MXPA01002024A - Highly active supported catalyst compositions - Google Patents

Abstract

This invention relates to metallocene catalyst compositions which are highly active for the polymerization of olefins, particularly prochiral&agr;-olefins. The catalyst compositions contain at least one metallocene, and at least one activator and a support that has been fluorided using a fluoride containing compound.

Description

bet SUPPORTING COMPOSITIONS SUPPORTED, HIGHLY ACTIVE Field of the Invention This invention relates generally to supported catalysts, and more particularly, to supported metallocene catalysts, and to methods for their production and use. BACKGROUND Metallocene catalyst systems and their use for olefin polymerization are well known. The metallocene catalysts are single-site, and are differently activated, compared to conventional Ziegler-Natta catalysts. A typical metallocene catalyst system includes a metallocene catalyst, a support, and an activator. By joining or "fixing" the catalyst to the support, the catalyst is generally referred to as a supported catalyst. For many polymerization processes, supported catalysts are required, and different methods for attaching metallocene catalysts to a support are known in the art. Suitable supports for use with the metallocene catalyst are generally porous materials, and may include organic materials, inorganic materials, and inorganic oxides. However, many media contain reactive functionalities. In some cases, these reactive functionalities they can deactivate or reduce the activity of the catalyst fixed to the support. When this occurs, it may be necessary to add more catalyst to the catalyst system to ensure a sufficient polymer production during the olefin polymerization. Increasing the catalyst concentration in the catalyst system to compensate for the reduction in activity caused by the reactive functionalities is generally undesirable for many reasons. For example, in general the addition of more catalyst may also require the addition of more activator. As such, increasing the concentrations of both catalyst and activator to overcome the effects of deactivation of the catalyst by the reactive functionalities, substantially increases the cost of the olefin polymerization. The hydroxyl groups are an example of a reactive functionality present in some supports that deactivate the metallocene catalysts. The hydroxyl groups are present on supports, such as inorganic oxides. An example of an inorganic oxide is silica gel. As such, when silica gel is used to support a metallocene catalyst, it is desirable to remove, reduce, or inactivate a sufficient number of the hydroxyl groups. Methods for removing or reducing hydroxyl groups include thermal and / or chemical treatments. The removal of the hydroxyl groups is known as dehydroxylation. Some examples of the previous treatment of the surface The materials of support include U.S. Patent No. 5,527,867, and European Patents Nos. EP-A-0090374, EP-A-081164, and EP-A-0166157. The heat treatment or heating of the support material generally prevents contamination of the support by undesirable chemicals. However, in the case of many porous supports, such as silica gel, the heating of the support may fail to achieve sufficient dehydroxylation. The chemical treatment of the support material can be expensive, and can result in contamination of the support. Accordingly, there remains a need to increase the activity of the supported metallocene catalyst systems. In a particular way, there remains a need for er supported metallocene catalysts, where the reactive functionalities of the support are reduced and / or deactivated. SUMMARY OF THE INVENTION The present invention provides a supported metallocene catalyst composition. In general, the inventor has discovered that, when at least one metallocene catalyst is bonded to a fluorinated support, the activity of this supported metallocene catalyst composition is higher, compared to the activity of the same metallocene catalyst bonded to a non-metal support. fluorinated These non-fluorinated supports include supports to which fluoride has not been added, or to that a different halide of fluorine has been added. In one embodiment, the supported metallocene catalyzed composition includes a metallocene catalyst and a support composition. The support composition can be represented by the formula: Sup F, where Sup is a support, and F is a fluorine atom bonded to the support. The support composition can be a fluorinated support composition. In another embodiment, the supported metallocene catalyst composition includes a support composition represented by the formula: Sup Ln. "Sup" can also be defined as a support selected from the group that includes talc, clay, silica, alumina, magnesia, zirconia, iron oxides, boria, calcium oxide, zinc oxide, barium oxide, thoria, gel of aluminum phosphate, polyvinyl chloride, and substituted polystyrenes and mixtures thereof. "L" is a first member selected from the group that includes (i) a link, enough to link the F to the His p; (ii) B, Ta, Nb, Ge, Ga, Sn, Si, P, Ti, Mo, Re, or Zr linked to the Sup and F; and (iii) 0 linked to the Sup and linked to the second member selected from the group consisting of B, Ta, Nb, Ge, Ga, Sn, Si, P, Ti, Mo, Re, or Zr, which is linked to F; "F" is a fluorine atom; and "n" is a number from 1 to 7. The support composition can desirably be a fluorinated support composition. The catalyst composition metallocene supported may also include boron, and may also include an activator, such as alkylalumoxane or MAO or haloarilboron, or aluminum compounds. The metallocene catalyst may be represented by the formula: CpraMRnXq, where Cp is a cyclopentadienyl ring, which may be substituted, or a derivative thereof, which may be substituted, M is a transition metal of Group 4, , or 6, R is a hydrocarbyl group or a hydrocarboxyl group having from 1 to 20 carbon atoms, X can be a halide, a hydride, an alkyl group, an alkenyl group, or an arylalkyl group, and m = 1 -3, n = 0-3, q = 0-3, and the sum of m + n + q is equal to the oxidation state of the transition metal. The present invention also provides a method for making the supported metallocene catalyst composition. The method step includes contacting the metallocene catalyst with a support composition, desirably a fluorinated support composition, under suitable conditions and for a sufficient time, where the support composition is represented by the formula Sup L Fn. The support composition, and particularly the fluorinated support composition, can be made by contacting a hydroxyl group containing support material, with at least one inorganic fluoride, under suitable conditions and for a sufficient time, where the fluoride becomes fixed to the support. The present invention also provides a method of olefin polymerization. The steps of the olefin polymerization method include contacting a polymerizable olefin with the supported metallocene catalyst composition under suitable conditions and for a sufficient time. Desirably, the polymerizable material is propylene. The polymerizable olefin can be formed into numerous articles, such as, for example, films, fibers, fabrics, and molded structures. Detailed Description of the Invention This invention relates to metallocene catalyst compositions comprising the reaction product of at least three components: (1) one or more metallocenes; (2) one or more activators; and (3) one or more fluorinated support compositions. As used herein, the phrase "fluorinated support composition" means a support, desirably particulate and porous, that has been treated with at least one compound containing inorganic fluorine. For example, the fluorinated support composition can be a silicon dioxide support, where a portion of the silica hydroxyl groups has been replaced with fluorine or with fluorine-containing compounds. As used herein, the term "support composition" means a support, desirably in particulate and porous, that has been treated with at least one compound containing fluorine. Suitable fluorine-containing compounds include, but are not limited to, fluorine-containing compounds inorganic, and / or compounds containing organic fluorine. In the specification, including the examples, certain abbreviations may be used to facilitate the description. These may include: Me = methyl, Et = ethyl, Bu = butyl, Ph = phenyl, Cp = cyclopentadienyl, Cp * = pentamethylcyclopentadienyl, Ind = indenyl, Ti = titanium; Hf = hafnium; Zr = zirconium, O = oxygen, Si = silicon, B = boron, Ta = tantalum, Nb = niobium, Ge = germanium, Mg = magnesium, Al = aluminum, Fe = iron, Th = thorium, Ga = gallium, P = phosphorus, Mo = molybdenum, Re = rhenium, and Sn = tin. Supports Suitable supports for use in this invention are generally porous materials, and may include organic materials, inorganic materials, and inorganic oxides. Desirably, carriers suitable for use in this invention include talc, clay, silica, alumina, magnesia, zirconia, iron oxides, boria, calcium oxide, zinc oxide, barium oxide, thoria, aluminum phosphate gel, chloride of polyvinyl, and substituted polystyrene, and mixtures thereof. Particulate silicon dioxide materials are well known and commercially available with a number of commercial suppliers. Desirably, the silicon dioxide used herein is porous, and has a surface area in the range of about 10 to about 700 square meters / gram, a total pore volume in the range of about 0.1 to about 4.0 cubic centimeters / gram, and an average particle diameter in the range of about 10 to about 500 microns. More desirably, the surface area is in the range of about 50 to about 500 square meters / gram, the pore volume is in the range of about 0.5 to about 3.5 cubic centimeters / gram, and the average particle diameter is in the range from about 15 to about 150 microns. More desirably, the surface area is in the range of about 100 to about 400 square meters / gram, the pore volume is in the range of about 0.8 to about 3.0 cubic centimeters / gram, and the average particle diameter is in the range of about 20 to about 100 microns. The average pore diameter of typical porous silicon dioxide support materials is in the range of about 10 to about 1000A. Desirably, the support material has an average pore diameter of from about 50 to about 500A, and more desirably from about 75 to about 350A. Fluorine Compounds Fluorine compounds suitable for providing fluorine for support are desirably compounds containing inorganic fluorine. These compounds containing inorganic fluorine can be any compound containing a fluorine atom, as long as it does not contain a carbon atom. Particularly desirable are compounds containing inorganic fluorine selected from the group consisting of NH4BF4, (NH4) 2SiF6, NH4PF6, NH4F, (NH4) 2TaF7, NH4NbF4, (NH4) 2GeF6, (NH4) 2SmF6, (NH4) 2TF6, (NH4) 2ZrF6, MoF6, ReF6, GaF3, S02C1F, F2, SiF4, SF6, C1F3, C1F5, BrF5, IF7, NF3, HF, BF3, NHF2, and NH4HF2. Of these, ammonium hexafluorosilicate and ammonium tetrafluoroborate are more desirable. Fluorine compounds of ammonium hexafluorosilicate and ammonium tetrafluoroborate are usually solid particulates, because they are the supports of silicon dioxide. A desirable method for the treatment of the support on the fluorine compound is to dry mix the two components, simply by mixing in a concentration of 0.01 to 10.0 millimoles F / gram of support, desirably in the range of 0.05 to 6.0 millimoles of F /. gram of support, and more desirably in the range of 0.1 to 3.0 millimoles of F / gram of support. The fluorine compound can be dry mixed with the support, either before or after being loaded into the vessel for dehydration or calcination of the support. According to the foregoing, the fluoride concentration present on the support is in the range of 0.6 to 3.5 weight percent of the support. Another method for treating the support with the fluorine compound is to dissolve the fluorine in a solvent, such as water, and then to contact the support with the solution containing fluorine. When water is used, and the support is silica, it is desirable to use an amount of water that is less than the total pore volume of the support. No dehydration or calcination of the silica is necessary before reacting with the fluorine compound. Desirably, the reaction between the silica and the fluorine compound is carried out at a temperature of from about 100 ° C to about 100 ° C, and more desirably from about 200 ° C to about 600 ° C, for about 2 to 8 hours . In one embodiment, the resulting support composition may be generically represented by the formula: Sup F "Sup" is a support, "F" is a fluorine atom bonded to the support. The fluorine atom can be linked, directly or indirectly, chemically or physically to the support. An example of the chemical or physical bond would be the covalent and ionic bond, respectively. The support composition can desirably be a fluorinated support composition. In another embodiment, the resulting support composition, such as a fluorinated support composition, may be generically represented by the formula: Sup L Fn. "Sup" is a support selected from the group that includes talc, clay, silica, alumina, magnesia, zirconia, iron oxides, boria, calcium oxide, zinc oxide, barium oxide, thoria, aluminum phosphate gel , polyvinyl chloride, and substituted polystyrene. "L" is a first member selected from the group that includes (i) a link, sufficient to link the F to the Sup; (ii) B, Ta, Nb, Ge, Ga, Sn, Si, P, Ti, Mo, Re, or Zr linked to the Sup and to the F; and (iii) 0 linked to the Sup and linked to a second member selected from the group consisting of B, Ta, Nb, Ge, Ga, Sn, Si, P, Ti, Mo, Re, or Zr, which is linked to the F; "F" is a fluorine atom; and "n" is a number from 1 to 7. An example of the linkage sufficient to link the F to the Sup would be a chemical or physical bond, such as, for example, a covalent and ionic bond. The support composition can desirably be a fluorinated support composition. Metallocenes As used herein, the term "metallocene" means one or more compounds represented by the formula CpraMRnXq, wherein Cp is a cyclopentadienyl ring, which may be substituted, or a derivative thereof, which may be substituted, M is a transition metal of group 4, 5, or 6, for example titanium, zirconium, hafnium, vanadium, niobium, tantalum, chromium, molybdenum, and tungsten, R is a hydrocarbyl group or a hydrocarboxyl group having from 1 to 20 atoms of carbon, X may be a halide, a hydride, an alkyl group, an alkenyl group, or an arylalkyl group, and m = l-3, n = 0-3, q = 0-3, and the sum of m + n + q is equal to the oxidation state of the transition metal. The methods for making and using metallocene are very well known in the art. For example, metallocenes are detailed in U.S. Patent Nos. 4,530,914; 4,542,199; 4,769,910; 4,808,561; 4,871,705; 4,933,403; 4,937,299; 5,017,714; 5,026,798, 5,057,475, 5,120,867, 5,132,381, 5,155,180, 5,198,401, 5,278,119; 5,304,614; 5,324,800; 5,350,723; 5,391,790; 5,436,305, and 5,510,502, each incorporated herein by reference in its entirety. Desirably, the metallocenes are one or more of those that consist of the formula: where M is a metal of group 4, 5, or 6 of the Periodic Table, desirably zirconium, hafnium, and titanium, most desirably zirconium; R1 and R2 are identical or different, desirably identical, and are one of a hydrogen atom, an alkyl group of 1 to 10 carbon atoms, desirably an alkyl group of 1 to 3 carbon atoms, an alkoxy group of 1 to 10 carbon atoms, desirably an alkoxy group of 1 to 3 carbon atoms, an aryl group of 6 to 10 carbon atoms, desirably an aryl group of 6 to 8 carbon atoms, an aryloxy group of 6 to 10 carbon atoms, desirably an aryloxy group of 6 to 8 atoms of carbon, an alkenyl group of 2 to 10 carbon atoms, desirably an alkenyl group of 2 to 4 carbon atoms, an arylalkyl group of 7 to 40 carbon atoms, desirably an arylalkyl group of 7 to 10 carbon atoms, alkylaryl group of 7 to 40 carbon atoms, desirably an alkylaryl group of 7 to 12 carbon atoms, an arylalkenyl group of 8 to 40 carbon atoms, desirably an arylalkenyl group of 8 to 12 carbon atoms, or a halogen atom , desirably chlorine; R5 and R6 are identical or different, desirably identical, and are one of a halogen atom, desirably a fluorine, chlorine, or bromine atom, an alkyl group of 1 to 10 carbon atoms, desirably an alkyl group of 1 to 4 carbon atoms, which may be halogenated, an aryl group of 6 to 10 carbon atoms, which may be halogenated, desirably an aryl group of 6 to 8 carbon atoms, an alkenyl group of 2 to 10 carbon atoms, desirably a alkenyl group of 2 to 4 carbon atoms, an arylalkyl group of 7 to 40 carbon atoms carbon, desirably an arylalkyl group of 7 to 10 carbon atoms, an alkylaryl group of 7 to 40 carbon atoms, desirably an alkylaryl of 7 to 12 carbon atoms, an arylalkenyl group of 8 to 40 carbon atoms, desirably an arylalkenyl group from 8 to 12 carbon atoms, a radical -NR215, -SR15, -OR15, -OSiR315, or -PR215, where R15 is one of a halogen atom, desirably a chlorine atom, an alkyl group of 1 to 10 atoms carbon, desirably an alkyl group of 1 to 3 carbon atoms, or an alkyl group of 6 to 10 carbon atoms, desirably an aryl group of 6 to 9 carbon atoms; R7 is: R11 R11 R11 R11 M2 M2 - M2 - M2 (CR213) - R12 R12 R12 R12 R11 R11 R11 O M2 O O M2 R12 R12 R12 -B (R11) -, -AKR11) -, -Ge-, -Sn-, -0-, -SO-, -S02-, -N (R) -, -CO-, -P (R) -, O -P (0) (R11) -; where: R11, R12, and R13 are identical or different, and are a hydrogen atom, a halogen atom, an alkyl group of 1 to 20 carbon atoms, desirably an alkyl group of 1 to 10 carbon atoms, a fluoroalkyl group of 1 to 20 carbon atoms, desirably a fluoroalkyl group of 1 to 10 carbon atoms, an aryl group of 6 to 30 carbon atoms, desirably an aryl group of 6 to 20 carbon atoms, a fluoroaryl group of 6 to 30 carbon atoms, desirably a fluoroaryl group of 6 to 20 carbon atoms , an alkoxy group of 1 to 20 carbon atoms, desirably an alkoxy group of 1 to 10 carbon atoms, an alkenyl group of 2 to 20 carbon atoms, desirably an alkenyl group of 2 to 10 carbon atoms, an arylalkyl group from 7 to 40 carbon atoms, desirably an arylalkyl group of 7 to 20 carbon atoms, an arylalkenyl group of 8 to 40 carbon atoms, desirably an arylalkenyl group of 8 to 22 carbon atoms, an alkylaryl group of 7 to 40 carbon atoms or, desirably, an alkylaryl group of 7 to 20 carbon atoms, or R 11 and R 12, or R 11 and R 13, together with the atoms that link them, can form ring systems; M2 is silicon, germanium, or tin, desirably silicon or germanium, more desirably silicon; R8 and R9 are identical or different, and have the meanings mentioned for R11; m and n are identical or different, and are 0, 1, or 2, desirably 0 or 1, where m + n 0, 1, or 2, desirably 0 or 1; the radicals R3, R4, and R10 are identical or different, and have the meanings mentioned for R11, R12, and R13. Two adjacent R10 radicals can be joined together to form a ring system, desirably a ring system containing from about 4 to 6 carbon atoms. "Alkyl" refers to straight or branched chain substituents. Halogen (halogenated) refers to fluorine, chlorine, bromine, or iodine atoms, desirably fluorine or chlorine. Particularly desirable transition metal compounds are the compounds of structures (A) and (B): where: M1 is Zr or Hf, R1 and R2 are methyl or chloro, and R5, R6, R8, R9, R10, R11, and R12 have the meanings mentioned above. Illustrative examples, but not limiting, of the Desirable transition metal compounds include: Dimethylsilandiylbis (2-methyl-4- (phenyl-1-indenyl) zirconium dimethyl; Dimethylsilandiylbis (2-methyl-4,5-benzoindenyl) zirconium dimethyl; Dimethylsilandiylbis (2-methyl-4 6-diisopropyl indenyl) dimethyl zirconium; Dimethylsilandiylbis (2-ethyl-4-phenyl-1-indenyl) zirconium dimethyl; Dimethylsilandiylbis (2-ethyl-4-naphyl-1-indenyl) zirconium dimethyl; Phenyl (methyl) silandiylbis (2-methyl-4-f-enyl-1-indenyl) zirconium dimethyl; Dimethylsilandiylbis (2-methyl-4- (l-naphyl) -1-indenyl) zirconium dimethyl; Dimethylsilandiylbis (2-methyl-4- (2-naphthyl) -1-indenyl) zirconium dimethyl; Dimethylsilandiylbis (2-methyl-indenyl) zirconium dimethyl; Dimethylsilandiylbis (2-methyl-4,5-diisopropyl-l-indenyl) zirconium dimethyl; Di-ethylsilandiylbis (2,4,6-trimethyl-1-indenyl) zirconium dimethyl; Phenyl (methyl) silandiylbis (2-methyl-4,6-diisopropyl-l-indenyl) zirconium dimethyl; 1,2-ethanediyl is (2-methyl-4,6-diisopropyl-1-indenyl) zirconium dimethyl; 1,2-butanediylbis (2-methyl-4,6-diisopropyl-l-indenyl) zirconium dimethyl; Dimethylsilandiylbis (2-methyl-4-ethyl-1-indenyl) zirconium dimethyl; Dimethylsilandiylbis (2-methyl-4-isopropyl-1-indenyl) zirconium dimethyl; Dimethylsilandiylbis (2-methyl-4-t-butyl-1-indenyl) zirconium dimethyl; Phenyl (methyl) silandiylbis (2-methyl-4-isopropyl-1-indenyl) zirconium dimethyl; Dimethylsilandiylbis (2-ethyl-4-methyl-1-indenyl) zirconium dimethyl; Dimethylsilandiylbis (2,4-dimethyl-l-indenyl) zirconium dimethyl; Dimethylsilandiylbis (2-methyl-4-ethyl-1-indenyl) zirconium dimethyl; Dimethylsilandiylbis (2-methyl-? I -acenaphth-l-indenyl) zirconium dimethyl; Phenyl (methyl) silandiylbis (-2-methyl-4,5-benzo-1-indenyl) zirconium dimethyl; Phenyl (methyl) silandiylbis (2-methyl-4-, 5- (methylbenzo) -1-inde-nyl) zirconium dimethyl; Phenyl (methyl) silandiylbis (2-methyl-4,5- (tetramethylbenzo) -1-i? Denyl) dimethyl zirconium; Phenyl (methyl) silandiylbis (2-methyl-α-acenaphth-1-indenyl) zirconium dimethyl; 1,2-ethanediylbis (2-methyl-4,5-benzo-1-indenyl) zirconium dimethyl; 1,2-butanediylbis (2-methyl-4,5-benzo-1-indenyl) zirconium dimethyl; Dimethyl silandylbis (2-methyl-4,5-benzo-1-indenyl) zirconium dimethyl; 1, 2-ethanediylbis (2,4,7-trimethyl-1-indenyl) zirconium dimethyl; Dimethylsilandiylbis (2-methyl-1-indenyl) zirconium dimethyl; 1, 2-ethanediylbis (2-methyl-1-indenyl) zirconium dimethyl; Phenyl (methyl) silandiylbis (2-methyl-1-indenyl) zirconium dimethyl; Diphenylsilandiylbis (2-methyl-1-indenyl) zirconium dimethyl; 1,2-butanediylbis (2-methyl-1-indenyl) zirconium dimethyl; Dimethylsilandiylbis (2-ethyl-1-indenyl) zirconium dimethyl; Dimethylsilandiylbis (2-methyl-5-isobutyl-1-indenyl) zirconium dimethyl; Phenyl (methyl) silandiylbis (2-methyl-5-isobutyl-l-indenyl) zirconium dimethyl; Dimethylsilandiylbis (2-methyl-5-t-butyl-1-indenyl) zirconium dimethyl; Dimethylsilandiylbis (2,5,6-trimethyl-1-indenyl) zirconium dimethyl; Dimethylsilandiylbis (2-methyl-4-phenyl-1-indenyl) zirconium dichloride, Dimethylsilandiylbis (2-methyl-4,5-benzoindenyl) zirconium dichloride, Dimethylsilandiylbis (2-methyl-4,6-diisopropylindenyl) zirconium dichloride, Dimethylsilandiylbis (2-ethyl-4-phenyl-1-indenyl) zirconium dichloride, Dimethylsilandiylbis (2-ethyl-4-naphthyl-1-indenyl) zirconium dichloride, Phenyl (methyl) silamylisobis (2-methyl-4-) dichloride phenyl-l-indenyl) zirconium, Dimethylsilandiylbis (2-methyl-4- (1-naphthyl) -1-indenyl) zirconium dichloride, dimethylsilandiylbis (2-methyl-4- (2-naphthyl) -1-indenyl) zirconium dichloride, dimethylsilandiylbis (2- methyl-indenyl) zirconium, Dimethylsilandiylbis (2-methyl-4,5-diisopropyl-1-indenyl) zirconium dichloride, dimethylsilandiylbis (2,4,6-trimethyl-1-indenyl) zirconium dichloride, dimethylsilandiylbis (2-methyl-4,6-dichloride) dichloride. diisopropyl-1-indenyl) zirconium, 1,2-ethanediylbis (2-methyl-4,6-diisopropyl-1-indenyl) zirconium dichloride, 1,2-butanediylbis (2-methyl-4,6-diisopropyl- l-indenyl) zirconium, dimethylsilandiylbis (2-methyl-4-ethyl-l-indenyl) zirconium dichloride, dimethylsilandiylbis (2-methyl-4-isopropyl-l-indenyl) zirconium dichloride, dimethylsilandiylbis (2-methyl-) dichloride. 4-t-butyl-l-indenyl) zirconium, phenyl (methyl) silandylbis (2-methyl-4-isopropyl-1-indenyl) zirconium dichloride, dimethylsilandiylbis (2-ethyl-4-methyl-1-indenyl) dichloride zirconium, Dimethylsilandiylbis (2,4-dimethyl-l-indenyl) zirconium dichloride, Dimethylsilandiylbis (2-methyl-4-ethyl-1-indenyl) zirconium dichloride, Dimethylsilandiylbis (2-methyl--acenaft-1-indenyl) zirconium dichloride, Phenyl (methyl) silanylisobis (2-methyl-4,5) dichloride. -benzo-l-indenyl) zirconium, phenyl (methyl) silandiylbis (2-methyl-4,5- (methylbenzo) -1-indenyl) zirconium dichloride, phenyl (methyl) silamylisobis (2-methyl-4,5) dichloride - (tetramethyl-benzo) -1-indenyl) zirconium, phenyl (methyl) silandylbis (2-methyl-a-acenaphth-1-indenyl) zirconium dichloride, 1,2-ethanediylbis (2-methyl-4,5) dichloride -benzo-1-indenyl) zirconium, 1,2-butandiylbis (2-methyl-4, 5-benzo-l-indenyl) zirconium dichloride, dimethylsilandiylbis (2-methyl-4,5-benzo-l-indenyl) dichloride ) zirconium, 1,2-ethanediylbis (2, 4, 7-trimethyl-l-indenyl) zirconium dichloride, Dimethylsilandiylbis (2-methyl-1-indenyl) zirconium dichloride, 1, 2-Ethanediylbis (2-methyl-1-indenyl) zirconium dichloride, phenyl (methyl) silanylbis (2-methyl-1-indenyl) zirconium dichloride, Diphenylsilandiylbis (2-methyl-1-indenyl) zirconium dichloride, 1,2-butandiylbis (2-methyl-1-indenyl) zirconium dichloride, Dimethylsilandiylbis (2-ethyl-1-indenyl) zirconium dichloride, Dimethylsilandiylbis (2-methyl-5-isobutyl-1-indenyl) zirconium dichloride, Phenyl (methyl) silamylisobis (2-methyl-5-isobutyl-1-dichloride) indenyl) zirconium, dimethylsilandiylbis (2-methyl-5-t-butyl-l-indenyl) zirconium dichloride, dimethylsilandiylbis (2, 5, 6-trimethyl-l-indenyl) zirconium dichloride, and the like. Many of these desirable transition metal compound components are described in detail in U.S. Patent Nos. 5,145,819; 5,243,001; 5,239,022; 5,329,033; 5,296,434; 5,276,208; 5,672,668; 5,304,614, and 5,374,752, and in the European patents Nos. EP 549 900 and 576 970, all of which are hereby incorporated by reference in their entirety, In addition, for use in this invention, the metallocenes, such as those described in US Pat. U.S. Patent No. 5,510,502, U.S. Patent No. 4,931,417, U.S. Patent No. 5,532,396, U.S. Patent No. 5,543,373, International Publication No. WO 98/014585, European Patent No. EP 611 773, and international publication No. WO 98/22486 (each fully incorporated herein by reference).

Activators Metallocenes are generally used in combination with some form of activator, in order to create an active catalyst system. The term "activator" is defined herein as any compound or component, or combination of compounds or components, capable of enhancing the ability of one or more metallocenes to polymerize olefins to polyolefins. Alkylalumoxanes, such as methylalumoxane (MAO), are commonly used as metallocene activators. In general, alkylalumoxanes contain from about 5 to 40 of the repeating units: R 'A1 °) x AIR2 for the linear species, R R (Al O) x for the cyclic species where R is an alkyl of 1 to 8 carbon atoms, including mixed alkyls. Particularly desirable are compounds wherein R is methyl. Alumoxane solutions, particularly methylalumoxane solutions, can be obtained from commercial vendors as solutions having different concentrations. There are a variety of methods for preparing alumoxane, the non-limiting examples of which are described in U.S. Patent Nos. 4,665,208, 4,952,540, 5,091,352, 5,206,199, 5,204,419, 4,874,734, 4,924,018, 4,908,463, 4,968,827, 5,308,815, 5,329,032, 5,248,801, 5,235,081, 5,103,031, and in European patents Nos. EP-A-0, 561, 476, EP-B1-0, 279, 586, EP-A-0, 594, 218, and in the international publication No. WO 94/10180, each fully incorporated herein by reference. (As used herein, unless otherwise reported, "solution" refers to any mixture, including suspensions). Ionizing activators can also be used to activate the metallocenes. These activators are neutral or ionic, or are compounds such as tris (n-butyl) ammonium tetrakis (pentafluorophenyl) borate, which ionize the neutral metallocene compound. These ionizing compounds may contain an active proton, or some other cation associated with, but not coordinated with, or only slightly coordinated with, the remaining ion of the ionizing compound. Combinations of activators can also be used, for example alumoxane and ionizing activators in combinations, see, for example, International Publication No. WO 94/07928. Descriptions of the ionic catalysts for coordination polymerization comprised of metallocene cations activated by non-coordinating anions appear in the first works of the European patents Nos. EP-A-0,277,003, EP-A-0,277, 004, and in the U.S. Patent No. 5,198,401, and in International Publication No. WO 92/00333 (incorporated herein by reference). These teach a desirable method of preparation, where the metallocenes (bisCp and monoCp) are protonated by an anion precursor, in such a way that an alkyl / hydride group of a transition metal is abstracted, to make it both cationic and balanced charge, by the anion no coordinator. Suitable ionic salts include borate or aluminum salts substituted by tetrakis, having fluorinated aryl constituents, such as phenyl, biphenyl, and naphthyl. The term "non-coordinating anion" (NCA) means an anion that does not coordinate with the cation, or that only weakly coordinates with the cation, thus being sufficiently labile to be displaced by a neutral Lewis base. The non-coordinating (compatible) anions are those that are not degraded until neutrality when the initially formed complex is decomposed. In addition, the anion will not transfer a substituent or anionic fragment to the cation so as to cause it to form a metallocene-4-neutral coordinate compound and a neutral by-product from the anion. The non-coordinating anions useful in accordance with this invention are those which are compatible, which stabilize the metallocene cation in the sense of balancing its ion charge in a +1 state, and yet retain sufficient lability to allow displacement by a monomer ethylenically or acetylenically unsaturated during the polymerization. The use of ionizing ionic compounds that do not they contain an active proton, but capable of producing both the active metallocene cation and a non-coordinating anion, it is also known. See, for example, European patents Nos. EP-A-0,426,637 and EP-A-0, 573, 403 (incorporated herein by reference). An additional method for making the ionic catalysts uses the ionization of the anion precursors, which are initially neutral Lewis acids, but form the cation and the anion after the ionizing reaction with the metallocene compounds, for example with the use of tris. (pentafluorophenyl) borane. See European Patent No. EP-A-0, 520, 732 (incorporated herein by reference). Ionic catalysts can also be prepared for the addition polymerization by oxidation of the metal centers of the transition metal compounds by the anion precursors containing metal oxidizing groups, together with the anion groups, see European patent No EP-A-0, 495, 375 (incorporated herein by reference). When metal ligands include halogen moieties (e.g., bis-cyclopentadienylzirconium dichloride) that are not capable of ionizing abstraction under conventional conditions, they can be converted by known alkylation reactions with organometallic compounds, such as lithium hydrides. or aluminum, or alkyls, alkylalumoxanes, Grignard reagents, and so on. See European patents Nos. EP-A-0, 500944 and EP-A1-0, 570, 982 (incorporated by hereinafter referred to as reference), for on-site processes, which describe the reaction of alkylaluminum compounds with metallocene compounds disubstituted by halogen, before, or with, the addition of activating anionic compounds. Desirable methods for supporting ionic catalysts comprising metallocene and NCA cations are described in U.S. Patent No. 5,643,847, in U.S. Patent Application No. 09/184358, filed November 2, 1998. , and in U.S. Patent Application No. 09/184389, filed November 2, 1998 (all fully incorporated herein by reference). When using the support composition, and particularly the fluorinated support composition of this invention, these NCA support methods generally comprise using neutral anion precursors that are Lewis acids strong enough to react with the reactive hydroxyl functionalities. present on the surface of the silica, in such a way that the Lewis acid becomes bound in a covalent manner. In one embodiment of this invention, the activator is one or more NCAs, and the support method described above is used. This reaction can be represented generically by the chemical formula: (1) [LnLlmM'R '] + [LA-0-SupLFnr, where [LnL, mM' R I] + is the catalytic transition metal cation- actively active, and LA-O- is the activating anion bonded to the support composition, particularly the fluorinated support composition, SupLFn. More specifically, Ln is one or more ligands (n is equal to ad ° -l, where d ° is the highest oxidation state of M ') covalently linked to M', L'm is a neutral non-oxidizing ligand having a dative link with M '(normally m is equal to 0 to 3), M' is a transition metal of Group 4, 5, 6, 9, or 10, R 'is a ligand that has a bond s with M', where a polymerizable monomer or macromonomer can be inserted for coordination polymerization. LA is a Lewis acid that is capable of forming the anionic activator, and O is oxygen. Neutral precursors of activating anions that serve as Lewis acid (LA) include any of the non-coordinating anion precursors, of sufficient acidity to accept the available electron pair of the oxygen atom of the hydroxyl group, and facilitate the protonation of the compound of transition metal or of a secondary proton acceptor (see below) by the proton of the silanol group. Neutral precursors of desirable activating anions that serve as Lewis acid (LA) are strong Lewis acids with non-hydrolyzable ligands, at least one of which is electron withdrawing, such as Lewis acids that are known to they abstract an anionic fragment from dimethylzirconocene (bis-cyclopentadienylzirconium dimethyl), for example, tris-perfluorophenylborane, tris-perfluoronaphthylborane, tris-perfluoro- biphenylborane. These precursors, therefore, must not possess reactive ligands, which can be protonated by any remaining hydroxyl groups on the support composition, particularly the fluorinated support composition. For example, any Lewis acids based on a Group 13 element having only alkyl, halogen, alkoxy, and / or amido ligands, which are easily hydrolyzed in aqueous media, can not be suitable. At least one LA ligand must have sufficient removal of electrons to reach the necessary acidity, for example tris-perfluorophenylborane, under the typical reaction conditions. Typical metal / metalloid centers for LA will include boron, aluminum, antimony, arsenic, phosphorus, and gallium. More desirably, LA is a neutral compound comprising a metalloid center of Group 13, with a complement of ligands together, of sufficient removal of electrons, such that the Lewis acidity is greater than or equal to that of A1C13. Examples include tris-perfluorophenylborane, tris (3,5-di (trifluoromethyl) phenyl) borane, tris (di-t-butylmethylsilyl) per-fluorophenylborane, and other highly fluorinated tris-arylborane compounds. Additionally, when the activator for the supported metallocene catalyst composition is an NCA, desirably first the NCA is added to the support composition, followed by the addition of the metallocene catalyst. When the activator is MAO, desirably the MAO and the catalyst are dissolved metallocene together in solution. The support is then contacted with the MAO / metallocene catalyst solution. Other methods and orders of addition will be apparent to those skilled in the art. Polymerization The supported metallocene catalyst composition is useful in the polymerization with coordination of unsaturated monomers that are conventionally known to be polymerizable under polymerization conditions with coordination. These conditions are also well known, and include solution polymerization, paste polymerization, and low pressure gas phase polymerization. The supported metallocene catalyst compositions of the present invention, therefore, are particularly useful in known operating modes employing fixed bed, moving bed, fluid bed, or paste processes, conducted in individual reactors., in series, or in parallel. The supported metallocene catalyst composition of this invention is particularly suitable for propylene polymerizations. Any process can be used, but propylene polymerizations are most commonly conducted using a paste process, where the polymerization medium can be a liquid monomer, such as propylene, or a hydrocarbon solvent or solvent, conveniently aliphatic paraffin, such as propane. , isobutane, hexane, heptane, cyclohexane, etcetera, or an aromatic diluent, such as toluene. The polymerization temperatures may be those considered low, for example less than 50 ° C, desirably from 0 ° C to 30 ° C, or may be in a higher range, such as up to about 150 ° C, desirably 50 ° C. ° C to approximately 80 ° C, or in any ranges between the indicated end points. The pressures may vary from about 100 to about 700 psia (0.69-4.8 MPa). A further description is given in U.S. Patent Nos. 5,274,056 and 4,182,810, and in International Publication No. WO 94/21962, which are each fully incorporated by reference. Propylene homopolymers can be formed with the supported metallocene catalyst composition, using conventional polymerization techniques. The microstructure of the homopolymer will desirably have a meso stretch measured by 13 C NMR of 70 percent or more relative to the total polymer produced. Copolymers can be formed with ethylene by the introduction of ethylene to the phase polymerization of paste or propylene gas, of the gaseous co-monomers of propylene and ethylene. Copolymers with ethylene desirably contain 0.1 to 10 weight percent co-monomer. Homopolymers and copolymers of stereo-regular α-olefins can be formed with this system, by introducing the appropriate monomer or monomers into a pulp or bulk propylene process.

Pre-polymerization can also be used for additional control of the morphology of the polymer particles in typical pulp or gas phase reaction processes according to conventional teachings. For example, this can be done by pre-polymerizing an α-olefin of 2 to 6 carbon atoms for a limited time, for example, contacting the ethylene with the supported metallocene catalyst composition, at a temperature of -15 °. C at 30 ° C, and at an ethylene pressure of up to about 250 psig (1724 kPa) for 75 minutes, to obtain a polymer coating on the polyethylene support of a molecular weight of 30,000 to 150,000. The pre-polymerized catalyst is then available for use in the polymerization processes referred to above. In a similar manner, the activated catalyst can be used on a support coated with a thermoplastic polymer previously polymerized in these polymerization processes. Additionally, it is desirable to reduce or eliminate poisons of polymerization that can be introduced by means of feed streams, solvents or diluents, by removing or neutralizing the poisons. For example, the monomer feed streams or the reaction diluent can be pretreated, or treated at the site during the polymerization reaction, with a suitable scavenger. Normally, this will be an organometallic compound used in processes such as those that use the organometallic compounds of Group-13 of U.S. Patent No. 5,153,157, and of the international publications Nos. WO-A-91/09882 and WO-A-94/03506, mentioned above, and of the international publication No. WO-A-93/14132. EXAMPLES The following examples are presented to illustrate the above description. All parts, proportions, and percentages are by weight, unless otherwise indicated. Although the examples may be directed to certain embodiments of the present invention, they should not be seen as limiting the invention in any specific aspect. Preparation of the supports The following example shows that silica can be fluorinated during the process of silica gel heat dehydration. Example 1 48.5 grams of SiO2, available from Grace Davison, a subsidiary of W.R. Grace Co.-Conn. such as Sylopol®952 ("silica gel 952"), with a N2 pore volume of 1.63 cubic centimeters / gram, and a surface area of 312 square meters / gram, were dry mixed with 1.5 grams of available ammonium hexafluorosilicate in Aldrich Chemical Company, Milwaukee, Wl. The aggregate ammonium hexafluorosilicate corresponds to 1.05 millimoles of F per gram of silica gel. The mixture is transferred He laughed at a Vycor glass tube 5 centimeters in internal diameter by 50 centimeters, with a plug of frit mediated 3.8 centimeters from one end. The tube was inserted in a tube furnace, and a flow of N2 (220 cubic centimeters / minute) was passed through the frit, to fluidize the silica bed. The oven was heated according to the following program: Raise the temperature from 25 ° C to 150 ° C for 5 hours. Maintain the temperature at 150 ° C for 4 hours. Raise the temperature from 150 ° C to 500 ° C for 2 hours. Maintain the temperature at 500 ° C for 4 hours. Remove the heating and allow to cool under N2. When cooled, the fluorinated silica was stored under N2. The Neutron Activation Analysis of Nuclear Analytical Services, from the Texas Unit in Austin, showed 1.68 + 0.6 percent by weight (% by weight) of fluorine. The following examples show that the weight percent of fluorine on the silica can be controlled by the amount and type of fluorine-containing compound, such as a compound containing inorganic fluorine, added to the silica gel before dehydration with heat. Examples 2 to 14 In a similar manner, silica gel 952 was treated as described in Example 1, except that different weights and fluorine compounds were used. The details can be seen in Table 1. Column 3 describes the percentage by weight of the fluorine compound present in the sample of silica / total fluorine compound before heating. Column 4 marked "aggregate" describes the percentage by weight of fluorine present in the sample before heating. Column 5 marked "found" describes the weight percentage of fluorine present in the sample after heating. The weight percentage of column 5 is higher than that of column 4, reflecting, to some degree, the loss of water during heating.

Table 1. Examples of Fluorinated Silica at 500 ° C 1. Undetermined. Examples 15 to 21 show that the silica gel can be fluorinated during dehydration with heat at different temperatures. Example 15 In a similar manner to Example 1, 48.15 grams of silica gel 952 were mixed dry with 1.85 grams of ammonium fluoride from Aldrich Chemical Company, Milwaukee, Wl. The ammonium fluoride added corresponds to 1.05 millimoles of F per gram of silica gel. The following heating program was used.

Raise the temperature from 25 ° C to 150 ° C for 5 hours.

Maintain the temperature at 150 ° C for 4 hours. Raise the temperature from 150 ° C to 600 ° C for 2 hours.

Maintain the temperature at 600 ° C for 4 hours. Remove the heating and allow to cool under N2. When cooled, the fluorinated silica was stored under N2 The Neutron Activation Analysis showed 2.00 + 0.09 weight percent of fluorine. Example 16 Silica gel 952 was treated as in Example 1, except that the following heating program was used.

Raise the temperature from 25 ° C to 150 ° C for 5 hours.

Maintain the temperature at 150 ° C for 4 hours. Raise the temperature from 150 ° C to 300 ° C for 2 hours. Maintain the temperature at 300 ° C for 4 hours. Remove the heating, and allow to cool under N2. When cooled, the fluorinated silica was stored under N2 Examples 17 to 21 In a similar manner, silica gel 952 was fluorinated as in Example 16, except that different weights and fluorine compounds were used. The details are shown in Table 2. In a manner similar to Table 1, column 3 describes the percentage by weight of fluorine compound present in the sample of the silica / total fluorine compound before heating. The column four marked "aggregate", describes the percentage by weight of fluorine present in the sample before heating. Column five marked "found" describes the weight percentage of fluorine present in the sample after heating. The percentage by weight in column five is higher than that in column four, reflecting, to some degree, the loss of water during heating. Table 2. Examples of Fluorinated Silica at 300 ° C 1. Undetermined. Examples 22 and 23 show silica gels from other manufacturers that can be fluorinated during dehydration with heat. Example 22 48.5 grams of Si02, available from The PQ Corporation, Valley Forge PA, as MS1340, with a surface area of 450 square meters / gram, and a pore volume of 1.3 cubic centimeters / gram, were mixed dry with 1.5 grams of ammonium hexafluorosilicate available from Aldrich Chemical Co. The mixture was transferred to the fluidized dehydrator described in the Example 1, and a flow of N2 (400 cubic centimeters / minute) was passed through the unit. The oven was heated according to the following program. Raise the temperature from 25 ° C to 150 ° C for 5 hours.

Maintain the temperature at 150 ° C for 4 hours. Raise the temperature from 150 ° C to 500 ° C for 2 hours.

Maintain the temperature at 500 ° C for 4 hours. Remove the heating, and allow to cool under N2. When cooled, the fluorinated silica was stored under N2 The Neutron Activation Analysis showed 1.93 + 0.045 of fluorine. Example 23 48.5 grams of SiO2, available from Crosfield Limited, Warrington England, as MD682CM, with a surface area of 280 square meters / gram, and a pore volume of 1.4 cubic centimeters / gram, were mixed dry with 1.5 grams of ammonium hexafluorosilicate available from Aldrich Chemical Co.

The mixture was transferred to the fluidized dehydrator described in Example 1, and a flow of N2 (202 cubic centimeters / minute) was passed through the unit. The oven was heated according to the following program: Raise the temperature from 25 ° C to 150 ° C for 5 hours.

Maintain the temperature at 150 ° C for 4 hours. Raise the temperature from 150 ° C to 500 ° C for 2 hours.

Maintain the temperature at 500 ° C for 4 hours. Remove the heating, and allow to cool under N2. When cooled, the fluorinated silica was stored under N2. The Neutron Activation Analysis showed 1.96 + 0.052 percent fluorine. Comparative Examples 1 to 10 describe the preparation of non-fluorinated dehydrated silicas, for comparison as supports with the fluorinated silicas. Comparative Example 1 50.0 grams of Si02 (silica gel 952) were transferred to a Vycor glass tube of 5 centimeters internal diameter by 50 centimeters, with a medium frit plug of 3.8 centimeters from one end. The tube was inserted into a tube furnace, and a flow of N2 (220 cubic centimeters / minute) was passed through the frit to fluidize the silica bed. The oven was heated according to the following program: Raise the temperature from 25 ° C to 150 ° C for 5 hours. Maintain the temperature at 150 ° C for 4 hours. Raise the temperature from 150 ° C to 800 ° C for 2 hours. Maintain the temperature at 800 ° C for 4 hours. Remove the heating, and allow to cool under N2. When cooled, the dehydrated silica was stored under N2. Comparative Example 2 In a similar manner, the silica gel 952 is dehydrated with the same program as Comparative Example 1, except that the maximum temperature was 600 ° C. When cooled, the dehydrated silica was stored under N2. Comparative Example 3 In a similar manner, silica gel 952 was dehydrated with the same program as Comparative Example 1, except that the maximum temperature was 500 ° C. When cooled, the dehydrated silica was stored under N2. Comparative Example 4 In a similar manner, the silica gel was dehydrated Sylopol®948 ("silica gel 948"), with a pore volume of 1.7 cubic centimeters / gram, and a surface area of 335 square meters / gram, available from Grace Davison, a subsidiary of F.R. Grace Co.-Conn., With the same program as Comparative Example 3. When cooled, the dehydrated silica was stored under N2. Comparative Example 5 In a similar manner, silica gel 952 was dehydrated with the same program as Comparative Example 1, except that the maximum temperature was 300 ° C. When cooled, the dehydrated silica was stored under N2. Comparative Example 6 describes the preparation of a chemically dehydrated, non-fluorinated silica, for a comparison as a support with the fluorinated silica. Comparative Example 6 .00 grams of the silica prepared in Comparative Example 4 was charged in a 1000 milliliter flask, and 250 milliliters of hexane were added. To the pulp under stirring, 5.3 milliliters of hexamethyldisilazane, available from Aldrich Chemical Company, Milwaukee, Wisconsin, United States, was added. After the drip addition was finished, the pulp was stirred for 30 minutes, and then refluxed for 120 minutes. When it cooled, the flask was taken to the dry box. The supernatant was decanted, and then the pulp was washed twice with hexane, twice with isopentane, and dried under vacuum at room temperature. 25.76 grams of chemically dehydrated silica gel were obtained. The dehydrated silica was stored under N2. Comparative Example 7 describes the preparation of fluorinated silica with a fluorinating agent at room temperature, for a comparison as a support with the fluorinated silica of the present invention. Comparative Example 7 15.0 grams of silica gel 952, previously dehydrated by heat with the heating program shown in Example 1, were charged into a 250 milliliter flask, and the flask was evacuated. The vacuum was replaced by N2, and the procedure was repeated three times. In the dry box under N2, a stir bar was added. In a separate flask, 42.25 grams of dry toluene and purged of N2 were combined with 0.615 grams of dimethylamine-sulfur trifluoride, available from Aldrich Chemical Co. The toluene solution was added slowly to the silica, and then the paste was heated at 50 ° C for 150 minutes, followed by more toluene (15.1 grams), and additional heating for 30 minutes. Stirring was stopped, and the supernatant was decanted. The residue was washed three times with portions of 20 to 25 grams of toluene. The final residue was dried in vacuo to a final temperature of 60 ° C. The dry weight of the treated silica was 1.35 grams. The Neutron Activation Analysis showed 1.70 + 0.1 percent fluorine. The fluorinated silica was stored under N2 before use. Comparative Examples 8 to 10 show that the silica gel can be halogenated with the congeners of fluorine during the dehydration with heat. Comparative Examples 8 to 10 In a manner similar to Example 15, non-fluorinated silica (silica gel 952) was mixed with other ammonium halide compounds in molar amounts equal to the millimoles of fluorine used, and then the mixture was heated as described. described earlier. When they cooled, the dehydrated silicas were stored under N2. The details are shown in Table 3. Column 3 describes the percentage by weight of halide compound present in the sample of silica compound / total halide. Column 4 marked "aggregate" describes the weight percentage of halide present in the sample before heating. Column 5 marked "found" describes the percentage by weight of halide present in the sample after heating. Table 3. Treated with Congenital Halogens 1. Equivalent to 1.05 millimoles per gram of silica. Catalysts Examples 24-25 and Comparative Examples 11-12, show that metallocene catalysts prepared with methylalumoxane and fluorinated silica dehydrated as the support, have a higher activity, comparing with the same catalysts prepared with methylalumoxane using dehydrated silica. Except as otherwise reported in the specific example, the polymerization procedure of Example 24 was followed. Example 24 In the dry box under N2, 0.0525 grams of rac-dimethylsilandiylbis (2-methylindenyl) zirconium dichloride were placed in a 50 milliliter beaker, and 4.55 grams of methylalumoxane were added as a 30 percent solution in toluene The resulting metallocene solution was stirred for 30 minutes with a magnetic bar. Then 15.0 grams of dry toluene and purged N2 were added, followed by another 5 minutes of stirring. Separately, 5.00 grams of the fluorinated silica prepared in Example 8 was transferred to a 150 milliliter beaker. The metallocene solution was added to the fluorinated silica gel in three aliquots with stirring. The resulting paste was stirred for an additional 60 minutes, and then the volatiles were removed in vacuo. Heat was applied to the drying catalyst, until a final temperature of 50 ° C, which was maintained for 60 minutes. The dry catalyst was 6.52 grams of a finely divided free-flowing solid. The Elemental Analysis showed 9.18 percent of Al, and 0.142 percent of Zr. Batch Polymerization A 2 liter autoclave reactor previously flooded hot with N 2, and cooled to room temperature, was charged with triethylaluminum (1 milliliter of an IM solution in hexane), followed by 1,100 milliliters of propylene. If necessary for polymerization, about 5 millimoles of hydrogen were added from a reservoir, by pressure difference, before propylene. After heating the reactor contents to 70 ° C, 100 milligrams of solid catalyst, made in paste in 2 milliliters of hexane, was flooded with 100 milliliters of propylene to initiate the reaction. After 1 hour, the reactor was cooled, vented, purged with N2 for 20 minutes, and then opened. The polypropylene was transferred to a glass dish, and allowed to dry in a vaporization hood overnight. The next day, the polymer was dried further under vacuum at 75 ° C for 1 hour. The dried polymer was weighed. Polymer Analysis: MFR was measured by the method of ASTM 1238, condition L. Bulk density was measured using the method of ASTM D-1895-89, Method A. Particle size was measured by the method of ASTM D 1921 -89, Method. The molecular weight (MW) and its distribution (MWD) were measured by GPC in a Waters 150-C at 145 ° C, using 1,2,4-trichlorobenzene as the solvent. 106.8 milligrams of the solid prepared as described in Example 24, gave 334.1 grams of polypropylene in 60 minutes. The productivity was 3.128 grams of PP / gram of catalyst. The activity was 200.9 Kg of PP / millimole of Zr. The analysis showed that the polymer has the following properties: 25.8 MFR, 149532 grams / mol molecular weight, and dispersity of 1.82. Example 25 In the dry box under N2, 0.705 grams of rac-dimethylsilylethylabisbis (2-methyl-4-phenyl-1-indenyl) zirconium dichloride was placed in a 50 milliliter beaker, and 4.55 grams of methylalumoxane were added as a solution to percent in toluene. The resulting metallocene solution was stirred for 30 minutes with a magnetic bar. Then 14.0 grams of dry toluene and purged with N2 were added, followed by another 5 minutes of stirring. Separately, 5.00 grams of the fluorinated silica prepared in Example 8 was transferred to a 150 milliliter beaker. The metallocene solution was added to the fluorinated silica gel in three aliquots with stirring. The resulting paste was stirred for an additional 60 minutes, heat was applied to the drying catalyst, to a final temperature of 50 ° C, which was maintained for 60 minutes. The dry catalyst was 6.48 grams of a finely divided free-flowing solid. The elemental analysis showed 9.55 percent of Al, and 0.153 percent of Zr. 109.8 milligrams of the solid gave 326.3 grams of polypropylene in 60 minutes. The productivity was 2,972 grams of PP / gram of catalyst. The activity was 177.2 kg of PP / millimole of Zr. The analysis showed that the polymer has the following properties: 577822 grams / mol of molecular weight, and dispersity of 2.12. Comparative Example 11 In the dry box under N2, 0.0532 grams of rac-dimethylsilandiylbis (2-methylindenyl) zirconium dichloride were placed in a 50 milliliter beaker, and 4.56 grams of methylalumoxane were added as a 30 percent solution in toluene The resulting metallocene solution was stirred for 30 minutes with a magnetic bar. Then 16.5 grams were added of dry toluene and purged with N2, followed by another 5 minutes of stirring. Separately, 5.00 grams of silica prepared in Comparative Example 3 was transferred to a 150 milliliter beaker. The metallocene solution was added to the silica gel in three aliquots with stirring. The resulting paste was stirred for an additional 60 minutes, and then the volatiles were removed in vacuo. Heat was applied to the drying catalyst to a final temperature of 50 ° C, which was maintained for 60 minutes. The dry catalyst was 6.67 grams of a finely divided free-flowing solid. The Elemental Analysis showed 9.12 percent of Al, and 0.128 percent of Zr. 102.7 milligrams of the solid gave 111.2 grams of polypropylene in 60 minutes. The productivity was 1.083 grams of PP / gram of catalyst. The activity was 77.2 kg of PP / millimole of Zr. The analysis showed that the polymer has the following properties: 23.4 MFR, 143867 grams / mol of molecular weight, and dispersity of 1.72. Comparative Example 12 In the dry box, under N2, 0.0709 grams of rac-dimethylsilandiylbis (2-methyl-4-phenyl-1-inde-nil) zirconium dichloride was placed in a 50 milliliter beaker, and 4.56 were added. grams of methylalumoxane as a 30 percent solution in toluene. The resulting metallocene solution was stirred for 30 minutes with a magnetic bar. Then 16.5 grams of dry toluene and purged with N2 were added, followed for another 5 minutes of agitation. Separately, 5.00 grams of the silica prepared in Comparative Example 3 was transferred to a 150 milliliter beaker. The metallocene solution was added to the silica gel in three aliquots with stirring. The resulting paste was stirred for an additional 60 minutes, and then the volatiles were removed in vacuo. Heat was applied to the drying catalyst, until a final temperature of 50 ° C, which was maintained for 60 minutes. The dry catalyst was 6.48 grams of a finely divided free-flowing solid. Elemental Analysis showed 9.19 percent of Al, and 0.120 percent of Zr. 103.3 grams of the solid gave 82.9 grams of polypropylene in 60 minutes. The productivity was 803 grams of PP / gram of catalyst. The activity was 61.0 kg of PP / millimole of Zr. The analysis showed that the polymer has the following properties: 689094 grams / mol of molecular weight, and dispersity of 2.17. The comparison of the results detailed above, shows that the fluorinated silica dehydrated catalyst has more than double the activity of the dehydrated silica catalyst, based on the content Zr. The following examples show that the metallocene catalysts prepared with a non-coordinating anion, and using the fluorinated silica dehydrated as the support, have a higher activity, compared to the same catalysts prepared using dehydrated silica.

Example 26 In the dry box under N2, 5.00 grams of the fluorinated silica prepared in Example 4 was transferred to a 250 milliliter flask containing a magnetic bar. In a 50 milliliter beaker, 0.18 grams of N, N'-diethylaniline, available from Aldrich Chemical Company, Milwaukee Wl, was diluted with 18.0 milliliters of dry hexane and purged of N2. This solution was added slowly to the silica with stirring to form a thick paste. The paste was diluted with 5.0 milliliters of hexane, and heat was applied as stirring was continued. At the end of 30 minutes, the temperature was 40 ° C. 0.55 grams of tris-perfluorophenylborane, available from Boulder Cientific Company, Mead, CO, was added and stirring - heating continued. After an additional 60 minutes, the temperature was constant at 50 ° C. 0.06 grams of rac-dimethylsilandiylbis (2-methylindenyl) zirconium dimethyl were added, and stirring - heating was continued. After 120 minutes, heating was stopped, and the paste was allowed to settle. The supernatant was removed, and the solids were dried in vacuo. Heat was applied as the catalyst was dried, to a final temperature of 30 ° C, which was maintained for 60 minutes. The dry catalyst was 5.85 grams of a finely divided free-flowing solid. Elemental analysis showed 0.20 percent of B, and 0.21 percent of Zr. 105.0 grams of the solid gave 135.7 grams of polypropylene in 60 minutes. The producti- The volume was 1,292 grams of PP / gram of catalyst. The activity was 56.1 kg of PP / millimole of Zr. The analysis showed that the polymer has the following properties: 105024 grams / mol of molecular weight, and dispersity of 1.96. Example 27 101.2 milligrams of the catalyst prepared in Example 26 were charged to the polymerization reactor containing hydrogen. 127.6 grams of polypropylene were prepared in 60 minutes. The productivity was 1.261 grams of PP / gram of catalyst. The activity was 54.8 kg of PP / millimole of Zr. The analysis showed that the polymer has the following properties: 107642 grams / mol of molecular weight, and dispersity of 2.03. Comparative Example 13 In a manner similar to Example 26, a catalyst was prepared, except that the silica of Comparative Example 3 was used. The dry catalyst was 5.75 grams of a finely divided free-flowing solid. The elemental analysis showed 0.19 percent of B, and 0.22 percent of Zr. 103.6 milligrams of the solid gave 8.7 grams of polypropylene in 60 minutes. The productivity was 84 grams of PP / gram of catalyst. The activity was 3.5 kg of PP / millimole of Zr. The analysis showed that the polymer has the following properties: 102315 grams / mol of molecular weight, and dispersity of 2.04. Comparative Example 14 99.2 milligrams of the catalyst prepared in Example Comparative 13 were charged to the polymerization reactor containing hydrogen. 13.6 grams of polypropylene were prepared in 60 minutes. The productivity was 137 grams of PP / gram of catalyst. The activity was 5.7 kg of PP / millimole of Zr. The analysis showed that the polymer has the following properties: 91845 grams / mol of molecular weight, and dispersity of 1.90. The comparison of the results detailed above shows that the dehydrated fluorinated silica catalyst has on average about 1,280 percent more activity than the dehydrated silica catalyst based on Zr. Example 28 In the dry box, under N2, 5.01 grams of the fluorinated silica prepared in Example 4 was transferred to a 250 milliliter flask containing a magnetic bar. In a 50 milliliter beaker, 0.18 grams of N, N'-diethylaniline, available from Aldrich Chemical Company, Milwaukee Wl, was diluted with 18.0 milliliters of dry hexane and purged of N2. This solution was added slowly to the silica with stirring to form a thick paste. The paste was diluted with 5.0 milliliters of hexane, and heat was applied as agitation continued. At the end of 30 minutes, the temperature was 40 ° C. 0.55 grams of tris-perfluorophenylborane, available from Boulder Cientific Company, Mead, CO, was added and stirring continued-heating. After an additional 50 minutes, the temperature The temperature was constant at 50 ° C. 0.08 grams of rac-dimethylsilandiylbis (2-methyl-4-phenyl-1-indenyl) zirconium dimethyl were added, and stirring-heating was continued. After 120 minutes, heating was stopped, and the paste was allowed to settle. The supernatant was removed, and the solids were dried in vacuo. Heat was applied as the catalyst was dried to a final temperature of 30 ° C, which was maintained for 60 minutes. The dry catalyst was 5.84 grams of a finely divided free-flowing solid. The elemental analysis showed 0.22 percent of B and 0.21 percent of Zr. 101.6 milligrams of the solid gave 155.3 grams of polypropylene in 60 minutes. The productivity was 1.529 grams of PP / gram of catalyst. The activity was 66.4 kg of PP / millimole of Zr. The analysis showed that the polymer has the following properties: 529068 grams / mol of molecular weight, and dispersity of 2.35. Example 29 102.5 milligrams of the catalyst prepared in Example '28 were charged to the polymerization reactor containing hydrogen. 237.0 grams of polypropylene were prepared in 60 minutes. The productivity was 2,312 grams of PP / gram of catalyst. The activity was 100.4 kg of PP / millimole of Zr. The analysis showed that the polymer has the following properties: 474587 grams / mol of molecular weight, and dispersity of 2.48. Comparative Example 15 In a manner similar to Example 28, a catalyst, except that the silica of Comparative Example 3 was used. The dry catalyst was 5.90 grams of a finely divided free flowing solid. The elemental analysis showed 0.19 percent of B, and 0.18 percent of Zr. 100.1 milligrams of the solid gave 22.0 grams of polypropylene in 60 minutes. The productivity was 220 grams of PP / gram of catalyst. The activity was 11.1 kg of PP / millimole of Zr. The analysis showed that the polymer has the following properties: 579479 grams / mol of molecular weight, and dispersity of 2.40. Comparative Example 16 105.1 milligrams of the catalyst prepared in Comparative Example 15 were charged to the polymerization reactor containing hydrogen. 120.7 grams of polypropylene were prepared in 60 minutes. The productivity was 1,148 grams of PP / gram of catalyst. The activity was 58.2 kg of PP / millimole of Zr. The analysis showed that the polymer has the following properties: 529068 grams / mol of molecular weight, and dispersity of 2.35. Comparison of the results detailed above shows that the fluorinated silica dehydrated catalyst has on average about 380 percent more activity on a Zr basis than the dehydrated silica catalyst. The following examples show that metallocene catalysts prepared with a non-coordinating anion, and using Other dehydrated fluorinated silicas as the support also show high activity, compared to similar catalysts prepared using dehydrated silicas. Example 30 In the dry box under N2, 5.00 grams of the fluorinated silica prepared in Example 2 was transferred to a 250 milliliter flask containing a magnetic bar. In a 50 milliliter beaker, 0.18 grams of N, N'-diethylaniline, available from Aldrich Chemical Company, Milwaukee, Wl, was diluted with 18.0 milliliters of dry hexane and purged of N2. This solution was added slowly to the silica with stirring to form a thick paste. The paste was diluted with 5.0 milliliters of hexane, and heat was applied as agitation continued. At the end of 30 minutes, the temperature was 40 ° C. 0.55 grams of tris-perfluorophenylborane, available from Boulder Cientific Company, Mead, CO, was added and stirring continued-heating. After an additional 60 minutes, the temperature was constant at 50 ° C. 0.08 grams of rac-dimethylsilandiylbis (2-methyl-4-phenyl-1-indenyl) zirconium dimethylol was added, and stirring - heating was continued. After 120 minutes, heating was stopped, and the paste was allowed to settle. The supernatant was removed, and the solids were dried in vacuo. Heat was applied as the catalyst was dried to a final temperature of 30 ° C, which was maintained for 60 minutes. The dry catalyst was 5.69 grams of a solid free flow finely divided. Elemental analysis showed 0.22 percent of B, and 0.18 percent of Zr. Examples 31 to 39 In a manner similar to Example 30, catalysts were prepared on other fluorinated silicas at 500 ° C. The details are shown in Table 4. The results of the polymerization are shown in Tables 5 and 6. Table 4. Catalysts Prepared on Fluorinated Silicas at 500 ° C 1. The units are millimoles of reagent per gram of silica.

Table 5. Polymerization Results for the Catalyst on Fluorescent Silicas at 500 ° C Table 6. Polymerization Results for the Catalyst on Fluorescent Silicas at 500"C1 1. Hydrogen added to the reactor. Examples 40 to 47 In a manner similar to Example 30, catalysts were prepared on other fluorinated silicas at 300 ° C. The details are shown in Table 7. The results of the polymerization are shown in Tables 8 and 9.

Table 7. Prepared Catalysts on Fluorescent Silicas at 300 ° C . The units are millimoles of reagent per gram of silica, Table 8. Polymerization Results for the Catalysts on Fluorescent Silicas at 300 ° C Table 9. Polymerization Results for Catalysts on Fluorescent Silicas at 300"C1 1. Hydrogen added to the reactor. Comparative Examples 17 to 23 In a manner similar to Example 30, catalysts were prepared, except that dehydrated silicas were used.

The details are shown in Table 10. The polymerization results are shown in Tables 11 and 12. Table 10. Catalysts Prepared On Dehydrated Silicas 1. The units are millimoles of reagent per gram of silica.

Table 11. Polymerization Results for Catalysts on Dehydrated Silicas Table 12. Polymerization Results for Catalysts on Dehydrated Silicas1 1. Hydrogen added to the reactor. The following example shows that a metallocene catalyst prepared with a non-coordinating anion on a chemically dehydrated silica does not have the high activity of a similar catalyst prepared on a dehydrated silica. fluoridated Comparative Example 24 In a manner similar to Example 30, the catalyst was prepared, except that silica treated with hexamethyldisilazane of Comparative Example 6 was used. The dry catalyst was 6.70 grams of a finely divided free flowing solid. The elemental analysis showed 0.29 percent of B, and 0.17 percent of Zr. 100.8 milligrams of the solid gave 6.7 grams of polypropylene in 60 minutes. The productivity was 66.5 grams of PP / gram of catalyst. The activity was 3.6 kg of PP / millimole of Zr. The following example shows that a metallocene catalyst prepared with a non-coordinating anion on an alternatively fluorinated silica does not have the high activity of a similar catalyst prepared on a fluorinated dehydrated silica. Comparative Example 25 In a manner similar to Example 30, the catalyst was prepared, except that silica treated with dimethylamine-sulfur trifluoride of Comparative Example 7 was used. The dry catalyst was 5.36 grams of a finely divided free-flowing solid. The elemental analysis showed 0.095 percent of B, and 0.096 percent of Zr. 98.7 milligrams of the solid was added to the polymerization reactor to test the activity. The solid was inactive for the polymerization of propylene.

The following examples show that metallocene catalysts prepared with a non-coordinating anion on a dehydrated silica halogenated with the congeners of fluorine do not have the high activity of a similar catalyst prepared on a dehydrated fluorinated silica. Comparative Example 26 In a manner similar to Example 30, the catalyst was prepared, except that the halogenated silica with ammonium chloride of Comparative Example 8 was used. The dry catalyst was 5.52 grams of a finely divided free flowing solid. The elemental analysis showed 0.12 percent of B, and 0.11 percent of Zr. 99.3 milligrams of the solid was added to the polymerization reactor to test the activity. The solid was inactive for the polymerization of propylene. Comparative Example 27 In a manner similar to Example 30, the catalyst was prepared, except that the halogenated silica was used with ammonium bromide of Comparative Example 9. The dry catalyst was 5.61 grams of a finely divided free-flowing solid. Elemental analysis showed 0.11 percent of B, and 0.16 percent of Zr. 99.7 milligrams of the solid was added to the polymerization reactor to test the activity. The solid was inactive for the polymerization of propylene. The following examples show that the advantages of using fluorinated silica as a catalyst support are not they lose or are reduced when larger quantities are fluorinated, nor is the high activity of the resulting catalysts compromised when a continuous polymerization process is used. Example 48 A fluorinated silica was prepared by Grace Davison from Sylopol®9522, and ammonium hexafluorosilicate, according to the procedure of Example 1. Elemental analysis showed that the fluorine content was 1.49 + 0.06 weight percent. Moreover, the fluorinated silica gel had the following properties: 1.69 cubic centimeters / gram of pore volume, 256 square meters / gram of surface area, and an average particle size of 35 microns. In the dry box under N2, 401 grams of this silica was transferred to a 4 liter flask. 6.4 grams of N, N'-diethylaniline were combined with 1.542 grams of dry hexane and dispersed with N2. All the liquid was added to the silica. The pulp was stirred mechanically, and heat was applied. After 30 minutes, 21.61 grams of trisperfluorophenylborane were added. After 60 minutes, 3.20 grams of rac-dimethylsilandiylbis (2-methyl-4-phenyl-1-inde-nyl) zirconium dimethyl were added. The temperature of the paste was 50 ° C. During the next 120 minutes, stirring was continued, and a final temperature of 51 ° C was reached. At this time, the heating was stopped, and the pasta was allowed to settle. The clear colorless supernatant was removed, and found to have less than 4 PPM of zirconium or boron, and 6 PPM of N.

Total amount of supernatant removed before drying was 575.4 grams. The solids were dried in vacuo. Heat was applied as the catalyst dried, until the free-flowing solid was maintained at a final temperature of 30 ° C for 120 minutes. The dry catalyst was 423.8 grams. The elemental analysis showed 0.101 percent of B, and 0.114 percent of Zr. 102.6 milligrams of the solid were loaded into the polymerization batch reactor at 70 ° C, along with about 5 millimoles of H2. The yield was 199 grams of polypropylene in 35 minutes. The productivity per hour was 3326 grams of PP / gram of catalyst. The activity per hour was 266 kg of PP / millimole of Zr. The analysis showed that the polymer has the following properties: 0.42 grams / milliliter of apparent density, 352052 grams / mol of molecular weight, and dispersity of 2.34. Example 48A Continuous Polymerization The polymerization was conducted in liquid propylene, in a pilot scale polymerization process, using two reactors in series. The reactors were equipped with sleeves to remove heat from the polymerization. The reactor temperature was set at 74 ° C in the first reactor, and 68 ° C in the second reactor. The catalyst prepared as described above was fed at a rate of 1 to 2 grams / hour. A solution of 1 percent by weight of TEAL in hexane was fed to a Speed of 4 to 5 cubic centimeters per minute. Propylene is fed at a rate of about 80 kilograms / hour to the first reactor, and at about 27 kilograms / hour to the second reactor. The concentration of hydrogen in the first reactor was 1,000 mppm and 1,300 mppm in the second. Residence times were about 2.5 hours in the first reactor, and about 1.9 hours in the second reactor. The speed of polymer production from the reactors was approximately 40 kilograms / hour. The productivitv of the catalyst was calculated from the total weight of the polymer made, and the total weight of the catalyst used. The productivity for the catalyst of Example 48 was 20.5 kilograms / gram of catalyst, and the activity was 1.639 kilograms / millimole of Zr. The polymer was discharged from the reactors as a granular product having the following properties: 2.62 MFR, bulk density of 0.46 grams / cubic centimeter, and average particle size of 999.3 microns. Examples 49 to 52 Examples 49 to 52 were generated in a manner similar to the continuous polymerization described in Example 48A, except that the polymerization was allowed to occur at different levels of hydrogen. The data is shown in Table 13.

Table 13. Continuous Polymerization Results for Catalyst Example 48 1. Molar parts per million. The following examples show that the advantages of using fluorinated silica as a catalyst support are reproducible. Example 53 A second fluorinated silica was prepared by Grace Davison from Sylopol®9522, and ammonium hexafluorosilicate, according to the heating program of Example 1. Elemental analysis showed that the fluorine content was 2.35 ± 0.05 percent in weigh. The fluorinated silica gel had the following properties: 1.62 cubic centimeters / gram of pore volume, 243 square meters / gram of surface area, and average particle size of 39 microns. In the dry box under N2, 465.4 grams of this silica was transferred to a 4 liter flask. 7.5 grams of N, N'-diethylaniline was combined with 1,800 grams of dry hexane and dispersed with N 2. All the liquid It was added to the silica. The pulp was stirred mechanically, and heat was applied. At the 30 minute mark, the temperature was 50.8 ° C, and 25.2 grams of tris-perfluorophenylborane were added. After 60 minutes, the temperature was 53 ° C, and 3.70 grams of rac-dimethylsilandiylbis (2-methyl-4-phenyl-1-indenyl) zirconium dimethyl were added. During the next 120 minutes, stirring was continued, and a final temperature of 55 ° C was reached. At this time, the heating was stopped, and the pasta was allowed to settle. The clear colorless supernatant was removed, and found to weigh 404.7 grams. The solids were dried in vacuo. Heat was applied as the catalyst dried, until the free-flowing solid was maintained at a final temperature of 35 ° C for 120 minutes. The dry catalyst was 486.93 grams. The elemental analysis showed 0.10 percent of B, and 0.11 percent of Zr. Example 54 to 58 Using the supported catalyst of Example 53, a series of batch polymerization runs were made, as described in Example 48. The results are shown in Table 14.

Table 14. Batch Polymerization Results for Catalyst Example 531 1. Hydrogen added to the reactor. Example 59 to 62 Using the supported catalyst described in Example 53, a series of continuous polymerization runs were made, as described in Example 48A. The data is shown in Table 15. Table 15. Results of Continuous Polymerization for Catalyst Example 53 1. Molar parts per million. Discussion Although the above examples deal primarily with a supported metallocene catalyst composition, it will be recognized that the attributes of the polymers produced by the supported metallocene catalyst composition of the present invention, will be lent for use in final product applications. Examples of these final product applications include articles made from films, thermoforming and blow molding, fibers, such as meltblown fibers, and spun fibers, and fabrics. Although the present invention has been described and illustrated with reference to particular embodiments, it will be appreciated by those of ordinary skill in the art that the invention lends itself to many different variations not illustrated herein. Then, for these reasons, reference should be made exclusively to the appended claims for the purposes of determining the true scope of the present invention. Although the appended claims have individual dependencies in accordance with the practice of United States patents, each of the features of any of the dependent claims may be combined with each of the features of other dependent claims or the main claim.

Claims (22)

1. CLAIMS 1. A supported metallocene catalyst composition comprising: a metallocene catalyst; and a support composition represented by a formula Sup F where Sup is a support and F is a fluorine atom bound to the support.
2. 2. The supported metallocene catalyst composition of claim 1, wherein the metallocene catalyst is represented by the formula CpmMRnXq wherein Cp is a cyclopentadienyl ring that can be substituted, or its derivative that can be substituted, M is a transition metal of group 4, 5 or 6, R is a hydrocarbyl group or hydrocarboxy group having from 1 to 20 carbon atoms, X can be a halide, a hydride, an alkyl group, an alkenyl group or an arylalkyl group, and = l-3, n = 0-3, q = 0-3, and the sum of m + n + q is equal to the oxidation state of the transition metal.
3. 3. A supported metallocene catalyst composition comprising: a metallocene catalyst; and a support composition represented by a formula Sup L Fn where Sup is a support selected from the group consisting of talc, clay, silica, alumina, magnesia, zirconia, iron oxides, boria, calcium oxide, zinc oxide, barium oxide, thoria, aluminum phosphate gel, polyvinylchloride or substituted polystyrene; "L" is a first member selected from the group consisting of (i) a link, sufficient to link F to Sup; (ii) B, Ta, Nb, Ge, Ga, Sn, Si, P, Ti, Mo, Re, or Zr bound to Sup and to F; or (iii) 0 linked to Sup and linked to a second member selected from the group consisting of B, Ta, Nb, Ge, Ga, Sn, Si, P, Ti, Mo, Re or Zr which is linked to F; "F" is a fluorine atom; and "n" is a number of 1-7.
4. 4. The supported metallocene catalyst composition of claim 3, wherein the support composition is a fluorinated support composition.
5. 5. The metallocene supported catalyst composition of claim 3, wherein the metallocene catalyst is represented by a formula: CpmMRnXq where Cp is a cyclopentadienyl ring that can be substituted, or a derivative thereof that can be substituted, M is a transition metal of group 4, 5 or 6, R is a hydrocarbyl group or a hydrocarboxyl group having from 1 to 20 carbon atoms, X can be a halide, a hydride, an alkyl group, an alkenyl group or an arylalkyl group , and m = l-3, n = 0-3, q = 0-3, and the sum of m + n + q is equal to the oxidation state of the transition metal.
6. 6. The supported metallocene catalyst composition of claim 3, further including an activator.
7. 7. The supported metallocene catalyst composition of claim 6, wherein the activator is an alkylalumoxane.
8. 8. The metallocene supported catalyst composition of claim 6, wherein the activator is a noncoordinating anion activator.
9. The supported metallocene catalyst composition of claim 3, wherein the metallocene is selected from the group consisting of: dimethylsilandylbis (2-methyl-4-phenyl-1-indenyl) zirconium dimethyl; dimethylsilandylbis (2-methyl-4,6-diisopropylindenyl) zirconium dimethyl; dimethylsilandylbis (2-ethyl-4-phenyl-1-indenyl) zirconium dimethyl; dimethylsilandylbis (2-ethyl-4-naphthyl-1-indenyl) zirconium dimethyl; dimethylsilandylbis (2-methyl-4- (1-naphthyl) -1-indenyl) zirconium dimethyl; dimethylsilandylbis (2-methyl-4 (2-naphthyl) -1-indenyl) zirconium dimethyl; dimethylsilandylbis (2-methyl-indenyl) zirconium dimethyl; dimethylsilandylbis (2-methyl-4,5-diisopropyl-l-indenyl) zirconium dimethyl; dimethylsilandylbis (2,4,6-trimethyl-l-indenyl) zirconium dimethyl; dimethylsilandylbis (2-methyl-1-indenyl) zirconium dimethyl; dimethylsilandylbis (2-ethyl-1-indenyl) zirconium dimethyl; dimethylsilandylbis (2,5,6-trimethyl-l-indenyl) zirconium dimethyl; dimethylsilandylbis (2-methyl-4-phenyl-1-indenyl) zirconium dichloride; dimethylsilandylbis (2-methyl-4,5-benzoindenyl) zirconium dichloride; dimethylsilandylbis (2-methyl-4,6-diisopropylindenyl) zirconium dichloride; dimethylsilandylbis (2-ethyl-4-phenyl-1-indenyl) zirconium dichloride; dimethylsilandylbis (2-ethyl-4-naphthyl-l-indenyl) zirconium dichloride; dimethylsilandylbis (2-methyl-4- (l-naphthyl) -1-indenyl) zirconium dichloride; dimethylsilandylbis (2-methyl-4- (2-naphthyl) -1-indenyl) zirconium dichloride; dimethylsilandylbis (2-methyl-indenyl) zirconium dichloride; dimethylsilandylbis (2-methyl-4,5-diisopropyl-1-indenyl) zirconium dichloride; dimethylsilandylbis (2,4,6-trimethyl-l-indenyl) zirconium dichloride; dimethylsilandylbis (2-methyl-1-indenyl) zirconium dichloride; dimethylsilandylbis (2-ethyl-1-indenyl) zirconium dichloride; or dichloride dimethylsilandylbis (2,5,6-trimethyl-1-indenyl) zirconium.
10. 10. The supported metallocene catalyst composition of claim 3, wherein the fluorine concentration is in the range of 0.01 to 10.0 millimoles of fluorine per gram of support.
11. 11. A method of making a supported metallocene catalyst composition comprising the step of: contacting a metallocene catalyst with a support composition under suitable conditions and for a sufficient time, wherein the support composition is represented by a formula Sup L Fn where Sup is a support selected from the group consisting of talc, clay, silica, alumina, magnesia, zirconia, iron oxides, boria, calcium oxide, zinc oxide, barium oxide, thoria, phosphate gel of aluminum, polyvinylchloride and substituted polystyrene; "L" is a first member selected from the group consisting of (i) a link, sufficient to link F to Sup; (ii) B, Ta, Nb, Ge, Ga, Sn, Si, P, Ti, Mo, Re, or Zr bound to Sup and to F; or (iii) O linked to Sup and linked to a second member selected from the group consisting of B, Ta, Nb, Ge, Ga, Sn, Si, P, Ti, Mo, Re, or Zr which is linked to F; "F" is a fluorine atom; and "n" is a number of 1-7.
12. 12. The method of claim 11, comprising the step of contacting the metallocene catalyst with an activator before contacting the metallocene with the support composition. .
13. 13. The method of claim 11, wherein the support composition is a fluorinated support composition.
14. 14. A polymerization method, comprising the step of: contacting a polymerizable olefin with a metallocene supported catalyst composition, under suitable conditions and for a sufficient time, wherein the supported metallocene catalyst composition comprises a metallocene catalyst; a support composition represented by a formula Sup L Fn where Sup is a support selected from the group consisting of talc, clay, silica, alumina, magnesia, zirconia, iron oxides, boria, calcium oxide, zinc oxide, barium, toria, aluminum phosphate gel, polyvinyl chloride and substituted polystyrene; "L" is a first member selected from the group consisting of (i) a link, sufficient to link F to Sup; (ii) B, Ta, Nb, Ge, Ga, Sn, Si, P, Ti, Mo, Re, or Zr bound to Sup and to F; or (iii) O linked to Sup and linked to a second member selected from the group consisting of B, Ta, Nb, Ge, Ga, Sn, Si, P, Ti, Mo, Re or Zr which is linked to F; "F" is a fluorine atom; and "n" is a number of 1-7.
15. 15. The method of claim 14, wherein the polymerizable olefin is propylene.
16. 16. An article incorporating a polymeric product of claim 14.
17. 17. The article of claim 16, comprising a member selected from the group consisting of films, fibers, fabrics, and molded structures.
18. 18. The method of claim 14, wherein the support composition is a fluorinated support composition.
19. 19. A metallocene supported catalyst composition, consisting essentially of: one or more metallocene catalysts; an activator; and a support composition represented by a formula Sup L Fn where Sup is a support selected from the group consisting of talc, clay, silica, alumina, magnesia, zirconia, iron oxides, boria, calcium oxide, zinc oxide, oxide barium, toria, aluminum phosphate gel, polyvinylchloride or substituted polystyrene, and mixtures thereof; "L" is a first member selected from the group consisting of (i) a link, sufficient to link F to Sup; (ii) B, Ta, Nb, Ge, Ga, Sn, Si, P, Ti, Mo, Re or Zr bound to Sup and to F; (iii) O linked to Sup and linked to a second member selected from the group consisting of B, Ta, Nb, Ge, Ga, Sn, Si, P, Ti, Mo, Re or Zr which is linked to F; "F" is a fluorine atom; and "n" is a number of 1-7.
20. 20. The supported metallocene catalyst composition of claim 19, wherein the support composition is a fluorinated support composition.
21. 21. The supported catalyst composition, of metallocene, of claim 19, wherein the metallocene catalyst is represented by a formula: CpraMRnXq wherein Cp is a cyclopentadienyl ring that can be substituted, or a derivative thereof that can be substituted, M is a transition metal of the group 4, 5 or 6, R is a hydrocarbyl group or a hydrocarboxy group having from 1 to 20 carbon atoms, X can be a halide, a hydride, an alkyl group, an alkenyl group or an arylalkyl group, and m = l-3 , n = 0-3, q = 0-3, and the sum of m + n + q is equal to the oxidation state of the transition metal.
22. 22. The supported metallocene catalyst composition of claim 19, wherein the fluorine concentration is in the range of 0.6 to 3.5% by weight of the support.