JP2002508010A - Catalyst supported on polymer for olefin polymerization - Google Patents

Abstract

SUMMARY OF THE INVENTION The present invention provides a process for high particle density polymerization of low soil and a) i) having a surface area of about 1 to 400 m ² / g, and ii) functionalizing with a proton-containing ammonium salt of a non-coordinating anion. B) an ancillary ligand, at least one unstable ligand which can be abstracted by protonation with said ammonium salt and at least one ligand into which an olefin monomer can be inserted for polymerization. An olefin polymerization catalyst composition comprising a reaction product with an organometallic transition metal compound having a stable ligand is provided. In a preferred embodiment, the polymeric support has a surface area of 10 m ² / g or less and is particularly suitable for use with highly active organometallic transition metal catalyst compounds.

Description

DETAILED DESCRIPTION OF THE INVENTION                 Catalyst supported on polymer for olefin polymerization Technical fields   The present invention relates to olefin polymerization with organometallic transition metal catalysts on a polymer support. I do. In the present invention, the transition metal catalyst is ionized for polymerization. Activated and stabilized in cationic form with non-coordinating anions. Background art   Organometallic transition metal cations are activated by compatible non-coordinating anions The use of ion catalysts for olefin polymerization, which are stabilized in It is well known in the art. Typically, such organometallic transition metal Thion helps stabilize organometallic transition metal compounds to an active positive state An auxiliary ligand and an unstable ligand, at least one of which is withdrawn Wherein the compound is cationic and at least one of which is an olefin inserted Attraction of Organometallic Transition Metal Compounds Having Both Ligands and Suitable Ligand Conductor. The inert support increases the insertion weight in both gas phase and slurry polymerizations. In addition, technology for supporting these ion catalysts is also known ing.   US Patent No. 5,427,991 and corresponding PCT Application Publication No. WO-A-93 / 11172 When used with a metallocene compound, the ion is physically adsorbed to the inert support. Desorption questions experienced when catalysts are used in solution or slurry polymerizations Of a non-coordinating anionic surfactant to produce a polyanionic surfactant which avoids the problem Chemical attachment to a support is described. The support is non-coordinated, chemically bound Inert monomers, oligomers and poly made to incorporate anions It is the core component of a polymer or metal oxide support. Portions from hydrocarbyl compounds The teaching of the preparation of lianionic activators (FIGS. 1, 5, 6) requires several reactions. I do. A typical reaction of a polymer core component is to convert a polymerizable monomer into a lithiating agent (li). thiating agent) treatment with n-BuLi or polymerizable monomer optionally with lithium Is a reaction that polymerizes the monomer into polymer segments. A polymer having a locarbyl lithium group or a crosslinked polymer is produced. Next, the polymers were converted to [DMAH]⁺[(pfp)_ThreeBP^-] (Wherein P is a polymer A component. ) For producing a polymer surface having a covalently bonded activator group First, the bulky Lewis acid trisperfluorophenylboron (B (pfp)_Three) , Dimethylanilinium hydrogen chloride ([DMAH]⁺[Cl]^-) With ion exchange reaction You. PCT Application Publication No. WO 96/04319 includes catalysts for Lewis acids and Group 4 transition metal compounds. The activator complex initially formed for protonation to the cation active as a medium Silanol groups on the silica-containing support that donate a hydroxy group proton A non-coordinating anion precursor covalently linked through A supporting method using Nylboron) is described.   In addition to the attachment of the anionic complex to the support substrate, the patent literature also discloses a transition metal ligand group. To the polymer support, and then reacting the ligand group with the transition metal compound, Organometallic compounds bound to polymer supports via clopentadienyl ligand Is described. Next, for example, alkylalumoxane and The use of an activating co-catalyst compound, such as phenyl borate, allows such compounds to be turned on. It can be suitable as a refining polymerization catalyst. U.S. Patent No. 4,463,135 No. 5,610,115 and PCT Application Publication No. WO 96/35726. WO96 / 35726 About 15m^TwoContaining Acrylate-Containing Copolymer Support with Surface Area of Less Than Use, for example 2.1m^TwoAn example showing a surface area of / g is described. These catalysts typically have polar moieties such as adsorbed water and hydroxyl groups. Requires fewer manufacturing steps because it is not present on the polymer support. Are taught to have advantages over metal oxides. But this The technology is based on the production of ligands bound to the support, for binding to the next transition metal. This limits the choice of available ligands for the reaction and also results in low reaction product yields and And undesired by-products, some of which may interfere with the next reaction or Poses the problem that it may compete with the next reaction.   Also, polymer resins for use with or for the production of heterogeneous catalyst species “Functionalization of Crosslinked Polystyrene by Chemical Modification ”, Chemisty and Properties of Crosslinked Polymers, (Academic Press, 1 977 Year) and Studies in Surface by Sun, L., Shariati, A., Hsu, J.C., Bacon, D.W.  Science and Catalysis, 1994, 89, 81 and U.S. Pat.No. 4,246,134. Please refer to. U.S. Pat.No. 4,246,134 has 30-700 m^Two/ G specific surface area Of macroporous copolymer of vinyl monomer and divinyl monomer The body as well as its use for vinyl polymer polymerization are described.   The use of supported or heterogeneous catalysts in gas-phase polymerizations is To achieve shapes and densities that improve reactor operability and facilitate handling. This is important as a means for increasing the method efficiency. Inefficient catalyst supports are polymers -Allows the formation of fine powders, resulting in fouling of reactor walls or tubes. This is an early For a number of possible reasons, including micronization of the support particles or desorption of the catalyst. And both support particle refining and catalyst desorption are reduced in controlling the polymerization. Can be brought. Polymer particle size and density are degraded and efficiency is lost. Also On-catalysts reduce the amount of co-catalyst needed, and often An important industry in providing safer and cheaper synthesis of activator compounds Provide strategic benefits. However, those catalysts are very sensitive to polar impurities And therefore can reduce the production of potentially interfering by-products A method of synthesis is preferred.Summary of the Invention   The present invention relates to a high particle density polymerization process with low soiling and a) i) about 1 to 400 m^Two/ g of surface area and ii) functionalized with a protonated ammonium salt of a non-coordinating anion. Polymer support and b) ancillary ligand, said ammonium salt At least one unstable ligand capable of abstraction by polymerization and Organic having at least one labile ligand into which an olefin monomer can be inserted An olefin polymerization catalyst composition comprising a reaction product with a metal transition metal compound is provided. . The present invention provides a polymer support which stabilizes a catalytically active transition metal cation. Protonated ammonium covalently bound to a non-coordinating anion Also encompassed are functionalized supports that are salt-containing intermediates. In a preferred embodiment, 10m polymer support^Two/ G surface area and a highly active organometallic transition metal Particularly suitable for use with a medium compound.Description of the invention   The functionalized polymer support according to the present invention can be used to process organometallic transition metal compounds. Activation by toning, essentially uniform distribution throughout the polymer resin support Of organometallic transition metal compounds without adversely affecting the ability to facilitate Before entering, it can be washed, stored, transported, handled or otherwise handled. Activator supported on a stable polymer that can be It is a polymer support A protonated, ammonium-based cation covalently attached to a And containing ammonium salt functional groups.   Nitrogen atom of the protonated ammonium salt function of the polymer support of the invention Is substituted with one to three groups, at least one of which is of the formulaA, [Po Remar- (R¹) (R^Two) (R^Three) NH]⁺[NCA]^- A (formulaAMedium, R¹, R^TwoAnd R^ThreeAre the same or different and represent hydrogen, hydrocarbyl and substituted Selected from the group consisting of¹, R^TwoAnd R^ThreeAt least one is water Not plain) Attach ammonium functionality to the polymer support as represented by R¹, R^TwoAnd R^ThreeHas preferably 1 to 30, more preferably 1 to 20, carbon atoms. I do. In the present invention, the term "substituted hydrocarbyl" also refers to hydrocarbyl. R group R¹, R^TwoAnd R^ThreeOne or more hydrogen atoms of halogen, and N, O, S and P A substantially hydrocarbyl having 1 to 3 heteroatoms selected from the group consisting of Groups; organometalloids substituted with hydrocarbyl; halogen-substituted An organometalloid; and 1 to 1 selected from the group consisting of N, O, S, and P Substituted with at least one substantially hydrocarbyl group having three heteroatoms Substituted by one of the groups selected from organometalloids A radical. NCA stands for compatible "non-coordinating anion".   R of the ammonium salt of the present invention¹, R^TwoAnd R^ThreeThe group includes an alicyclic ring having a ring nitrogen atom. Alternatively, a compound in which two or three R groups are bonded to form an aromatic ring is also included. See, for example, the compounds below.   The term non-coordinating anion as used for compounds of the present invention refers to the transition gold Does not coordinate to the genus cation or is weakly coordinated to said cation, Anions that remain unstable enough to be displaced by a neutral Lewis base Is a technical term recognized as meaning. A "compatible" non-coordinating anion is To neutral when a complex is formed between them and the transition metal cation catalyst compound. Not something. Further, the anion is composed of a neutral four-coordinate metal compound and an anion. Anionic substituents or fragments to form neutral by-products from the cation Do not transfer to Useful non-coordinating anions of the present invention are compatible and Stabilizes the transition metal cation of the present invention in the sense of balancing ionic charges Sufficient to allow substitution by the olefinically unsaturated monomer during the polymerization. Maintain instability. The anion useful in the present invention is used in the polymerization step. The transition metal cations of the present invention by Lewis bases other than polymerizable monomers that may be present Have a sufficient molecular size to partially prevent or help prevent neutralization of You. Suitable non-coordinating anions are described in U.S. Patent Nos. 5,198,401, 5,278,119, 5,40. No. 7,884, 5,599,761; preferably, they are Unstable proton-containing nitrogenous salt of the described metal or metalloid compound . Organoboron and organoaluminum salts are preferred. According to US Patent Practice All references are incorporated by reference.   The olefin polymerization catalyst composition of the present invention comprises an activator supported on the polymer of the present invention. Essentially any suitable for olefin polymerization when activated by protonation at Of the organometallic transition metal compoundAThe product of the reaction achieved by contacting It is. This product combines organometallic transition metal cations and supplemental non-coordinating anions. A supported ionic catalyst composition having a polymer support matrix. It is homogeneously dispersed in the Rix. Further, the transition metal cation and the polymer support It is believed that there is a donor interaction between the amine function of the matrix, You are not bound by this idea. The strength of this interaction depends on the transition metal It should depend on the Lewis acidity of the amine and especially on the Lewis basicity of the amine function. This phase Interactions reduce the tendency of ionic catalytic species to desorb from the polymer support matrix Acts to be. Has a very strong Lewis base and / or minimal steric bulk The Lewis base must be strongly coordinated to a free coordination position in the center of the cationic metal. It is noted that is known (eg, pyridine). In general, this means It means that primary amines are preferred over primary amines.   The contacting is effected by the permeation of the organometallic transition metal compound into the matrix of the polymer support. It must be done to make mistakes. Therefore, preferably, the supported activity is The treatment is performed by treating the agent particles with a solution of an organometallic transition metal compound. Organic Suitable solvents for the metal transition metal compound include the linkage, the chemical composition of the support material and the support May be aliphatic or aromatic, depending on the degree of cross-linking. Toluene and hex The sun is typical. Support is about 50m^Two/ G or less surface area It is particularly desirable to use a solvent for swelling. Contact temperature and pressure It can vary as long as the reagent, solvent and carrier do not degrade and become unreactive. Ambient atmosphere The conditions are suitable. By analogy, organometallic transition metallization suitable for olefin polymerization Activation of compounds by protonation and stabilization with non-coordinating anions is well Known, for example, US Pat.No. 5,198,401 for a description of the mechanisms involved, See No. 5,278,119 and PCT application WO 96/04319. US special All documents are hereby incorporated by reference in accordance with accepted practice.   The polymer support typically comprises essentially a hydrocarbon polymer compound. Good Preferably, such a hydrocarbon polymer compound is laced on the polymer chains constituting the support. It is essentially uniformly distributed throughout the support mass due to the functional groups incorporated into the Surface low enough to prevent excessive monomer contact with active catalyst sites It has a product. Including hydrocarbon polymer compounds. The term low surface area , Single point nitrogen E. FIG. T. (By Brunauer, S., Emmmet, PH, Teller, E. JACS, 1938, 60, 309)^Two/ G or less surface area, This may be exemplified by the use of polystyrene based beads or gels. These beads or The gel is lightly cross-linked and randomly functionalized with ammonium salt compounds. I have. An important feature of those catalyst support compounds is the ability to produce supported catalysts. In or in the solvent used in the use in polymerizing the monomer Particle size and temperature, pressure related to insolubility, effectiveness for use in fluidized bed reactors And overall rupture resistance under charging conditions. Therefore, the support is subjected to a normal polymerization operation. Must be insoluble under growing conditions. Preferably, the beads have uniform dimensions Spheres in the usual size range of 400 to 100 US mesh sizing (30 to 100 μm).   Suitable supports are obtained in the form of homogeneously crosslinked polymers, which are Most suitable. A suitable functionalized essentially hydrocarbon polymer support or support The body is commercially available, for example, a polystyrene bead or gel, or It can be produced synthetically by general knowledge in the art. For example, the background above See Technology. The synthesis is generally carried out with the vinyl monomer and the ammonia of the present invention. Consists of copolymerization with a comonomer having a functionalization suitable for nucleophilic displacement This copolymerization may be by direct copolymerization or by copolymerization and subsequent formation of a support. By derivation of a chemical reaction to place suitable functional groups in the hydrocarbon polymer chain . Specific examples include polystyrene-divinylbenzene copolymer gels or beads Is mentioned. Relative strength and rupture resistance are divinylbenzene (DVB) comonomer And the commercial products contain 2 to 20% by weight of DVB. You. Higher ranges of DVB, such as 10-20% by weight DVB, may provide additional strength. The additional cross-linking provided, however, causes the beads to shrink and shrink as required for normal polymerization operations. It resists movement by making it resistant to swelling. Effective porosity is divinyl It is adjusted by selecting the benzene content. For example, a DVB content of 5-10% by weight A limited polymerization motion suitable for high activity polymerization catalysts can be obtained; % DVB content is less restrictive, suitable for lower activity polymerization catalysts A polymerization movement can be provided. The term “highly active” is defined as about 1 × 10⁷g poly -Mer / Mole Transition Metal Compounds-Catalyst Systems Capable of an Activity Greater than Pressure-Time With respect to "low activity" may be understood to be less than approximately that amount.   Suitable as an olefin polymerization catalyst by coordination polymerization or insertion polymerization according to the present invention. The transition metal compounds are catalyzed by the cocatalyst activators described for the present invention. Useful in traditional Ziegler-Natta coordination polymerization when it can be activated Known transition metal compounds and also known to be useful in coordination polymerization Metallocene compounds. They typically have their transition metal State, i.e., the group 4 to 10 group whose transition metal has the highest oxidation number. A transition metal compound, wherein at least one metal ligand is attracted by the cocatalyst activator. And their ligands include, in particular, hydrides, alkyls and silyls. Included. Ligands that can be abstracted and transition gold with them Genus compounds include those described in the background. For example, U.S. Pat. See Nos. 8,401 and 5,278,119. The synthesis of those compounds has been published Are well known from the literature. In addition, the metal ligand has the activation catalyst of the present invention. Including halogen, amide or alkoxy moieties that cannot be extracted with a medium (e.g., , Biscyclopentadienyl zirconium dichloride) when they are lithium Muhydride, aluminum hydride, or alkyl, alkylalumoxane, A known alkylation reaction using an organometallic compound such as a Lignard reagent Can be converted. Also, before the addition of the activating anion compound, the organoaluminum compound The reaction of the product with a dihalo-substituted metallocene compound is described in European Patent Application Publication (EP- A1) See No. 0570982. All references according to US patent practice Is incorporated by reference.   Extraction to form catalytically active transition metal cations A meta that includes or can be alkylated to include at least one ligand capable of Additional descriptions of locene compounds can be found in the patent literature, e.g., European Patent Application Publication 0129368. No. 4,871,705, No. 4,937,299, No. 5,324,800, European Patent Application JP0418044, European Patent Application Publication No. 0591756, PCT Application Publication WO92 / 00333 and And PCT Application Publication No. WO 94/01471. Such metallocene compounds are In the present invention, 4,5,6,9 substituted with mono- or bi-cyclopentadienyl Or a Group 10 transition metal compound, wherein the auxiliary ligand is itself substituted with one or more groups. And can be cross-linked to each other or to a transition metal by a heteroatom . The size and composition of the auxiliary ligand and the bridging element are determined by the ion catalyst of the present invention. Although not critical to the production of the system, it increases the desired polymerization activity and polymer characteristics. It has to be chosen as described in the literature for greatness. Preferably, When crosslinked, the cyclopentadienyl ring (indenyl, fluorenyl , Azulenyl, or substituted cyclopentadiene, including substituted analogs thereof Enyl-based fused ring systems) are lower alkyl (C 2₁-C₆) (Without similar 4-position substituents in the fused ring system), additionally alkyl, cycloa Including alkyl, aryl, alkylaryl and / or arylalkyl substituents In the latter case, the latter have linear, branched or polycyclic structures, for example U.S. Pat. And substituents such as cyclic structures including the structures described in US Pat. No. 5,304,614. That Such substituents each have essentially the characteristics of a hydrocarbyl, typically 30 Having from 1 to 5 non-hydrogen / carbon atoms, such as N, S, O, It can be a heteroatom with P, Ge, B and Si.   Linear polyethylene or ethylene-containing copolymer (at least two copolymers Metallocene compounds suitable for the production of It is one of those known in the art, and for a particular catalog, Patent Application Publication No. 277,004, PCT Application Publication No. WO92 / 00333 and US Patent No. 5,001,20. See Nos. 5, 5,198,401, 5,324,800, 5,308,816 and 5,304,614. I want to be. For producing isotactic or syndiotactic polypropylene The choice of metallocene compounds used for their synthesis and their synthesis is well understood in the art. Specific references can be made to both the patent literature and the academic literature. For example, Journal of Organometallic Chemisry, 369, 359-370 (1989) Please refer to. Typically, these catalysts are sterically rigid, asymmetric, chiral or Is a bridged chiral metallocene. For example, U.S. Pat.No. 4,892,851, National Patent No. 5,017,714, U.S. Patent No. 5,296,434, U.S. Patent No. 5,278,264, PC T application publication 93/19103, European patent application publication (EP-A2) 0577581, European patent Published application (EP-A1) 0578838 and academic literature, Spaleck, W. et al. "The Influence of Aromatic Substituents on the Polymerization Befhvior of Bri dged Zirconocene catalysts ”, Organometallics, 1994, Volume 13, pages 954-963 And “Brownzinger, H. et al.“ Ansa-Zirconocene Polymerization Catalysts with Annelated Ring Ligands-Effects on Catalyti c Activity and Polymer Chain Lengths ”, Organometallics, 1994, Volume 13, 9 See pages 64-970. These documents are incorporated herein by reference. Many of the above are It is directed to catalyst systems with alumoxane activators, but with metal halogens, amides or Can be abstracted by the alkoxy-containing ligand (if it occurs), for example as described above. Substituted with a ligand that can be abstracted by the alkylation reaction described above, A group into which the ten group -C = C- can be inserted, for example hydride, alkyl or silyl; In some cases, analogous metallocene compounds may be used as co-catalysts of the invention for active coordination catalyst systems. Useful with sexual agents. All references cited in accordance with U.S. patent practice Use it.   Typical metallocene compounds include pentamethylcyclopentadienyl titanium Sopropoxide, pentamethylcyclopentadienyltribenzyltitanium, Tylsilyltetramethylcyclopentadienyl-tert-butylamido titanium dichloro Lido, pentamethylcyclopentadienyl titanium trimethyl, dimethylsilylte Tramethylcyclopentadienyl-tert-butylamidozirconium dimethyl, di Methylsilyltetramethylcyclopentadienyldodecylamidohafnium dihi Dolide, dimethylsilyltetramethylcyclopentadienyl dodecylamide haf Monocyclopentadienyl compounds such as dimethyl dimethyl, bis (1,3-butyl, (Tylcyclopentadienyl) zirconium dimethyl, pentamethylcyclopenta Non-bridged biscycles such as dienyl-cyclopentadienyl zirconium dimethyl Lopentadienyl compound; dimethylsilylbis (dehydroindenyl) zirconium A crosslinked biscyclopentadienyl compound such as mudichloride, Rilbisindenyl zirconium dichloride, dimethylsilylbisindenyl Funium dimethyl, sidimethylsilylbis (2-methylbenzindenyl) zircon Dichloride, dimethylsilylbis (2-methylbenzindenyl) zirconi Bridged bisindenyl compounds such as dimethyl dimethyl; and US Pat. Nos. 017,714, 5,324,800 and EP 0591756. And other mono- and bis-cyclopentadienyl compounds such as But not limited to these.   A typical traditional Ziegler-Natta transition metal compound is tetrabenzylzil Conium, tetrabis (trimethylsilylmethyl) zirconium, oxotris ( (Trimethylsilylmethyl) vanadium, tetrabenzylhafnium, tetraben Zir titanium, bis (hexamethyldisilazide) dimethyl titanium, tris (trimethyl (Silylmethyl) niobium dichloride, tris (trimethylsilylmethyl) tantalum Contains dichloride. An important feature of such compositions for coordination polymerization is that A ligand that can be extracted by rotonation and an ethene (olefin) group Is the ligand to get. These characteristics are due to the extraction of transition metal compounds and the accompanying It allows the production of the corresponding ionic catalyst composition of the present invention.   Other organometallic transition metal compounds suitable as olefin polymerization catalysts according to the present invention are Can be converted to an active cation as a catalyst by ligand abstraction, Non-arrangements that are unstable enough to be displaced by such olefinically unsaturated monomers Which can be stabilized in its active electronic state by a coordinating or weakly coordinated anion One of the Group 10 compounds. Examples of those compounds are described in the patent literature Compounds are included. U.S. Pat.No. 5,318,935 teaches the insertion polymerization of α-olefins. And Uncrosslinked Bisamide Transition Metal Catalyst Compounds of Group 4 Metals Is described. PCT Application Publication No. WO 96/23010 contains ion activation and Diimine nickel and palladium compounds suitable for refin polymerization are described . Low coordination polyanionic ancillary coordination with active transition metal center in high oxidation state Transition metal polymerization catalyst systems from Group 5-10 metals stabilized by the No. 5,502,124 and its divisional application US Pat. No. 5,504,049. D.H.McConvill crosslinked bis (arylamide) group 4 compound for olefin polymerization e, et al., Organometallics, 1995, Vol. 14, pages 5478-5480. Combination Synthesis methods and characterization of compounds are shown. Macromolole by D.H.McConvillie et al. cules, 1996, Vol. 29, pages 5241-5243, include cross-linked bis That the (arylamide) group 4 compound is an active catalyst for the polymerization of 1-hexane Has been described. Other transition metal compounds that are more suitable according to the invention include those described on February 7, 1997 No. 08 / 798,401, filed Feb. 24, 1997, filed on Feb. 24, 1997 United States Patent Application No. 08 / 803,687, U.S. patent application Ser. No. 08 / 806,181, filed Feb. 25, 1997, 1997 US Patent Application No. 60/041258 filed March 17 and PCT Application Publication No. WO 96 / Includes compounds described in No. 40806. Those according to US patent practice The references are each incorporated by reference. Description of synthesis of support-bound components CompoundAIs the following formulaB: Polymer- (R¹) (R^Two) (R^Three) NB (R¹, R^Two, R^ThreeIs as defined above) From the corresponding neutral amine as defined in at least 0.1 molar equivalent of acid or Excess acid H⁺X^-, Followed by a compatible non-coordinating anion M ′⁺NCA^- Can be produced by ion exchange with a salt of In the most general terms, M '⁺Yes Some cation species, X^-Is any anionic species. H⁺X^-IsB PK lower than the conjugate acid of_aThat you must be chosen to have It will be clear to those skilled in the art. Besides, M '⁺And X^-Is the ion exchange reaction The by-products are selected to be soluble in the reaction solvent of choice or in a compatible washing solvent. I have to do it. Representative suitable X^-Groups include halides, chlorates, Perchlorate, triflate, perhaloborate and And perhaloanitimonate, but not limited to Not determined. Representative suitable M '⁺Groups include alkali metal cations and ammonia Cations, but are not limited thereto. Finally, ammonium Protonation of amines to form salts is a technique well known in the art. Yes, H⁺X^-It should be noted that this will make the selection easier. Preferably,ARaw The adult isBOf at least 0.1 molar equivalent of the compatible non-coordinating anion. Ammonium salt, R^FourR^FiveR⁶NH⁺NCA^-Single reaction smell by reacting with Can be manufactured. R^Four, R^FiveAnd R⁶⁺Is the above R¹, R^TwoAnd R^ThreeThe same group as the group of And they areAPK of the product_aPK lower than_aAmmonium with value With the additional criterion that they must be chosen to obtain a salt. pK_a Are well known in the art, and the pK calculated experimentally is_a Are known for various amines. Thereby, common to those skilled in the art Knowledge of the guiding principle is provided (e.g., aryl substitution compared to alkyl substituents) Base pK_aIs low). For example, p by Perrin, D.D., Dempsey, B., Serjeant, E.P. K_a Predictions for Organic Acids and Bases (Chapman and Hall, London ( 1981)). Suitable solvents include aliphatic and aromatic hydrocarbons, ethers (Including cyclic ethers) and halogen-containing carbon compounds (both aliphatic and aromatic) (Including the halogen-containing carbon compound).   BIs a functionalized monomer and a monomer precursor of the polymer support of the present invention. Can be produced by direct copolymerization of In particular, p-dimethylaminostyrene is Amine-functionalized precursors of the catalysts of the present invention which can be copolymerized with benzene and divinylbenzene Generate Preferably,BThe compound ofC: Polymer-YC Where Y is the amine functional group R described above.¹R^TwoR^ThreeCan be easily converted to N- Is a known functional group) From a functionalized polymer precursor of A wide variety of functional groups can be Methods for converting to functional groups are well known in the art and include suitable functional groups. Groups include alkanes, alkenes, alkyl halides, aryl halides, Azides, nitro compounds, alcohols, aldehydes and ketones, nitriles And organometalloids (for a general description, see "C. omprehensive Organic Transformations: a guide to functional group prepara options, "pp. 385-438, VCH publishers, 1989) Not done.   Known for reactions in the art that proceed with high selectivity and essentially measurable yields There are many reactions of the type described above, so that The active agent is in essentially pure form, i.e., without significant amounts of reaction by-products. It can be easily manufactured as one molecular structure. Optimal reaction conditions with infrared spectroscopy Useful for monitoring the extent of the reaction to further ensure high purity products Analytical methods are provided. In particular, commercially available chloromethylated polystyrene-divinyl vinyl Benzene copolymer beads with various dihydrocarbyl secondary amines Light precursorBTo produce a weak base anion exchange resin. Damage of those substances By reaction with tylanilinium tetrakis (perfluorophenyl) borate, typeA, A polymer functionalized with the protonated ammonium salt of the present invention A support is obtained.   Typically, the polymer support is used in an amount of 0.01-0.7 mg equivalent per gram of polymer. More preferably the olefin polymerization of the present invention having 0.03-0.3 mg equivalent of transition metal compound A catalyst composition is used. The co-catalyst activator supported on the polymer of the present invention is Suitably contains 0.02-0.9 mg equivalent of metal or metalloid atoms per gram .   When using the supported ionic catalysts of the present invention, one additional catalyst is added to the overall catalyst system. A maintenance scavenging compound may be included. The meaning of the term "scavenging compound" is Contains compounds that are effective in removing polar impurities from the environment. The impurities are Unintentionally introduced with any of the It can adversely affect catalyst activity and stability. Impurities reduce catalytic activity, May fluctuate or even be eliminated. Polar impurities, or catalyst poisons, include water, oxygen, Metal impurities and the like are included. Before such is supplied to the reaction vessel, for example , After or during the synthesis or manufacture of various components, by chemical treatment or careful separation techniques It is preferable that the following steps be performed. Some small amounts of scavenging compounds are still usually heavy It can be used in the joining process itself.   Typically, the scavenging compound is disclosed in U.S. Patent Nos. 5,153,157, 5,241,025 and PCT Group 13 organics of published applications WO 93/14132, WO 94/07927 and WO 95/07411 Organometallic compounds such as metal compounds. Examples of such compounds include triethyl Aluminum, triethyl borate, triisobutyl aluminum, methyl Alumoxane, isobutylalumoxane and tri (n-octyl) aluminum I will. Metals or metalloids to minimize deleterious interactions with active catalysts Bulk or C shared at the center₈-C₂₀Having a linear hydrocarbyl substituent Scavenging compounds are preferred. Supported transition metal cation-noncoordinating anion pairs and The amount of scavenging agent used is usually that amount effective to increase activity during the polymerization reaction. To minimize.   In the gas phase method, a supported catalyst is used, and ethylene produced by coordination polymerization is used. It is carried out under gas phase conditions suitable for homopolymers or copolymers. Examples of those are rice No. 4,543,399, 4,588,790, 5,028,670, 5,352,749, 5,382,638 , 5,405,922, 5,422,999, 5,436,304, 5,453,471 and 5,463,999 In WO 94/28032, WO 95/07942 and WO 96/00245 Can be Each is incorporated by reference according to United States patent practice. Typically The method is carried out at a temperature of about -100 ° C to 150 ° C, preferably about 40 ° C to 120 ° C, about 700 ° C. The operation is performed at a pressure of 0 kPa or less, typically about 690 kPa to 2415 kPa. Fluidized bed And a continuous process using a recycle stream as the fluid medium.   In a slurry polymerization method in which the immobilized catalyst system of the present invention can be used, the polymerization medium is propylene. A liquid monomer such as butane or a hydrocarbon solvent or diluent, advantageously propane, Aliphatic paraffins such as isobutane, hexane, heptane, cyclohexane, etc. Or a method that can be an aromatic compound such as toluene, typically be written. The polymerization temperature is preferably lower than the temperature considered low, e.g. 0 ° C to 30 ° C or higher, up to about 150 ° C, preferably 50 ° C It can be at a temperature of from about 80 ° C. or any range between the indicated endpoints. Pressure The force can vary from about 100 psia to 700 psia (0.76-4.8 MPa). Other notes Nos. 5,274,056 and 4,182,810 and PCT application publication WO 94/21962. And are incorporated by reference in accordance with U.S. Patent Practice.   In the method embodiments described above using the catalysts of the invention described herein, Saturated monomers, i.e., olefinic or ethylenically unsaturated monomers, may have Or about 3 × 10⁶Molecular weight (weight average or M_wTo produce a polymer product having Can be polymerized. Most typically, the polymer product will have from about 1000 to about 1.0 x 10⁶ M_wHaving. Suitable unsaturated monomers include ethylene, C_Three-C₂₀Linear or minute Branched α-olefin, C_Four-C₂₀Cyclic olefin, C_Four-C₂₀Non-conjugated diolefin , C_Four-C₂₀Geminally unsubstituted olefins, C₈-C₂₀Stille Olefin or C₂₀-C₁₀₀α-olefin macromers are included. Preferably The polymer products are polyethylene homopolymers and copolymers, especially polyethylene. Renplastics, plastomers and elastomers; atactic, syn Polypropylene homo including geotactic or isotactic polypropylene Polymers and copolymers; and cyclic olefin copolymers, especially ethylene- One of the rubornene copolymers.Industrial applicability   The supported catalyst according to the invention is a catalyst derived from olefinically unsaturated monomers. Useful for industrial means of making addition or insertion polymers. In particular, the catalyst of the present invention , As being implemented on a large scale industrially and globally according to the previous description of those methods Particularly suitable for use in a gas phase or slurry process. Such polymer production The method is applicable to a large amount of plastics, thermoplastic elastomers, films and fibers. For packaging, packaging, adhesive substrates and molded articles used in normal use Used for mer. Alternatively, the method of the present invention is a combined method of catalyst evaluation. It is easily spread out to take advantage of. The activator supported on the polymer is a proton Library structures useful for optimizing novel single-site catalyst systems that can be activated by It is a valuable intermediate for construction and screening.Example general   Non-functionalized polystyrene-divinylbenzene copolymer beads (1% DVB, 200- 400 mesh) provided by Biorad Laboratories (Hercules, CA). And carefully washed before use. Chloromethylated beads were obtained from Biorad (4.0 mg (Equivalent Cl / g, 200-400 mesh; and 1.35 mg equivalent Cl / g, 200-400 mesh) And Acros Organics (Pittsburgh, PA) (0.4 mg equivalent Cl / g, 100- 200 mesh), use either of the The aqueous K to avoid hydrolysis_TwoCO_ThreeChange to stirring for 1/2 hour in The above washing step was modified. Bubble argon for 1/2 hour before use By CH_TwoCl_TwoWas degassed. Used when receiving other solvents and reagents . Low functionalization by the method of T. Lett., 1975, 53, 4367 by J.T.Sparrow Chloromethylated beads (0.15 mg equivalent Cl / g) were produced. Agitated temperature controlled In hexane with hexene and tri-isobutylaluminum in a reaction vessel To carry out slurry polymerization at a constant ethylene head pressure. Example Abbreviations in include: THF (tetrahydrofuran), Ph ( Phenyl), Me (methyl), Bn (benzyl). PS-CH_TwoN (CH_Three)_TwoH]⁺[B (C₆F_Five)_Four]^-   Chloromethylated polystyrenedivinylbenzene loaded with 0.15-4.0 mg equivalent of Cl / g Zen copolymer beads in dimethylamine solution in THF (2M, Aldrich) Swell and stir at room temperature for 2 days. Then they were added in THF, 2: 1 THF / water, 1: 2 THF / water, water (twice), 1: 2 THF / water, 2: 1 THF / water and Rinse with THF (twice) and dry under vacuum at 60 ° C. overnight. Aminated beads to C H_TwoCl_TwoMedium [PhNMe_TwoH] [B (C₆F_Five)_Four] (1.5 eq) with a 0.07 M solution for 1.5 hours, then filtration And CH_TwoCl_TwoRinse (4 times), bead with boron loading of 0.15-1.1 mg equivalent boron / g Got. Boron loading was determined gravimetrically and by IR analysis. Then those Were treated with various Group 4 metallocenes and the product of 0.14-0.7 mg equivalent catalyst / g of beads The active catalyst species in the above was produced. Metallocene loading is metallocene and boric acid Estimated by quantitative reaction with chloride beads. The borated beads were typically treated with three equivalents of the metallocene compound. PS-CH_TwoNPh (CH_Three)_TwoH]⁺[B (C₆F_Five)_Four]^-   Chloromethylated polystyrene divinylbenzene loaded with 0.4-4.0 mg equivalent of Cl / g Swelling the Zen copolymer beads in straight N-methylaniline and at room temperature Stir for 2 days. Then they were combined in THF, 2: 1 THF / water, 1: 2 THF / Rinse with water, water (twice), 1: 2 THF / water, 2: 1 THF / water and THF (twice) , Dried at 60 ° C under vacuum overnight. CH aminated beads_TwoCl_TwoMedium [Ph_TwoNH_Two] [B (C₆F_Five)_Four] (1.5 equiv.) For 1.5 h, then filtered and rinsed with CH2Cl2 (4 Times), beads having a boron loading of 0.36-0.87 mg equivalent boron / g were obtained. Boron product The load was determined by weighing after careful drying.Example 1 -Production of catalyst A   In a glove box in an inert atmosphere, make 0.500 g. Having 0.67 mmol of available functional groups per gram of beads (ie, 0.67 mmol g equivalent) Protonated ammonium salt activator PS-CH_TwoN (CH_Three)_TwoH]⁺[B (C₆F_Five)_Four]^-To 10 35 m with stirring with a magnetic stirrer at 25 ° C. under nitrogen in a 0 ml round bottom flask of dry, oxygen-free toluene and then 0.609 g of Bis (tetramethylcyclopentadienyl) hafnium dimethyl was added little by little ( (As a solid). The reaction was stirred for 1 hour, then the supported activator was removed by vacuum filtration. Washed with four 15 ml portions of dry, oxygen-free toluene isolated by filtration And titrated with about 15 ml of dry, oxygen-free pentane. Then, carried The dried catalyst was dried in vacuum overnight to give 0.52 mmol of transition metal per g of final catalyst. 0.522 g of final catalyst with a calculated loading of (some material loss due to transfer Lost).Example 2 -Production of catalyst B   Catalyst B was prepared similarly to Catalyst A, but with a 0.27 mmol / g bead. Protonated ammonium salt activator with usable functional groups (i.e. 0.27 mg equivalent) PS-CH_TwoN (CH_Three)_TwoH]⁺[B (C₆F_Five)_Four]^-With 0.057 g of bis (tetramethylcyclopenta (Dienyl) hafnium dimethyl to give 0.24 mmol / g final catalyst 0.113 g final catalyst with calculated loading of transition metal (some due to transfer Material loss).Example 3 -Production of catalyst C   Catalyst C was prepared similarly to Catalyst A, but with a 0.67 mmol / g bead. Protonated ammonium salt activator with usable functional groups (i.e. 0.67 mg equivalent) PS-CH_TwoN (CH_Three)_TwoH]⁺[B (C₆F_Five)_Four]^-With 1.138 g of bis (tetramethylcyclopenta (Dienyl) hafnium dimethyl to give 0.52 mmol / g final catalyst. 1.200 g of final catalyst with calculated loading of transition metal (some due to transfer Material loss). Double the volume of solvent and washings and run the reaction in a 250 ml round bottom flask. I went all over the place. Example 4-Preparation of activator beads with reduced borate loading   100 g of chloromethylated polystyrene having a chloride content of 1.00 mg eq / g Beads (200-400 mesh, 1% divinylbenzene cross-linked) (ie 1.00 mmol / g of available reactive functional groups per g of beads) And 800 ml of a THF solution for 16 hours. Reaction completed by IR spectroscopy It was proved. Then rinse the beads and at 60 ° C under vacuum Dried for 16 hours. 10.00 g of this aminated bead is transferred to an inert environment And then swelled in toluene (150 ml). 100ml hot torr Dimethylanilinium tetrakis (perfluorophenyl) borane dissolved in ene Acid salt (0.806 g) was added to the swollen beads with vigorous stirring of the suspension. Was. After 1 hour, the solution was filtered, washed twice more with 100 ml of toluene, (100 ml) for 15 minutes and finally dried at 60 ° C under vacuum for 16 hours To give beads with a calculated loading of 0.09 mg eq / g.Example 5 -Catalyst D production   Catalyst D was prepared in the same manner as catalyst A, but with 0.09 mmol / g of beads. Example 4 assumed to have functional groups available (ie, 0.09 mg equivalent). -Produced protonated ammonium salt activator PS-CH with reduced loading_Two N (CH_Three)_TwoH]⁺[B (C₆F_Five)_Four]^-(Ie 0.67 mg equivalent) was used. 50ml of the beads Swell / slurry in toluene and add 0.09 g of bis (1,3-butyl-methylcyclopentene) (Tadienyl) zirconium dimethyl and stirred for 2 hours, then filtered and Washed twice with 30 ml of Ruen, slurried with 50 ml of pentane for 15 minutes, filtered, Dry for 12 hours at room temperature in vacuo to give 0.09 mmol of transition gold / g final catalyst 1.92 g (some material loss due to transfer) pale yellow with calculated loading of genus The final catalyst was obtained.Example 6 -Catalyst E production   Bis (1,3-butyl-methylcyclopentadienyl) zirconium dimene of Example 5 0.151 g of dimethylsilylbis (tetrahydroindenyl) zirco Catalyst E was prepared exactly as catalyst D, except for using dimethyl dimethyl. Ultimate 1.77 g with a calculated loading of 0.09 mmol of transition metal per g of catalyst (by transfer An off-white final catalyst (with some material loss) was obtained.Example 7 -Production of catalyst F   Catalyst F was prepared similarly to Catalyst A, but with a 0.6 mmol / g bead. Protonated ammonium salt activator with usable functional groups (i.e. 0.6 mg equivalent) PS-CH_TwoN (CH_Three)_TwoH]⁺[B (C₆F_Five)_Four]^-(Beads are 200-400 mesh, 2% 12.0 g of bis (1,3-butylmethylcyclyl) (Lopentadienyl) zirconium dimethyl to give 0.5 mg / g final catalyst. 55.7 g of orange final catalyst having a calculated loading of remoles of transition metal (Some loss of material due to migration) was obtained. Increase the amount of solvent and washing solution by 10 times, Was performed in a 1000 ml round bottom flask.Example 8 Phase ethylene-hexene polymerization in n-hexane   Mechanical agitator, external water jacket for temperature control, bulkhead inlet and dry nitrogen And 11-volume autoclave reactor with controlled feed of ethylene The polymerization was performed in a slurry phase. The reactor was dried at 115 ° C and completely I noticed. Hexane (400 cc) was added as a diluent, and pentane was 0.6 cc of a 1.25 M solution of triisobutylaluminum in carbon 45 ml of hexene was added via ure. 75 psig (5.17 (Bar) of ethylene. 0.060g of catalyst in a 10cc stainless steel cylinder A (a cylinder loaded in an inert atmosphere glove box) is charged and swaged. The reactor was fitted with a swagelock fitting. Then the reactor The catalyst was introduced. Keep the reaction vessel within 3 ° C of 40 ° C and with a constant ethylene flow The polymerization was continued for 30 minutes while maintaining 75 psig ethylene pressure (5.17 bar). Cool down quickly The reaction was stopped by venting. 33.0 g of ethylene-hexencopo The limer was recovered. The polyethylene has a weight average molecular weight of 99,600 and a molecular weight of 2.9. It had a volume distribution and 21% hexene by weight. Touch the polymer yield By dividing by the total charge of the medium, dividing by the time, and dividing by the absolute monomer pressure at atmospheric pressure, The activity of the bulk polymerization was calculated to give a value of 2189 g PE / g catalyst-time-pressure. Poly Divider yield is divided by the total mmol of transition metal contained in the catalyst charge and divided by time. Calculate the specific polymerization activity by dividing by the absolute monomer pressure at atmospheric pressure. gPE / mmol catalyst-time-atmosphere values were given. Similar polymerization using catalysts B and C Short run and long run times (all other conditions were the same). related Some data are summarized in Table 1. Example 9Phase ethylene-hexene polymerization in 1-isobutane   Mechanical agitator, external water jacket for temperature control, bulkhead inlet and dry nitrogen And 11-volume autoclave reactor with controlled feed of ethylene The polymerization was performed in a slurry phase. The reactor was dried at 115 ° C and completely I noticed. Add isobutane (400cc) as a diluent and use a hermetic syringe to 0.6 cc of a 1.25 M triisobutylaluminum solution in tan is added as scavenger, Different amounts of hexene (35 ml for catalyst D, 15 ml for catalyst E) depending on the cannula Was added. The reactor was charged with 75 psig (5.17 bar) ethylene at 60 ° C ( That is, an ethylene overpressure of 75 psig was used at the head of the diluent vapor pressure). 10cc Catalyst in a stainless steel cylinder (capacity in an inert atmosphere glove box). Was loaded and attached to the reactor with Swagelok fittings. . Next, a catalyst was introduced into the reactor. Keep the reaction vessel within 3 ° C of 60 ° C and constant The polymerization continued for 30 minutes while maintaining 75 psig ethylene pressure (5.17 bar) with a stream of Tylene. I did. The reaction was stopped by rapid cooling and degassing. Conduct polymerization activity Calculated as in Example 8. The relevant data is summarized in Table 2.   In all slurry polymerization examples, the product is the starting material of polystyrene beads. High bulk density (> 0.4g / cc) discontinuous exposure with size distribution similar to size distribution Isolated in the form of round spherical beads. In the case of catalyst B which was carried out for 2 hours, Had dimensions in millimeters. This means that each polymer bead is Suggesting that particle breakage is essentially the result of polymerization from individual catalyst beads I have. Analysis of the ethylene uptake data shows that the consumption rate during the first 15 minutes of the polymerization is Shows a controlled increase in degrees, the speed of which is essentially maintained thereafter. (After 2 hours, the speed is still a maximum of> 90%). these Observations demonstrate the long active life of the catalysts of the present invention. 2 hours polymerization in Table 1 MWD shows that the ethylene concentration is essentially constant during the course of the reaction Dramatic change in hexene concentration (> 50% hexene consumed) You can understand it when you look at it.   A sample of the previously described supported catalyst F was prepared as described below for gas phase ethylene / Used for 1-hexene copolymerization studies. Like catalyst efficiency, built-in capacity and 1-hexene At 300 psig (20.7 bar) total pressure, 175 F Operating at a reactor temperature of ° (79.4 ° C) and a cycle gas velocity of 0.7 ft / sec (21 cm / sec) A continuous fluidized bed gas phase reactor was used. Do not charge scavenger to reactor during polymerization Was. The catalyst was charged at a rate sufficient to maintain the desired production rate. Operation Day Were included in Table 3. After at least three bed turnovers, the polymer -Samples were collected and analyzed. Example 10-Production of catalyst G   Catalyst G was prepared similarly to catalyst A, but with a 0.3 mmol / g bead. Protonated ammonium salt activator PS-CH having functional group usable_TwoN (CH_Three)_TwoH]⁺[B (C₆F_Five)_Four]^-(I.e., 0.6 mg equivalent) was replaced with 0.628 g of dimethylsilylbis (tetrahydro (Indenyl) zirconium dimethyl to give 0.27 mmol / g final catalyst 4.03 g of final yellow catalyst with a calculated loading of transition metal Some material loss). The amount of solvent and washings was doubled and the reaction was Performed in a 1 volume round bottom flask.Example 11 -Aggregation phase propylene polymerization using catalyst G   Mechanical agitator, external water jacket for temperature control, bulkhead inlet and dry nitrogen And an 11-volume autoclave reactor with a controlled feed of propylene The polymerization was carried out in the slurry phase. The reactor was dried at 115 ° C and completely Degassed. 1.25 M in pentane, added as a scavenger, using an airtight syringe Propylene (400 ml) was added together with 0.6 cc of the triisobutylaluminum solution of . 0.40 g of catalyst G (inert environment glove box) was placed in a 10 cc stainless steel cylinder. Reaction with a Swagelok fitting I put it in the bowl. Next, a catalyst was introduced into the reactor. While maintaining the reaction vessel at 40 ° C The polymerization was continued for 60 minutes. The reaction was stopped by rapid cooling and degassing. 39.8 g of isotactic polypropylene was recovered. Polymer yield as catalyst By dividing by the total number of moles of transition metal contained and dividing by time, the bulk polymerization activity The properties were calculated to give a value of 99.5 gi-PP / g catalyst-time. In this embodiment, the Chiral cross-linked metallo for producing ctic polypropylene (i-PP) Illustrates the use of Sen.

[Procedure of Amendment] Article 184-4, Paragraph 4 of the Patent Act [Date of Submission] October 2, 1998 (1998.10.2) [Details of Amendment] Claims 1. a) a) a polymer support having a surface area of about 1 to 50 m ² / g, and ii) functionalized with a protonated ammonium salt of a non-coordinating anion; and b) an auxiliary ligand; Organometallic transition metals having at least one labile ligand that can be abstracted by protonation and at least one labile ligand into which an olefin monomer can be inserted for polymerization An olefin polymerization catalyst composition containing a reaction product with a compound. 2. The catalyst composition according to claim 1, which is an organometallic transition metal compound or a monocyclopentadienyl ligand-containing Group 4 metal compound. 3. The catalyst composition according to claim 1, wherein the organometallic transition metal compound is a group 4 metal compound containing a biscyclopentadienyl ligand. 4. 2. The organic metal transition metal compound is a Group 4 metal compound containing a monocyclopentadienyl ligand or a Group 4 metal compound other than a Group 4 metal compound containing a biscyclopentadienyl ligand. Catalyst composition. 5. The catalyst composition according to any one of claims 2 to 4, wherein the non-coordinating anion is a non-coordinating anion derived from an organic boron compound or an organic aluminum compound. 6. The catalyst composition according to claim 1, wherein the organometallic transition metal compound has a high activity for olefin polymerization, and the polymer support i) has a surface area of about 10 m ² / g or less. 7. A polymer-supported activator comprising a polymer support having a surface area of about 1 to 50 m ² / g and functionalized with a protonated ammonium salt of a non-coordinating anion. [Amendment of Proceedings] Article 184-8, Paragraph 1 of the Patent Act [Date of Submission] May 10, 2001 (2001.10.10) [Content of Amendment] [Correction 1] 12 pages from the bottom of page 8 of the specification Correct "all" to "all". [Error 2 Correction] 10 lines from the bottom of page 8 of the specification, "To be pulled out" is corrected to "To be pulled out". [Correction 3] Lines 4 to 3 from the bottom of page 8 of the specification “In the present invention, a group 4, 5, 6, 9 or 10 transition metal compound substituted with mono- or bi-cyclopentadienyl, To "may be described herein as a Group 4, 5, 6, 9 or 10 transition metal compound substituted with mono- or bis-cyclopentadienyl." [Mistranslation Correction 4] After the description, page 9, line 12, "Can.", Add "All references are incorporated by reference for purposes of US patent practice." [Mistranslation Correction 5] "Dimethylsilylbis (dehydroindenyl) zirconium dichloride" is corrected to "dimethylsilylbis (dehydroindenyl) zirconium dichloride" at line 9 to line 8 from the bottom of the specification. [Correction 6] From page 10 of the specification, lines 6 to 5 from the bottom: "Sidimethylsilylbis (2-methylbenzindenyl) zirconium dichloride" corrected to "dimethylsilylbis (2-methylbenzindenyl) zirconium dichloride" . Correct In the correction of the incorrect translation 7] specification page 12, 9 to 10 rows ^{- -} the "acid or molar excess of the acid H ⁺ X" According to "to molar with acid excess of acid H ⁺ X". [Mistranslation Correction 8] specification page 12, line 15 "by-product is," a "by-product, M ^'+ X ^- is" correct to. [Mistranslation Correction 9] From the bottom of page 13 of the specification, the 7th line, "Because there is a reaction," is corrected to "Because there is a reaction (synthesis of amine, protonation of amine, ion exchange)." [Error Correction 10] Specified on page 14, lines 9 to 10 "Correct one" is corrected to "One or more". [Error 11 Correction] Eight lines from the bottom of page 14 of the specification, "triethyl baud rate" is corrected to "triethyl borane". [Mistranslation Correction 12] From the bottom of page 14 of the specification, 5 lines from the bottom, "center" is corrected to "center". [Correction 13] From the bottom of page 15 of the specification, the 4th line “Unsubstituted” is corrected to “Disubstituted”. [Error 14 Correction] The 19th page, 1 page, "10.00g" is corrected to "10.00g". [Mistranslation Correction 15] Delete page 12, line 12 (ie, 0.67 mg equivalent) of the specification. [Mistranslation correction 16] The description on page 19, line 13, "0.09g" is corrected to "0.90g". [Mistranslation Correction 17] “Lump polymerization activity” in Table 1 on page 21 of the specification is corrected to “Lot productivity”. [Mistranslation Correction 18] In the title of Table 2 on page 21 of the specification, “isobutylene” is corrected to “isobutane”. [Incorrect Translation 19] The "bulk polymerization" in Table 2 on page 21 of the specification is corrected to "lot productivity". [Correction 20] Correction from page 22, line 6, “Maximum value of> 90%” to “> 90% of maximum value”. To correct the second stage of the correction of the incorrect translation 21] specification, page 23, Table 3 the "H ₂ concentration (mol%)" in the "H ₂ concentration (ppm)". [Mistranslation Correction 22] From page 23, the bottom of the specification, line 13 “corrected protonated ammonium salt activator” is corrected to “5.04 g protonated ammonium salt activator having functional group”. [Error Translation 23] The claims are corrected as follows. "1. a) a polymer support having a surface area of 10 m ² / g or less, ii) functionalized with a protonated ammonium salt of a non-coordinating anion and b) an auxiliary ligand, said ammonium Organometallic transition metals having at least one labile ligand capable of being abstracted by protonation of the salt and at least one labile ligand into which an olefin monomer can be inserted for polymerization Olefin polymerization catalyst composition comprising a reaction product with a compound 2. The catalyst composition of claim 1, wherein the polymer support is made from a polystyrene-divinylbenzene copolymer gel or bead. An olefin polymerization method comprising contacting the above ethylenically unsaturated olefin with the catalyst composition according to claim 1 under suitable polymerization conditions. ”

────────────────────────────────────────────────── ─── Continuation of front page    (81) Designated country EP (AT, BE, CH, CY, DE, DK, ES, FI, FR, GB, GR, IE, I T, LU, MC, NL, PT, SE), AU, BR, C A, JP, KR, SG (72) Inventors Diaz, Anthony Jai             77062, Texas, United States             Newton, Quiat Green Co             G 1411 (72) Inventors Freiche, Jean M. Jay             United States, California             94611-1851, Auckland, Swain             Land Road 6414 (72) Inventor Roscoe, Stephen Bee             C, 55125, Minnesota, United States             Budbury, Number 112, Century             ー Circle 1701

Claims (1)

[Claims] 1. a) a polymer support having a surface area of about 1 to 400 m ² / g, ii) functionalized with a protonated ammonium salt of a non-coordinating anion, and b) an auxiliary ligand, Organometallic transition metals having at least one labile ligand that can be abstracted by protonation and at least one labile ligand into which an olefin monomer can be inserted for polymerization An olefin polymerization catalyst composition containing a reaction product with a compound. 2. The catalyst composition according to claim 1, wherein the organometallic transition metal compound is a group 4 metal compound containing a monocyclopentadienyl ligand. 3. The catalyst composition according to claim 1, wherein the organometallic transition metal compound is a group 4 metal compound containing a biscyclopentadienyl ligand. 4. 2. The organic metal transition metal compound is a Group 4 metal compound containing a monocyclopentadienyl ligand or a Group 4 metal compound other than a Group 4 metal compound containing a biscyclopentadienyl ligand. Catalyst composition. 5. The catalyst composition according to any one of claims 2 to 4, wherein the non-coordinating anion is a non-coordinating anion derived from an organic boron compound or an organic aluminum compound. 6. Organometallic transition metal compound has a high activity to olefin polymerization, the polymeric support i) has a surface area of less than about 50 m ² / g, the catalyst composition of claim 1. 7. A polymer-supported activator comprising a polymer support having a surface area of about 1 to 400 m ² / g and functionalized with a protonated ammonium salt of a non-coordinating anion. 8. An olefin polymerization process comprising contacting one or more ethylenically unsaturated olefins with the catalyst composition of claim 1 under suitable polymerization conditions. 9. 9. The method according to claim 8, which is performed under gas phase polymerization conditions. 10. 9. The method according to claim 8, which is performed under slurry polymerization conditions. 11. Olefin is ethylene and C ₃ -C ₈ alpha-olefin and are selected from those combinations, the method according to claim 9 or claim 10. 12. The method according to claim 9, wherein the olefin is selected from ethylene, propylene, 1-butene, 1-hexene and 1-octene and combinations thereof. 13. The method of claim 10 wherein the olefin is propylene, optionally with ethylene. 14． The method according to claim 10, wherein the olefin is selected from ethylene, cyclic olefins and styrenic olefins and combinations thereof. 15.1) a) Formula: polymer- (R ¹ ) (R ² ) (R ³ ) N wherein the polymer is essentially a hydrocarbon polymer bead having a surface area of about 50 m ² / g or less. , R ¹ , R ² and R ³ are the same or different and are selected from the group consisting of hydrogen, hydrocarbyl and substituted hydrocarbyl) b) with a acid at least 0.1 molar equivalent with respect to the molar concentration of the amine 8. A method for producing a polymer-loaded activator according to claim 7, comprising rotonating and 2) performing an ion exchange reaction with a compatible non-coordinating anion salt. 16. a) type, polymers ^{- (R 1) (R 2} ) (R 3) N ( wherein the polymer is essentially a hydrocarbon polymer beads having a surface area of less than about ^{50m 2 / g, R 1,} R ² and R ³ are the same or different and are selected from the group consisting of hydrogen, hydrocarbyl and substituted hydrocarbyl) b) at least 0.1 molar equivalent of a compatible non-anionic anion with respect to the molar concentration of the amine The method for producing a polymer-supported activator according to claim 7, comprising reacting with an ammonium salt of the following. 17． The olefin polymerization catalyst composition according to claim 1, wherein the polymer support contains 0.01 to 0.7 mg equivalent of the transition metal compound per g of polymer. 18. 18. The olefin polymerization catalyst composition according to claim 17, wherein the polymer support contains 0.03 to 0.3 mg equivalent of the transition metal compound per g of polymer. 19. 8. The polymer-loaded activator of claim 7, wherein the polymer support contains from 0.02 to 0.9 mg equivalent of metal or metalloid atoms per g of polymer.