (5-dimetilaluminumoxi-2-naphthyl) tris (pentafluorophenyl) borate, 4- (4-dimetilaluminumoxi-1-phenyl) phenyltris (pentafluorophenyl) borate, 4- (2- (4- (dimetilaluminumoxifenil ) propane-2yl) phenyloxy) tris (pentafluorophenyl) borate, (4-dietilaluminumoxi-1-phenyl) tris (pentafluorophenyl) borate, (4-dietilaluminumoxi-3,5-di (trimethylsilyl) -1-phenyl) tris ( pentafluorophenyl) borate, (4-dietilaluminumoxi-3,5-di (t-butyl) -1-f il) tris (pentaf I uorof in i I) borate, (4-DIETI lal um in umoxi- 1 - be nci I) tris (pentaf luorofenil) borate, (4-dietilaluminumoxi-3-methyl-1-phenyl) tris (pentafluorophenyl) borate, (4-di etilaluminumoxi-tetrafluoro-1-phenyl) tris ( pentafluorophenyl) (5-diethylaluminumoxy-2-naphthyl) tris (pentafluorophenyl) borate, 4- (4-diethylaluminumoxy-1-phenyl) phenyltris (pentafluorophenyl) borate, 4- (2- (4- (diethylaluminumoxyphenyl) propane-2-yl) phenyloxy ) tris (pentafluorophenyl) borate, (4-diisopropylaluminumoxy-1-phenyl) tris (pentaf luorophenyl) borate, (4-diisopropylaluminumoxy-3,5-di (trimethylsilyl) -1-phenyl) tris (pentafluorophenyl) borate, (4-) diisopriolaluminumoxy-3,5-di (t-butyl) -1-phenyl) tris (pentafluorophenyl) borate, (4-diisopropylaluminumoxy-1-benzyl) tris (pentafluorophenyl) borate, (4-diisopropylaluminumoxy-3-methyl-1-phenyl) tris (pentafluorophenyl) borate, (4-diisopropylaluminumoxy-tetrafluoro-1-phenyl) tris (pentafluorophenyl) borate, (5-diisopropylamino-2-naphthyl) tris (pentafluorophenyl) borate, 4- (4-diisopropylaluminumoxy-1-phenyl) phenyltris (pentafluorophenyl) borate , and il) phenyloxy) tris (pentaflurophenyl) borate. An especially preferred ammonium compound is (4-diethylaluminumoxy-1-phenyl) tris (pentafluorophenyl) borate methylditetradecylammonium, (4-diethylaluminumoxy-1-phenyl) tris (pentafluorophenyl) borate methyldihexadecylammonium, (4-diethylaluminumoxy-1-phenyl) tris (pentafluoropheni I) methyldioctadecyl ammonium borate, and mixtures thereof. The above complexes are described in WO96 / 28480, which is equivalent to USSN 08 / 610,647, filed March 4, 1996 and in USSN 08 / 768,518, filed December 18, 1996. Another ion formation activating cocatalyst comprises a salt of a cationic oxidation agent and a non-coordinating compatible anion represented by the formula: (Ox8 +) d (A'd-) e, wherein Ox + is a cationic oxidizing agent having a charge of +; d and e are integers from 1 to 3; and A, d "is an anion which is not charge coordinating d 'Examples of cationic oxidation agents include: ferrocenium, hydrocarbyl substituted ferrocenium, Ag + or PbA The preferred embodiments of A, d" are those anions previously defined with with respect to activation cocatalysts containing Bronsted acid, especially tetrakis (pentafluorophenyl) borate. Other suitable ion formation activating cocatalysts comprise a compound which is a one-carbon salt and a non-coordinating compatible anion represented by the formula: wherein A + is an ion carbenium of C1-20; and A '"is a compatible anion that is not coordinating and has a charge of -1. A preferred carbenium ion is the trifluoride cation, which is triphenylimethylthio. An additional, suitable ion formation activating cocatalyst comprises a compound which is a salt of a silyl ion and a non-coordinating compatible anion represented by the formula: R3Si (X ') A'-wherein: R is C1-10 hydrocarbyl; X 'is hydrogen or R; and A '"is as previously defined The preferred silyl salt activating cocatalysts are trimethylsilyl tetrakispentafluorophenylborate, triethylsilyl tetrakispentafluorophenyl tertiary and substituted ether adducts thereof Silyl salts have been previously described generically. Chem. Soc. Chem. Comm., 1993, 383-384, as well as Lambert, JB, et al., Orqanometallics, 1994, 13, 2430-2443.The use of silyl salts as activating cocatalysts for polymerization catalysts by Additions are claimed in US-A-5,625,087 Certain complexes of alcohols, mercaptans, silanols and oximes with tris (pentafluorophenyl) borane are also effective catalyst activators and can be used in accordance with the present invention. A-5, 296, 433. The molar ratio of metal complexes / cocatalysts, if a cocatalyst is used, preferably ranges from 1: 10,000 to 10: 1, more preferred. from 1: 5000 to 10: 1, more preferably from 1: 1000 to 1: 1. When used in alumoxane by itself as an activating cocatalyst, it is preferably employed in a large molar ratio, generally at least 100 times the amount of the metal complex on a molar basis of. tris (pentafluorophenyl) borane when used as an activating cocatalyst is preferably employed in a molar ratio with the metal complex of 0.5: 1 to 10: 1, more preferably from 1: 1 to 6: 1, even more preferably from 1: 1 to 5: 1. The remaining activating cocatalysts are generally preferably used in approximately an equimolar amount with the metal complex. The catalysts can be used to polymerize ethylenically and / or acetylenically unsaturated monomers having from 2 to 100,000 carbon atoms either alone or in combination. Preferred monomers include the C2-20 α-olefins, especially ethylene, propylene, isobutylene, 1-butene, 1-pentene, 1-hexene, 3-methyl-1-pentene, 4-methyl-1-pentene, 1- octene, 1-decene, long chain macromolecular α-olefins and mixtures thereof. Other preferred monomers include styrene, styrene substituted with C 1-4 alkyl, tetrafluoroethylene, vinylbenzocyclobutane, ethylidenedronbornene, 1,4-hexadiene, 1,7-octaidene, vinylcyclohexane, 4-vinylcyclohexene, divinylbenzene and mixtures thereof with ethylene. The long chain macromolecular α-olefins are vinyl terminated polymeric remnants formed in situ during the continuous solution polymerization reactions. Under suitable processing conditions, such long chain macromolecular units are readily polymerized in the polymer product together with ethylene and other short chain olefin monomers to give small amounts of long chain branching in the resulting polymer. More preferably, the current supported catalysts are used in the polymerization of propylene to prepare polypropylene having a high degree of isotacticity. The preferred isotactic polypropylene polymers using the supported supported catalysts have an isoctacticity as measured by 13 C NMR spectroscopy of at least 80 percent, preferably at least 90 percent and more preferably at least 95 percent. In general, polymerization can be achieved under conditions well known in the prior art of Ziegler-Natta or Kaminsky-Sinn type polymerization reactions, at temperatures of 0-250 ° C and pressures of atmospheric to 1000 atmospheres (0.1 to 1000 MPa). The grout or gaseous phase process conditions are more convenient. The supports are preferably employed in an amount to provide a weight ratio of catalysts (based on metal): support from 1: 100,000 to 1:10, more preferably from 1: 50,000 to 1:20 and more preferably from 1: 10,000 to 1:30 Suitable gas phase reactions may use condensation of the monomer or monomers used in the reaction, or of an inert diluent to remove heat from the reactor. In most polymerization reactions the molar ratio of catalyzed polymerizable compounds used is 10"12: 1 to 10" 1: 1, more preferably 10"12: 1 to 1 O" 5: 1. Suitable diluents for polymerization via a process of grout are inert non-coordinated liquids. Examples which 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; perfluorinated hydrocarbons such as perfluorinated C-α alkanes and aromatic and alkyl substituted aromatics such as benzene, toluene and xylene. Suitable diluents also include liquid olefins which can act as monomers or comonomers including ethylene, propylene, 1-butene, butadiene, cyclopentene, 1-hexene, 3-methyl-1-pentane, 4-methyl-1-pentene, 1,4-hexadiene, 1,7-octadiene, 1-octene, 1-decene, styrene, divinylbenzene, ethylidenedronbornene, allylbenzene, vinyltoluene (including all isomers alone or as a mixture), 4-vinylcyclohexene and vinylcyclohexane. Mixtures of the above are also suitable. The catalysts can also be used in combination with at least one additional homogeneous or heterogeneous polymerization catalyst in the same reactors or separately, connected in series or in parallel to prepare mixtures of polymers having desired properties. Advantageously present catalyst compositions are employed in a process for preparing propylene homopolymers, random block copolymers of propylene, and an olefin selected from the group consisting of ethylene, C 4 -α olefins, and C 4 -dienes. 0 and random terpolymers of propylene and olefins selected from the group consisting of ethylene and C4-10 olefins. C-10 olefins include linear or branched olefins such as, for example, 1-butene, isobutylene, 1-pentene, 3-methyl-1-butene, 1-hexene, 3,4-dimethyl-1-butene , 1-heptene, and 3-methyl-1-hexene. Examples of C4.10 dienes include 1,3-butadiene, 1,4-pentadiene, isoprene, 1,5-hexadiene and 2,3-dimethyl-1,3-hexadiene. Preferred polypropylene products have a molecular weight (Mp) of at least 10,000, more preferably at least 50,000 and even more preferably at least 100,000 and a molecular weight and distribution, Mp / Mn less than 6.0, more preferably less than 4.0 and more preferably less than 2.5. The polymerization is generally carried out under continuous or semi-continuous slurry polymerization conditions in hydrocarbon diluents such as propylene, propane, butene, butene-2, isobutane, hexane, heptane and mixtures thereof, generally at temperatures of 50 to 100. ° C and pressures from atmospheric to 1MPa. The polymerization can be carried out in one or more tubular tank reactors with continuous agitation or fluidized bed reactors, or gas phase reactors, or both, connected in series or in parallel. The condensed monomer or solvents can be added to the gas phase reactor as is well known in the art. The supported catalyst can also be prepolymerized before being used as previously described. In a continuous reaction system, the reaction mixture is normally maintained at conditions at which the polymer is produced as a slurry of powder in the reaction mixture. The use of highly active and highly stereospecific catalyst systems in propylene polymerization substantially eliminates the need to remove catalyst or atactic polymer components from the polymer product. The mixture of the reaction components is fed continuously or at frequent intervals into the reactor system and continuously monitored so as to ensure an efficient reaction of the desired product. For example, it is well known that supported coordination catalysts and catalyst systems of the type described above are highly sensitive, to varying degrees, to catalyze contaminants such as water, oxygen, carbon oxides, acetylenic compounds and sulfur compounds. The introduction of said compounds can result in the calibration of the reactor and the production of secondary grade product. Normally, computer control systems are used to keep process variables within acceptable limits, often by measuring polymer variables such as viscosity, density and tacticity or catalyst productivity. In the process, reagents and diluents, which may be a mixture of propylene, hydrogen, nitrogen, unreacted comonomers and inert hydrocarbons, are continuously recycled into the reactor, optionally with sweeping to remove impurities and condensation to remove the polymerization heat. The catalysts and cocatalysts, fresh monomers or comonomers and selectivity control agents, branching agents or chain transfer agents, if desired, are likewise continuously fed to the reactor. The polymer product is removed continuously or semi-continuously and the volatile components are removed and recycled. Suitable processes for preparing polypropylene polymers are known in the art and are illustrated by those taught in US-A-4,767,735, US-A-4, 975,403, and US-A-5,084,513, among others. Using the catalysts of the present invention, copolymers having a high comonomer incorporation and correspondingly low density, still having a low melt index, can be easily prepared. Additionally, high molecular weight polymers are easily obtained by using the present catalysts, even at elevated reactor temperatures. This result is highly convenient since the molecular weight of the α-olefin copolymers can be easily reduced by the use of hydrogen or similar chain transfer agent, however, the molecular weight increase of the α-olefin copolymers usually only it is obtained by reducing the polymerization temperature of the reactor. As a disadvantage, the operation of a polymerization reactor at reduced temperatures significantly increases the operating cost since the heat must be removed from the reactor to maintain the reduced reaction temperature, while, at the same time, heat must be added to the effluent of the reactor. reactor to vaporize the solvent. In addition, productivity increases due to improved solubility of the polymer, decreased solution viscosity and higher polymer concentration. Using the present catalysts, α-olefin hopolymers and copolymers having densities of 0.85 g / cm 3 to 0.96 g / cm 3 and melt flow rates of 0.0001 to 10.0 dg / min, are easily obtained in a process at high temperatures. The catalysts of the present invention are particularly advantageous for the production of ethylene homopolymers and ethylene / α-olefin copolymers having high levels of long chain branching. The use of the catalysts of the present invention in the continuous polymerization processes, especially the continuous solution polymerization processes, allows high reactor temperatures that favor the formation of vinyl-terminated polymer chains that can be incorporated into a polymer of growth, thus giving a long chain branching. The use of the catalyst systems herein advantageously allows the economical production of ethylene / α-olefin copolymers having processability similar to low density polyethylene produced by free radicals at high pressures. The supported catalysts present can be advantageously employed to prepare olefin polymers having improved processing properties by polymerizing ethylene alone or mixtures of ethylene / α-olefin with low levels of diene that induces "H" branches, 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 advantageously allows economical production of polymers having excellent physical properties and processability. Preferably said polymers comprise ethylene, an α-olefin of C3-20 and a branching comonomer in "H". The supported catalysts present are also suitable for the preparation of EP and EPDM copolymers with high yield and productivity. The process preferably employed is a slurry process such as that described in US-A-5,229,478. In general terms, it is convenient to produce EP and EPDM elastomers under conditions of increased reactivity of the diene monomer component. The reason for this is explained in the '478 Patent identified before as follows, which still remains real despite the advances obtained in said reference, a main factor that affects the production costs and, therefore, the usefulness EPDM is the cost of diene monomer. The dihene is a more expensive monomer material than ethylene or propylene. In addition, the reactivity of diene monomers with the metallocene catalysts previously known is lower than that of ethylene and propylene. Consequently, to achieve the required degree of diene incorporation to produce EPDM with an acceptably fast curing regime, it has been necessary to use a diene monomer concentration, which, expressed as a percentage of the total concentration of the monomers present, is in a substantial excess compared to the percentage of the desired diene that has been incorporated into the final EPDM product. Since substantial amounts of unreacted diene monomer should be recovered from the polymerization reactor tributary for recycling, the production cost is unnecessarily increased. In addition to the increased cost of producing an EPDM, there 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 required level of diene incorporation in the The final EPDM product often reduces the rate or activity at which the catalyst causes the polymerization of 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 advantageously allows the increased reactivity of the diene, thus preparing EPDM polymers with high yield and productivity. Additionally, the supported catalysts of the present invention achieve economical production of EPDM polymers with diene contents of up to 20 weight percent or higher, which polymers have highly convenient rapid cure rates. The non-conjugated diene monomer can be a straight chain, branched chain or cyclic hydrocarbon diene having from 6 to 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-1,6-octadiene; 3,7-dimethyl-1, 7-octadiene and mixed isomers of dihydromyricenne and dihydroocinene; dienes to single-ring icicles such as 1,3-cyclopentadiene; 1,4-cyclohexadiene, 1,5-cyclooctadiene and 1,5-cyclododecadiene; and fused ring alicyclic dienes with multiple rings such as tetrahydroindene, tetrahindroindene methyl, dicyclopentadiene; bicyclo- (2,2, 1) -hepta-2,5-diene; alkenyl, alkylidene, cycloalkenyl norbornenes and cycloalkylidene such as 5-methylene-2-norbornene (MNB); 5-propenyl-2-norbornene, 5-propiopropylidene-2-norbornene, 5- (4-cyclopentenyl) -2-norbornene, 5-cyclohexylidene-2-norbornene, 5-vinyl-2-norbornene and norbornadiene.

Of the dienes normally used to prepare EPDM, 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 dicilopentadiene (DCPD). Especially preferred dienes are 5-ethylidene-2-norbornene (ENB) and 1,4-hexadiene (HD). Preferred EPDM elastomers can contain from 20 to 90 percent ethylene, more preferably from 30 to 85 percent by weight of ethylene, more preferably from 35 to 80 percent by weight of ethylene. The alpha-olefins suitable for use in the preparation of elastomers with ethylene and dienes are preferably C3.16 alpha-olefins. Illustrative non-limiting examples of the alpha-olefins are propylene, 1-butene, 1-pentene, 1-hexene, 1-octene, 1-decene and 1-dodecene. Alpha-olefins are generally incorporated in the EPDM polymer at 10 to 80 weight percent, more preferably 20 to 65 weight percent. Non-conjugated dienes are generally incorporated in the EPDM at 0.5 to 20 weight percent; more preferably from 1 to 15 weight percent and even more preferably from 3 to 12 weight percent. If desired, more than one diene may be incorporated simultaneously, for example HD and ENB, with total diene incorporation within the limits specified above.

At all times, the individual ingredients as well as the catalyst components must be protected from oxygen and moisture. Therefore, the components of catalysts and catalysts must 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. The ethylene is generally added to the reaction vessel in an amount to maintain a differential pressure in excess of the combined vapor pressure of the α-olefin and diene monomers. The ethylene content of the polymer was determined by the differential pressure ratio of ethylene to the total reactor pressure. Generally the polymerization process was carried out with an ethylene differential pressure of 70 to 7000 kPa, more preferably 30 to 300 kPa. The polymerization was generally carried out at a temperature of 25 to 200 ° C, preferably 75 to 170 ° C and even more preferably greater than 95 to 140 ° C. The polymerization can be carried out in the form of batches or in a continuous polymerization process. A continuous process is preferred, in which case the supported catalysts, ethylene, α-olefin, and optionally diluent and diene, are continuously supplied to the reaction zone and the polymer product is continuously removed from it. The supported catalysts of the present may also be employed to have an advantage in the gas phase polymerization of olefins. The gaseous phase processes for the polymerization of olefins, especially the copolymerization 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-1- Pentene, are well known in the cooling provided by the cooled recycled gas, is to feed a volatile liquid to the bed to provide an evaporative cooling effect. The volatile liquid used in this case can be, for example, a volatile inert liquid, for example, a saturated hydrocarbon having from 3 to 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 fed to the bed to provide an evaporative cooling effect. Examples of olefin monomers that can be used in this form are olefins containing from 3 to 8, preferably from 4 to 6 carbon atoms. The volatile liquid evaporates in the hot fluidized bed to form gas that mixes with the fluidizing gas. If the volatile liquid is a monomer or comonomer, will undergo polymerization in the bed. The evaporated liquid then emerges from the reactor as part of hot recycled gas and enters the compression / heat exchange part of the recycling cycle. The recycled gas is cooled in the heat intercavity and if the temperature at which the gas cools is below the dew point, the liquid will precipitate out of the gas. This liquid is conveniently recycled continuously to the fluidized bed. It is possible to recycle the precipitated liquid to the bed as liquid droplets carried in the stream of recycled gas. This type of pss was described, for example in EP 89691; US-A-4,543,399; WO 94/25495 and US-A-5,352,749. A particularly preferred method for recycling the liquid to the bed is to separate the liquid from the recycle gas stream and re-inject it directly into the bed, preferably using a method that generates fine droplets of the liquid within the bed. This type of process was described in WO 94/28032. The polymerization reaction that occurs in the gas fluidized bed is catalyzed by the continuous or semi-continuous addition of catalyst. Said catalyst can be prepolymerized as described above, if desired. The polymer is produced directly in the fluidized bed by catalyzed copolymerization of the monomer and one or more comonomers of the fluidized particles of supported catalysts within the bed. The start of the polymerization reaction was achieved using the bed of preformed polymer particles, which are preferably similar to the white polyolefin. These processes are commercially used on a large scale for the manufacture of high density polyethylene (HPDE), medium density polyethylene (MDPE), linear low density polyethylene (LLDPE). English) and polypropylene.

The gaseous phase process employed can be, for example, of the type employing a mechanically stirred bed or a fluidised gas bed as the polymerization of the reaction zone. The process is preferred in which the polymerization reaction is carried out in a vertical cylindrical polymerization reactor containing a fluidized bed of polymer particles supported above a perforated plate in the fluidization grid by a flow of fluidizing gas. The gas used to fluidize the bed comprises the monomer or monomers that will be polymerized, and also serves as a heat exchange medium to remove the heat of reaction from the bed. Hot gases emerge from the upper part of the reactor, usually via a tranquilization zone, also known as a velocity reduction zone, which has a wider diameter of the fluidized bed and where the particles introduced into the gas stream have a opportunity to return by gravity to the bed, it may also be advantageous to use a cyclone to remove ultrafine particles from the hot gas stream. The gas is normally recycled to the bed by means of a blower or compressor and one or more heat exchangers to separate the gas from the heat of the polymerization. A preferred method of cooling the bed involves the use of a condensed liquid which evaporates in the reactor removing the heat from it. Said condensation agent is generally recondensed and recycled together with the unreacted monomers. The monomers and any other liquids or gases that are desired to be charged to the reactor, such as, for example, a diluent gas or hydrogen chain transfer agent, conveniently are vigorously dried and purified before use. Suitably, said materials may be contacted with beds of alumina or zeolite or purified in some manner before use. The gas phase processes suitable for the practice of this invention are preferably continuous processes that provide the continuous supply of reactants to the reaction zone of the reactor and the removal of products from the reaction zone of the reactor, thus providing a stateful environment. stable on a macro scale in the reaction zone of the reactor. The produced polymer is discharged continuously or discontinuously from the fluidized bed as desired. Normally, the fluidized bed of the gas phase process is operated at temperatures greater than 50 ° C, preferably 60 ° C to 110 ° C, more preferably 70 ° C to 110 ° C. Normally, the molar ratio of comonomer to monomer used in the polymerization depends on the density desired for the composition that is being produced and is 0.5 or less. Conveniently, when materials with a density scale of 0.91 to 0.93 are produced, the ratio of comonomer to monomer is less than 0.2, preferably less than 0.05, even more preferably less than 0.02 and may even be less than 0.01. In addition, normally the ratio of hydrogen to monomer is less than 0.5, preferably less than 0.2, more preferably less than 0.05, even more preferably less than 0.02 and may even be less than 0.01. The scales described before process variables are appropriate 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 the gas phase processes that can be adapted for use in the process of this invention, particularly, US-A-4,588,790; US-A-4,543,399 US-A-5,352,749 US-A-5,436,304 US-A-5,405,922; US-A-5,462, 999 US-A-5,461,123 US-A-5,453,471 US-A-5,032,562; US-A-5,028,670 US-A-5,473,028 US-A-5,106,804 US-A-5,541,270 and applications EP 659,773; 692,500; and PCT Applications WO 94/29032, WO 94/25497, WO 94/25495, WO 94/28032, WO 95/13305; WO 94/26793 and WO 95/07942. Examples The experts will appreciate that the invention described herein can be practiced in the absence of any component that has not been specifically described. The following examples are provided as an additional illustration of the invention and should not be construed as limiting. Unless otherwise stated, all parts and percentages are expressed on a weight basis. All the syntheses of air or water sensitive compounds were carried out under a nitrogen or argon atmosphere using a combination of glove box and high vacuum techniques. The solvents were purified by passing through double columns loaded with activated alumina and a supported metal catalyst (Q-5® available from Englehardt Chemical Company). The term "during the night" if used, refers to a time of approximately 16-18 hours. The term "room temperature", if used, refers to a temperature of 20-25 ° C. Example 1 Synthesis of silicate-magnesium airgel with exchanged ammonium ions 112 g of NH4NO3 were dissolved in 1.8 L of deionized water in 2 L Erlenmeyer flask at room temperature under magnetic stirring, after which 40 g of montmorillonite clay ( I) were added to the prepared solution. The resulting clay slurry was heated to 80 ° C and maintained at this temperature for 2 hours, then recovered by centrifugation and filtration. The clay solid with exchanged ions (II) recovered afterwards was redispersed in 1 liter of deionized water to disperse a homogeneous dispersion using ultrasound (550 Sonic Dismembrator, Fisher Scientific, Power Calibration from 9 to 30 minutes). The homogeneous dispersion was divided into four aliquots in 1 liter round bottom flasks and frozen with liquid nitrogen while rotating the flasks. The water was removed under vacuum (Labconco 8 Freeze Dryer, 2 days) to produce aluminum-magnesium silicate airgel with exchanged ions (III). The volume density was 0.005 g / cm3. Example 2 Synthesis of aluminum-magnesium silicate airgel with exchanged ammonium ions, calcined. The aluminum-magnesium silicate airgel with exchanged ions of Example 1 was heated in a high temperature oven at 500 ° C for 6 hours under nitrogen to give an aluminum-magnesium silicate airgel with exchanged ions, calcined (IV), which has a volume density of 0.004g / cm3. The residual water content was less than 0.1 percent by weight. Example 3 Synthesis of aluminum-magnesium silicate airgel calcined with exchanged anilinium ions. 0.5 g of the calcined solid (IV) of Example 2 were dispersed in 100 ml of toluene under magnetic stirring for 1 hour resulting in a homogeneous suspension. 20 ml of 99.5 percent dimethianiline (Aldrich Chemical Company, Inc.) were added to the homogenized suspension. The resulting suspension was stirred continuously overnight at room temperature in a water box. By filtration and solvent removal (room temperature 1 x 10"5 Torr for 24 hours), an aluminum-magnesium silicate airgel was recovered, calcined with exchanged anilinium ions (V) .The volume density was 0.004 g / l. cm3 Example 4 Synthesis of aluminum-magnesium silicate airgel calcined with exchanged ions of chemically modified anilinium 250 mg of aluminum-magnesium silicate airgel, calcined with exchanged ions (V) of example 3 were dispersed in 150 ml of toluene dry, to give an airgel slurry in homogeneous toluene.This slurry was mixed with 0.6 g of 100 percent tripropylaluminum and stirred for one hour.Filtering and removing the solvent (room temperature 1 x 10"5 Torr for 24 hours) ), the aluminum-magnesium silicate airgel was recovered, calcined, with exchanged anilinium ions being chemically modified (VI). The volume density was 0.004 g / cm3. Example 5 Synthesis of supported catalyst To a toluene slurry of aluminum-magnesium silicate airgel, calcined from exchanged anilinium ions, chemically modified (VI) of Example 4 (250 mg) was added 1 mL of 0.0025 toluene solution. M of dimethylsilyl bis (2-methyl-4-phenylinden-1-yl) zirconium 1,4-diphen-1, 3-butadiene. The solvent was removed under reduced pressure to form a supported polymerization catalyst (VII). Polymerization of Propylene. The supported catalyst (Vil) of Example 5 was slurried in toluene (5 ml) and added to a stirred 2 liter jacketed stainless steel reactor under an argon atmosphere containing 1 liter of hexane. The reactor was charged with 70 kPa of propylene gas and heated to 75 ° C for 3 hours with propylene being supplied on demand. After the reactor was vented and the reaction mixture was stirred and filtered to remove the crystalline polymer. After drying under reduced pressure at 120 ° C, 40 g of isotactic propylene was recovered. The yield is 1 kg / mg zirconium. The isoctacticity measured by 13 C NMR was 97 percent. Example 6 Synthesis of silylated aluminum-magnesium silicate airgel 40 g of montmorillonite clay (I) were added to 1 liter of deionized water in a 2 liter round bottom flask. The resulting clay slurry was charged at 80 ° C and kept at this temperature for 2 hours and then separated by centrifugation at 2000 rpm for 60 minutes. The lamellar gel contained in the supernatant was divided into four aliquots in 1 liter round bottom flasks and frozen with liquid nitrogen. The water was removed under vacuum (Labconco Freeze 8 Dryer, 2 days). After the complete removal of water vapor, a flabby lamellar airgel (Vil) was obtained, (density 0.04 g / cc). To a 1 liter of hexane was added 5 g of the dry layered airgel with mechanical agitation at room temperature. After uniform dispersion of the airgel, 47 g of trimethylchlorosilane were added dropwise with vigorous stirring for 15 minutes. The resulting mixture was refluxed for two hours, centrifuged and decanted to recover the silylated laminar airgel. The airgel material was washed three times by resuspending in 500 ml of hexane, centrifuging and decanting. The washed material was then removed by vacuum to remove the organic and inorganic volatiles in a water bath at 50 ° C. The separation by vacuum was continued for several hours. The dried, silylated airgel was then suspended in 500 ml of 1M HCl with vigorous stirring for 2 hours, centrifuged, washed and resuspended in 500 ml of water. The suspension was then dried by freezing to form a silylated sheet airgel, treated with acid (density 0.05 g / cc). To 150 ml of toluene 0.125 g was added to the layered airgel, silylated, treated with acid with stirring. The resulting slurry was mixed with 0.3 ml of 1M tripropylaluminum solution and 0.5 ml of 2.5 μM of 1,4-dimethyl-1,3-butadiene toluene solution of dimethylsilane bis (2, methyl-4-phenylinden-1- il) zirconium to form an active polymerization catalyst. The catalyst slurry in an argon atmosphere is connected to a 70 kPa propylene gas stream at 70 ° C for 1 hour. 17.4 g of isotactic polypropylene of high molecular weight were obtained. Example 7 10 g of purified montmorillonite was dispersed in 1000 ml of a 1M HCl solution at ambient conditions for 12 hours in an Erlenmeyer flask. The slurry was filtered to recover a clay gel treated with HCl. The montmorillonite with ion exchange was washed once by resuspension in 500 ml of deionized water for 30 minutes, and recovered by filtration. The montmoriionite cake with ion exchange recovered was then frozen in liquid nitrogen, either directly or after resuspending in 500 ml of deionized water and then freeze dried in a Labconco 8 freeze dryer. A very fluffy layered airgel was obtained after the water was removed by freeze drying. The layered airgel sample was removed from the dryer by freezing, transferred to a narrow neck flask and placed in a high vacuum line and exposed to a high vacuum for 24 hours at room temperature. The same method was also used to form aluminum-magnesium silicate aerogels of hectorite clays (Optigel®, available from Sud Chemie AG), laponite and fluoromica. 0.125 g of the aluminum-magnesium silicate airgel treated with the above acid were dispersed in 150 ml of toluene to form a slurry, 0.3 ml of a 1M solution of tripropylaluminium and then 0.5 ml of a 2.5 μM solution of 1,4-diphenylbutadiene from bis (2-methyl-4-phenylinden-1-yl) zirconium were added to the slurry under an argon atmosphere at room temperature. The slurry was then exposed to propylene at 700 ° C at 70 kPa for one hour. 14.5 g of isotactic polypropylene were produced. Example 8 5 g of silylated sheet airgel from Example 6 were added to 600 ml of deionized water under magnetic stirring at room temperature overnight. Centrifugation of the slurry at 2000 RPM for 1 hour was used to discard the precipitate in the bottom of the vessel. The acidic ion exchange resin (Dowex HCRS) was then gradually introduced into the supernatant until the pH of the slurry reached 2-3. The mixture was further stirred magnetically for 2 hours at room temperature before decanting the liquid to remove the solid acid resin. The recovered liquid was quickly cooled with liquid nitrogen, then dried inside a Labconco 8 Freezing Dryer. A very fluffy laminar airgel (density 0.05g / cc) was obtained after the water was removed by freeze drying. The layered airgel sample was removed from the dryer by freezing, transferred to a narrow neck flask, placed on a high vacuum line and exposed to a high vacuum for 24 hours at room temperature. 0.250 g of the protonated, protonated silane airgel, above, was dispersed in 150 ml of toluene to form a slurry. 0.6 ml of a solution of 1M tripopylaluminium and 1.0 ml of 2.5 μM solution of 1,4-dimethylisobutadiene of dimethyl silane bis (2-methyl-4-phenylinden-1-yl) zirconium were added to the slurry at room temperature under a argon atmosphere. The slurry was then exposed to propylene at 700 ° C at 70 kPa for one hour. 17.0 g isotactic polypropylene was produced. Example 9 Preparation of agglomerated aluminum-magnesium silicate airgel In a 500 ml flask, 8 g of the layered airgel (Vl) of Example 6 were added to 1000 ml of deionized water with stirring at room temperature. After uniform dispersion, 16 g of a 40 percent solution of potassium silicate and 12 g of formamide and an additional 100 ml of deionized water were added sequentially to the slurry. The resulting slurry was added to a dispersion of 500 ml of o-dichlorobenzene containing 5 g of cetyltrimethylammonium bromide and 2 g of a finely divided silica having particle sizes in the range of 20-30 nm. By stirring at 300 rpm for ten minutes, a uniform water-in-oil emulsion was formed. Stirring was continued for 30 minutes at 90 ° C and the emulsion was then diluted with 500 ml of acetone and the resulting solid spheroidal particles were isolated by filtration. The agglomerated laminar airgel was treated with 500 ml of 1M aqueous hydrochloric acid overnight with stirring, separated and dried by air. The material was then molded into smaller particles using a ball mill and calcined at 540 ° C for 24 hours. In a glove box, at room temperature for a period of two hours, a solution of 30 ml of toluene and 15 ml of a solution of 1 M hexane of triethyl aluminum was added to 1.5 g of the above agglomerated laminar airgel. The resulting product was washed with toluene and recovered after vacuum drying. The lamellar, agglomerated, dried airgel was then added to 30 ml of a toluene solution of 1.25 μM 1,4-dimethylbutadiene dimethyl silane bis (2-methyl-4-phenylinden-1-yl) zirconium. After mixing for 30 minutes at room temperature, the resulting solid was separated, washed with toluene and dried under vacuum overnight, thereby forming a supported agglomerated polymerization catalyst having a density of 5 g / cc and a surface area of 500 M2 / g. 11 mg of the catalyst and 6 g of the liquid propylene were sealed in an autoclave reactor and heated at 70 ° C for one hour. 1.2 g of isotactic polypropylene was recovered. Example 10 Preparation of lamellar airgel with ammonium ion exchange In an Erlenmeyer flask, 6 g of hectorite (Laponite RD, Southern Ciar Product, Inc.) were dispersed in 500 mL of deionized water (pH about 5) containing 2 g of water. N, N, -dimethylaniline chloride and was kept overnight at room temperature. The slurry was filtered to give Laponite RD with ion exchange. Laponite RD with ion exchange was washed once by resuspension in 500 mL of deionized water for 30 minutes and then recovered by filtration. The recovered filter cake was resuspended in 500 mL of deionized water and dried by freezing as described in Example 1. A very fluffy layered airgel was obtained with a light blue color. EXAMPLE 11 Preparation of silylated layered airgel with exchanged ammonium ion A 2 liter round bottom flask was charged with 40 g of montmorillonite (University of Missouri, Swy-1, Crook County, Wyoming, USA).; or montmorillonite purified by CWC Lot # PC-054-98 of Nanocor) and 1 liter of deionized water. With magnetic stirring or sound treatment, the temperature of the slurry was raised to 80 ° C and then maintained at that temperature for 2 hours. The resulting gel-like slurry was subjected to centrifugation for 60 minutes at 2000 RPM and filtered. The filtered layered silicate suspension was freeze-dried substantially according to the procedure of Example 1. A flask was charged with 5 g of freeze-dried montmorillonite layered airgel prepared as described above, and formed in 1 liter of hexane. at room temperature with mechanical agitation. From an addition funnel, 47 g of chlorotrimethylsilane (Aldrich) was ded into the slurry for a period of 15 minutes. The system was heated to reflux for 2 hours. The product was centrifuged and the liquid was decanted to recover the silylated laminar airgel material. This product was washed three times by resuspending in 500 mL of hexane, centrifuging and decanting. The washed lamellar airgel product was then transferred to a 1 liter flask and the volatiles were removed by rotovaporation under a vacuum pump in a water bath at a temperature of 50 ° C. The dried silylated layered airgel solid was further treated under vacuum (10"2 torr) for several hours and then recovered.

The silylated laminar airgel was transferred to a 1 liter Erlenmeyer flask and suspended in 500 mL of deionized water with vigorous stirring. To this suspension, 2.0 g of N, N-dimethylanilinium chloride was added and the slurry was filtered openly to the laboratory atmosphere overnight. The lamellar airgel with exchanged ammonium ions was then recovered by filtration, washed once by resuspending in 500 mL of fresh deionized water and recovered by filtration. The layered airgel was formed with 100 mL of deionized water in a 500 mL flask and again dried by freezing. The freeze dried product was further treated under vacuum (<10"6 torr) for 18 hours at room temperature Example 12 Preparation of modified fluoromica airgel with ferrocenium salt In a 1 liter Erlenmeyer flask, 10 g of fluoromica (NaMg2.5 (Si4O10) F2 Coop Me-100, <0.2 percent by weight loss below 800 ° C) were dispersed in 600 mL of deionized water at ambient conditions for one hour.The white fluoromica was observed to sponge and It was dispersed in water giving a semi-transparent slurry In a separate flask, 2.5 g of ferrocenium (Aldrich) was added to 20 mL of concentrated sulfuric acid and the resulting mixture was kept under ambient conditions for one hour, producing a dark blue solution. The solution was diluted with 200 mL of deionized water and mixed with fluoromica slurry under magnetic stirring.A large agglomerates of blue color were observed.The mixture was stirred at room temperature for 30 min. cough, then filtered giving a blue gel. The blue gel was washed by resuspension in 800 mL of deionized water for 30 minutes and recovered by filtration. This product was then dispersed in 500 mL of deionized water and dried by freezing. The dry fluoromica laminar airgel was maintained in a high vacuum line (<10"6 torr) at 150 ° C overnight.Polymerization of Homogeneous Solution A stirred 2.0-liter reactor was charged with 740 g of mixed alkane solvent of Isopar-E ™ (available from Exxon Chemical Inc.) and 118 g of 1-octene comonomer Hydrogen was added as a molecular weight control agent by expansion at differential pressure from a 75 ml addition tank at 2070 kPa The reactor was heated to the polymerization temperature of 140 ° C and saturated with ethylene at 3.4 MPa The catalyst ((t-butylamido) dimethyl (tetramethyl-cyclopentadienyl) slanotitanium (II) 1,3-pentadiene) and the layered airgel, 1.0 μmol each, (as solutions of 0.005 M or 0.010 M in toluene) were mixed and transferred to a catalyst addition tank and injected into the reactor.The polymerization conditions were maintained for 15 minutes with ethylene added on demand. The resulting solution was removed from the reactor and 10 ml of toluene solution containing approximately 67 mg of hindered phenol antioxidant (Irganox ™ 1010 from Ciba Geigy Corporation) and 133 mg of a phosphorus stabilizer (Irgafos 168 from Ciba Geigy Corporation) were added. Between the polymerization operations there is a wash cycle in which 850 g of Isopar-E ™ was added to the reactor and the reactor was heated to 150 ° C. The reactor was emptied of the heated solvent immediately before starting a new polymerization operation. The results are contained in Table 1. Table 1 # of airgel μmoles exotherm Redimiento Eficiencia g Laminar operation Cat / Airgel (° C) (g) polymer / μg TI? Example 11 0.25 / 50? 76 22.4 1.87 2 Example 12 0.25 / 50 4.1 110.1 9.20 3 * "0.25 / 12 0.8 73.5 6.14 * In addition to the catalyst and layered airgel, 12.5 μmol of triisopropylaluminum was added to the catalyst formulation, giving a molar ratio of Al / Ti of 50.

Claims

CLAIMS 1. An aluminum-magnesium silicate airgel or fluorinated magnesium silicate airgel that has ion exchange.
2. The airgel of claim 1, which was calcined, chemically modified or functionalized by treatment with a chemical modifying agent, exchanged ions, impregnated, coated with any chemical coating or formed into particles.
3. The airgel of claim 1, which was calcined, was contacted with a chemical modifying agent, treated with a catalyst activating material capable of forming active polymerization catalysts of the group 3-10 metal complexes. and contacted a complex or metal compound of group 3-10.
The airgel of claim 2 or 3, wherein the chemical modifying agent is selected from the group consisting of trihydrocarbylalumino compounds and trihydrocarbylchlorosilane compounds and hydrocarbylsiloxane compounds containing from 3 to 20 atoms that do not include hydrogen.
5. A support material to be used for the preparation of supported catalysts for addition polymerizations comprising an aluminum-magnesium silicate airgel or fluorinated magnesium silicate airgel.
6. The support material of claim 5, in the form of agglomerated particles.
7. The support material of claim 5, wherein the airgel has ions exchanged with a cation selected from the group consisting of H +, conjugated Lewis base acids, reducible Lewis acid cations and reducible metal cations.
The support material of claim 7, wherein the airgel was also calcined, contacted with a functionalizing agent, treated with a catalyst activating material, treated with a reinforcing agent or agglomerated.
9. The support material of any of claims 5-8, which was treated with one or more metal complexes of the group 3-10 so that it deposits the complex on an aluminum-magnesium silicate airgel in an amount of 0.00001 to 1,000 mg / g of support.
10. A process for polymerizing an addition polymerizable monomer comprising contacting the monomer or a mixture comprising the monomer with a composition according to claim 9.
11. The process of claim 10, wherein the ethylene, propylene and optionally one or more comonomers are polymerized.
12. The process of claim 10, which is a gas phase polymerization.
13. The process of claim 10, wherein the process is carried out in a slurry.
14. - An aluminum-magnesium silicate or fluorinated magnesium silicate material, having a volumetric density of 0.5 to 0.0001 g / cm3, which has been subjected to ion exchange.
15. An aluminum-magnesium silicate material or fluorinated magnesium silicate material, according to claim 14, which has been subjected to ion exchange with a cation selected from H +, conjugated acids from Lewis bases, cations reducible Lewis acid and reducible metal cations.