MXPA99012043A - Zwitterionic catalyst activator - Google Patents

Abstract

A catalyst activator particularly adapted for use in the activation of metal complexes of metals of Group 3-10 for polymerization of ethylenically unsaturated polymerizable monomers, especially olefins, comprising a zwitterionic compound corresponding to the formula (I) or (II), wherein:L+ is a protonated derivative of an element of Group 15 of the Periodic Table of the Elements, additionally bearing two hydrocarbyl substituents of from 1 to 50 carbons each, or a positively charged derivative of an element of Group 14 of the Periodic Table of the Elements, said Group 14 element being substituted with three hydrocarbyl substituents of from 1 to 50 carbons each;R1 is a divalent linking group of from 1 to 40 non-hydrogen atoms;R2 independently each occurrence is a ligand group of from 1 to 50 nonhydrogen atoms with the proviso that in a sufficient number of occurrences to balance charge in the compound. R2 is L+-R1-;R4 is a bridging hydride or halide group or a divalent linking group of from 1 to 40 non-hydrogen atoms;M1 is boron, aluminum or gallium;Arf independently each occurrence is a monovalent, fluorinated organic group containing from 6 to 100 non-hydrogen atoms;Y is a Group 15 element;and Z is a Group 14 element.

Description

ACTIVATOR OF ZWITERIONIC CATALYST DESCRIPTION OF THE INVENTION The present invention relates to a compound that is useful as a catalyst activator. More particularly, the present invention relates to compounds which are particularly adapted for use in the addition polymerization of unsaturated compounds in combination with a metal complex of Group 3-10, said activator comprising at least a zwitterionic compound capable of activating the metal complex to cause addition polymerization. Said activator is particularly advantageous for use in a polymerization process, wherein the catalyst, the catalyst activator and at least one polymerizable monomer are combined under polymerization conditions to form a polymeric product. Previously, it is known in the art to activate Ziegler-Natta polymerization catalysts, particularly such catalysts comprising Group 3-10 metal complexes containing aplocated, delocalised ligand groups through the use of Bronsted acid salts capable of transferring a proton to form a cationic derivative or other catalytically active derivative of said metal complex of Group 3-10. Preferred Bronsted acid salts are such compounds that contain a cation / anion pair that is capable of making the metal complex of Group 3-10 catalytically active. Suitable activators include fluorinated aryl borate anions, preferably tetrakis (pentafluorophenyl) borate anions. Additional suitable anions include sterically protected diboro anions corresponding to the formula: X1 / A? B BA? CS2 wherein: S is hydrogen, alkyl, fluoroalkyl, aryl or fluoroaryl, ArF is fluoroaryl, and X1 is either hydrogen or halide, described in US-A-5,447,895. Additional examples include carborane compounds such as described and claimed in US-A-5,407,884. Examples of preferred charged charge activators (cation / anion pair) are ammonium, sulfonium or phosphonium salts capable of transferring a hydrogen ion, described in US-A-5, 198,401 (equivalent to EP-A-277,004, EP- A-468,537 and EP-A-561-479), US-A-5,132,380, US-A-5,470,927 and US-A-5, 153, 157, as well as oxidation salts such as carbonate, ferrocenium and silylium salts, described in US-A-5,350,723, US-A-5, 189, 192 and US-A-5,625,087. Other suitable activators for the above metal complexes include strong Lewis acids including (trisperfluorophenyl) borane and tris (perfluorobiphenyl) borane. The initial composition has previously been described for the end use set forth in EP-A-520,732, while the latter composition is similarly described by Marks, et al., In J. Am. Chem. Soc. 118, 12451-12452 (1996 ). Despite the satisfactory operation of the above catalyst activators under a variety of polymerization conditions, there remains a need for improved cocatalysts to be used in the activation of various metal complexes under a variety of reaction conditions. In particular, previously known activators comprising a salt of Bronsted acid capable of transferring a proton to a ligand of the metal complex, generally and simultaneously produce a neutral by-product such as an amine or phosphine compound. Such by-products are generally difficult to remove from the resulting catalyst composition and can adversely affect the catalytic performance of the resulting catalyst composition. Accordingly, it could be desirable if catalyst activators are provided which can be employed in solution, slurry, gas phase or high pressure polymerizations and under homogenous or heterogeneous process conditions having improved activation properties. In accordance with the present invention, zwitterionic compounds corresponding to the formula are now provided: R1 / -2 + -Rl-M "l - (Arf) 3, R 2M M1R22 \ / ZR22 R1 / R ^ M1 R22 \ / YR¿ where: L + is a protonated derivative of an element of Group 15 of the Periodic Table of the Elements, additionally carrying two hydrocarbyl substituents of 1 to 50 carbons each, or a positively charged derivative of a Group 14 element of the Periodic Table of the Elements, said Group 14 element being substituted with three hydrocarbyl substituents of 1 to 50 carbons each; R is a divalent linking group of 1 to 40 atoms that are not hydrogen; R2 independently of each occurrence is a ligand group of 1 to 50 atoms that are not hydrogen, provided that in a sufficient number of occurrences to balance the charge on the compound, R2 is L + -R1; R4 is a hydride or halide bridge group or a divalent linking group of 1 to 40 atoms that are not hydrogen; M1 is boron, aluminum or gallium; ArF independently of each occurrence in an organic, fluorinated, monovalent group, containing from 6 to 100 atoms that are not hydrogen; And it is an element of Group 15; and Z is an element of Group 14. Further, according to the present invention, there is provided a catalyst composition capable of polymerizing a polymerizable, ethylenically unsaturated monomer comprising, in combination, a metal complex of Group 3-13 and the zwitterionic compound described above, or the reaction product resulting from said combination. Further, according to the present invention, there is provided a process for the polymerization of one or more polymerizable, ethylenically unsaturated monomers comprising contacting them, optionally in the presence of an aliphatic, alicyclic or aromatic inert hydrocarbon, with the composition of catalyst described above. The above zwitterionic boron compounds are only capable of forming active catalyst compositions from Group 3-10 metal complexes without generating separate Lewis base byproducts capable of coordinating the resulting active metal species. As a result, the compounds possess improved catalyst activation properties. Also, they are only adapted for use in the activation of a variety of metal complexes, especially Group 4 metal complexes, under standard and atypical polymerization conditions. All references herein to elements belonging to a certain Group refer to the Periodic Table of the Elements, published and registered by CRC Press, Inc., 1995. Also, any reference to the Group or Groups should be to the Group or Groups as it is reflected in this Periodic Table of Elements using the IUPAC system to list groups. The compounds of the invention are further characterized in the following manner. Examples of preferred zwitterionic boron compounds according to the present invention correspond to the formula: HL '+ -R1-B "(Arf) 3, wherein: R1 is a hydrocarbylene group or a hydrocarbylene group halogen-, alkoxy-, N, N-dihydrocarbylamino-, silyl-, or gerri-substituted, said R1 having from 2 to 40 atoms not representing hydrogen atoms; L 'is dihydrocarbyl substituted nitrogen or a phosphorus group, having from 1 to 50 carbons in each hydrocarbyl group and Arf independently of each occurrence is a fluorinated, monovalent organic group, containing from 6 to 100 atoms not representing hydrogen atoms, highly preferred are the zwitterionic compounds corresponding to the formula: HN + (R5) 2-R1-B "(Arf); wherein: R1 is an alkylene group of C -? - 40 or an arylene group of C6-40; R5 independently of each occurrence is a hydrocarbyl group of C? -50; and Arf in each occurrence is perfluorophenyl, perfluoronaphthyl or perfluorobiphenyl. Generally, the solubility of the compounds of the invention in the aliphatic compounds is increased through the incorporation of one or more oleophilic R5 groups, such as long chain alkyl groups.; long chain alkenyl groups; or long-chain alkyl or halogen-, alkoxy-, amino-, silyl-, or germyl-substituted alkenyl groups or alkenyl groups. By the term "long chain" is meant groups having from 10 to 50 atoms that are not hydrogen in said group, preferably in a non-branched form. It is understood that the catalyst activator can comprise a mixture of groups R5 of different lengths. For example, a suitable activator (wherein L is nitrogen) can be derived from the commercially available long chain amine, which comprises a mixture of two C14, C16 or C18 alkyl groups, and a methyl group. Said amines are available from Witco Corp., under the tradename Kemamine ™ T9701, and from Akzo-Nobel under the trade name of Armeen ™ M2HT. The highly preferred zwitterionic compounds for use herein are: H (R 5) 2 N + - C 2 H 4 - B - (C 6 F 5) 3 H (R 5) 2 N + - C 2 H 4 - B - (C 2 F 9): 3 < H (R? 5Í> v) 2N M ++ - (C2H4) - B- (C6F5) 3, or H (R5) 2N + -C18H36 B- (C12F9) 3, wherein R5 is methyl, phenyl or a mixture of C1-18 alkyl- The zwitterionic compounds herein are easily synthesized through the treatment of a triaryl trialkyl boron compound with an organometallic compound such as an appropriately substituted Grignard reagent or an organic lithium reagent followed by protonation. Catalysts suitable for use in combination with the above cocatalysts include any compound or complex of a metal of Groups 3-10 of the Periodic Table of the Elements, capable of being activated to polymerize ethylenically unsaturated compounds through the activators of the present . Examples include diimine derivatives of Group 10 corresponding to the formula: CT-CT N // \\ M * K2A "where N N is Ar * -N N-Ar * (N M * is Ni (ll) or Pd (li); K is halogen, hydrocarbyl or hydrocarbyloxy; Ar * is an aryl group, especially a 2,6-diisopropylphenyl or aniline group; CT-CT is 1, 2-ethanediyl, 2,3-butanediyl, or form a fused ring system, wherein the two T groups together are a 1,8-naphthanediyl group; and A "is the anionic component of the above separate charge activators. Catalysts similar to the above are described by M. Brookhart, et al., in J. Am. Chem. Soc., 118, 267-268 (1996) and J. ^ Am. Chem. Soc, 117, 6414-6415 (1995), as being polymerization active catalysts especially for the polymerization of α-olefins, either alone or in combination with polar comonomers such as vinyl chloride, alkyl acrylates and alkyl methacrylates The additional catalysts include derivatives of Group 3, 4 or lanthanide metals, which are in the formal oxidation state +2, +3, or + 4. Preferred compounds include metal complexes containing from 1 to 3 groups anionic ligands attached apo neutral, which may be apionic, delocalized, cyclic or noncyclic bound anionic ligand groups Examples of such anionic ligand groups ap are dienyl groups, allyl groups, boratabenzene groups, and arene groups , conjugated or non-conjugated, cyclic or non-cyclic. By the term "attached to p" is meant that the ligand group is attached to the transition metal by sharing electrons from a partially delocalized p-junction. Each atom in the group ap independently delocalized can be substituted with a radical selected from the group consisting of hydrogen, halogen, hydrocarbyl, halohydrocarbyl, substituted hydrocarbyl metalloid radicals, wherein the metalloid is selected from Group 14 of the Periodic Table of the Elements and said hydrocarbyl or substituted hydrocarbyl metalloid radicals are further substituted with a portion containing a heterogeneous atom of Group 15 or 16. Included within the term "hydrocarbyl" are the C 1-20 straight, branched and cyclic alkyl radicals, radicals C6-2o aromatics, C7-2o substituted alkyl aromatic radicals, and substituted C7-2 alkyl or aryl radicals. In addition, two or more of said radicals together can form a fused ring system, including fused ring systems, partially or fully hydrogenated, or can form a metallocycle with the metal. Suitable substituted hydrocarbyl organic metalloid radicals include mono-, di- and tri-substituted organic metalloid radicals of the Group 14 elements, wherein each of the hydrocarbyl groups contains from 1 to 20 carbon atoms. Examples of suitable substituted hydrocarbyl organic metalloid radicals include tri-methylsilyl, triethylsilyl, ethyldimethylsilyl groups, triphenylgermyl and trimethylgermyl. Examples of portions containing a heterogeneous atom of Group 15 or 16 include amine moieties, phosphine, ether or thioether or its divalent derivatives, for example, amide, phosphide, ether or thioether groups attached to the transition metal or lanthanide metal, and attached to the hydrocarbyl group or to the group containing a substituted hydrocarbyl metalloid. Examples of suitable delocalised, anionic, ap-linked groups include cyclopentadienyl, indenyl, fluorenyl, tetrahydroindenyl, tetrahydrofluorenyl, octahydrofluorenyl, pentadienyl, cyclohexadienyl, dihydroanthracenyl, hexahydroanthracenyl, decahydroantacenyl groups, and boratabenzene groups, as well as their substituted hydrocarbyl CMO derivatives or C ^. or substituted hydrocarbyl, substituted silyl. The anionic, delocalized p-linked groups are cyclopentadienyl, pentamethylcyclopentadienyl, tetramethylcyclopentadienyl, tetramethylsilylcyclopentadienyl, indenyl, 2,3-dimethylindenyl, fluorenyl, 2-methylindenyl, 2-methyl-4-phenylindenyl, tetrahydrofluorenyl, octahydrofluorenyl and tetrahydroindenyl. Boratabenzenes are anionic ligands that are benzene analogs that contain boron. They are previously known in the art and have been described by G. Herberich et al. In Organometallics. 14,1, 471-480 (1995). The preferred boratabenzenes correspond to the formula: wherein R "is selected from the group consisting of hydrocarbyl, silyl or germyl, said R" having up to 20 non-hydrogen atoms. In complexes involving divalent derivatives of said groups attached to delocalized p, one atom thereof is bound through a covalent bond or a divalent group covalently bound to another atom of the complex, thus forming a bridge system. A suitable class of catalysts are the transition metal complexes corresponding to the formula: Lp? MXmX'nX "p or a dimer thereof wherein: Lp is a p-linked, delocalized, anionic group that is attached to M, containing up to 50 non-hydrogen atoms, optionally two Lp groups can be linked together forming a bridge structure, and optionally an Lp can be linked to X; M is a metal of Group 4 of the Periodic Table of the Elements in the formal oxidation state +2, +3, or +4; X is a divalent, optional substituent of up to 50 non-hydrogen atoms, which together with Lp forms a metallocycle with M; X 'is an optional neutral ligand having up to 20 non-hydrogen atoms; X "in each occurrence is an anionic, monovalent moiety having up to 40 non-hydrogen atoms, optionally, two X groups" can be covalently linked to form a divalent dianonic moiety having both valences attached to M, u, optionally, two X groups " they can be covalently bound to form a neutral, conjugated or unconjugated diene that is bound by pa M (so M is in the oxidation state + 2), or in addition optionally one or more groups X "and one or more groups X 'may be linked together thereby forming a portion that is both covalently linked to M and coordinated thereto via a Lewis base functionality; is 0, 1 or 2, m is 0 or 1, n is a number from 0 to 3, p is an integer from 0 to 3, and the sum, l + m + p, is equal to the formal oxidation state of M , except when two groups X "together form a conjugated or unconjugated neutral diene which is bound by pa M, in which case the sum of l + m is equal to the formal oxidation state of M. Preferred complexes include those which already contain be one or two groups Lp. The last complexes include those that contain a bridge group linking the two Lp groups. Preferred bridge groups are those corresponding to the formula (ER * 2) X, where E is silicon, germanium, tin or carbon, R * independently of each occurrence is hydrogen or a selected group of silyl, hydrocarbyl, hydrocarbyloxy and combinations thereof, said R * having up to 30 carbon or silicon atoms, and x is from 1 to 8. Preferably, R * independently of each occurrence is methyl, ethyl, propyl, benzyl, tert-butyl, phenyl, methoxy, ethoxy or phenoxy. Examples of the complexes containing two Lp groups are compounds corresponding to the formula: wherein: M is titanium, zirconium or hafnium, preferably zirconium or hafnium, in the formal oxidation state +2, +3 or +4; R3 in each occurrence, independently is selected from the group consisting of hydrogen, hydrocarbyl, silyl, germyl, halogen and combinations thereof, said R3 having up to 20 non-hydrogen atoms, or adjacent R3 groups together form a divalent derivative (is say, a hydrocarbhaltyl group, if I ad ii lo or germadiil) thus forming a fused ring system, and X "independently of each occurrence is an anionic ligand group of up to 40 non-hydrogen atoms, or two X groups" together form a divalent anionic ligand group of up to 40 atoms that are not hydrogen or together are a conjugated diene having from 4 to 30 non-hydrogen atoms forming a p complex with M, whereby M is in the formal oxidation state + 2, and R *, E and x are as previously defined. The above metal complexes are especially suitable for the preparation of polymers having stereo-regular molecular structure. In said capacity, it is preferred that the complex possess Cs symmetry or possess a stereo-rigid, chiral structure. Examples of the first type are compounds possessing different systems attached to p, delocalised, such as a cyclopentadienyl group and a fluorenyl group. Similar systems based on Ti (IV) or Zr (IV) were described for the preparation of syndiotactic olefin polymers in Ewen, et al., J. Am. Chem. Soc, 110, 6255-6256 (1988). Examples of chiral structures include complexes of bis-indenyl rae. Similar systems based on Ti (IV) or Zr (IV) were described for the preparation of isotactic olefin polymers in Wild et al., J. Organomet. Chem., 232, 233-47, (1982). Exemplary bridge ligands containing two ap-linked groups are: dimethylbis (cyclopentadienyl) silane, dimethylbis (tetramethylcyclopentadienyl) silane, dimethylbis (2-ethylcyclopentadien-1-yl) silane, dimethylbis (2-t-cyclopentadien-1-yl) ) silane, 2,2-bis (tetramethyl-cyclopentadienyl) propane, dimethylbis (inden-1-yl) silane, dimethyl bis- (tetrahydroinden-l-yl) silane, dimethylbis (fluoren-1-yl) silane, dimethylbis (tetrahydrofluoren) -1-yl) silan, di methyl bis (2-methyl-4-phenylinden-1-yl) silane, dimethylbis (2-methylinden-1-yl) silan, dimethyl (cyclopentadienyl) (fluoren -1-yl) silane, dimethyl (cyclopentadienyl) (octahydro-fluoren-1-yl) silane, dimethyl (cyclopentadienyl) (tetrahydrofluoren-1-yl) -silane, (1,1,2, 2-tetramethyl-1, 2-bis (cyclopentadienyl) disilane, (1,2-bis- (cyclopentadienyl) ethane, and dimethyl-8-cyclopentadienyl) -1 - (fluoren-1-yl) -methane The preferred "X" groups are selected from hydride, hydrocarbyl, silyl groups , germyl, halohydrocarbyl, halosilyl, sil il h id rocarbilo and aminohidrocarb ilo, or two X groups "together form a divalent derivative of a conjugated diene or any together form a conjugated diene, attached to p, neutral. The most preferred "X" groups are C1.2o hydrocarbyl groups. An additional class of metal complexes used in the present invention correspond to the preceding formula, Lp? MXmX'nX "p, or a dimer thereof, wherein X is a divalent substituent of up to 50 non-hydrogen atoms which together with Lp forms a metallocycle with M. Preferred divalent X substituents include groups containing up to 30 non-hydrogen atoms comprising at least one atom which is oxygen, sulfur, boron or a member of Group 14 of the Periodic Table of the Elements directly attached to the group attached to delocalized ap, and a different atom, selected from the group consisting of nitrogen, phosphorus, oxygen or sulfur which is covalently bound to M. A preferred class of said metal coordination complexes of Group 4 used according to the present invention correspond to the formula: RJ wherein: M is titanium or zirconium, preferably titanium in the formal oxidation state +2, '3 or +4; R3 in each occurrence independently is selected from the group consisting of hydrogen, hydrocarbyl, silyl, germyl, cyano, halogen and combinations thereof, said R3 having up to 20 non-hydrogen atoms, or adjacent R3 groups together form a divalent derivative ( Each X "is a halogen, hydrocarbyl, hydrocarbyloxy or silyl group, said group having up to 20 non-hydrogen atoms, or two X groups" together, ie, a hydrocarbyl, siladiyl or germadiyl group) thus forming a fused ring system. they form a conjugated diene of C5-3o or a divalent derivative thereof; And it is -O-, -S-, -NR *, -PR * -; and Z is SiR * 2, CR * 2, SiR * 2SiR * 2, CR * 2CR * 2, CR * = CR *, CR * 2SiR * 2, or GeR * 2, where R * is as previously defined. Illustrative Group 4 metal complexes that may be employed in the practice of the present invention include: cyclopentadienyl trimethyl titanium, cyclopentadienyl triethyl titanium, cyclopentadienyl triisopropyl titanium, cyclopentadienyl triphenyl titanium, cyclopentadienyl titanium 2,4-tribencyl titanium. -cyclopentadienyl dimethylpentadienyl, cyclopentadienyl titanium-2,4-dimethylpentadienyl D, triethyl phosphine, cyclopentadienyl titanium-2,4-dimethylpentadienyl D, trimethyl phosphine, cyclopentadienyl titanium dimethyl methoxide, cyclopentadienyl titanium dimethyl chloride, trimethyl titanium of pentamethylcyclopentadienyl, trimethyl indenyl titanium, indenyl triethyl titanium, triphenyl indenyl titanium, triphenyl indenyl titanium, tetrahydroindenyl tribenzyl titanium, pentamethylcyclopentadienyl triisopropyl titanium, pentamethylcyclobenzyl titanium pentadienyl, titanium dimethyl methoxide of pentamethylcyclopentadienyl; pentamethylcyclopentadienyl titanium dimethyl chloride; titanium bis (? 5-2,4-dimethylpentadienyl), titanium bis (? 5-2,4-dimethylpentadienyl) D, trimethyl phosphine, titanium bis (? 5-2,4-dimethyphenylene) D, triethyl phosphine , trimethyl octahydrofluorenyl titanium, trimethyl tetrahydroindenyl titanium, trimethyl tetrahydrofluorenyl titanium, dimethyl titanium (tert-butylamido) (1,1-dimethyl-2,3,4,9,10-? -1,4) ,6,7,8-hexahydronaphthalenyl) dimethylsilane, dimethyl titanium (tert-butylamido) (1,1, 2,3-tetramethyl-2,3,4,9, -? - 1,4,5,6,7,8-hexahydronaphthalenyl) dimethylsilane, dibenzyl titanium (tert-butylamido) (tetramethyl-? 5-cyclopentadienyl) -dimethylsilane, dimethyl (tert-butylamido) titanium (tetramethyl) 5-cyclopentadienyl) -dimethylsilane, dimethyl titanium of (tert-butylamido) (tetramethyl-? 5-cyclopentadienyl) -1,2-ethanediyl, dimethyl titanium of (tert-butylamido) (tetramethyl-? 5-indenyl) -dimethylsilane, titanium (III) 2- (dimethylamino) benzyl of (tert-butylamido) (tetramethyl-? 5-cyclopentadienyl) dimethylsilane; titanium (III) allyl (tert-butylamido) (tetramethyl-? 5-cyclopentadienyl) -dimethylsilane, titanium (III) 2,4-dimethylpentadienyl (tert-butylamino) (tetramethyl-? 5-cyclopentadienyl) dimethylsilane, titanium (II) 1, 4-diphenyl-1,3-butadienyl (tert-butylamido) (tetramethyl-? 5-cyclopentadienyl) dimethylsilane, titanium (II) 1,3-pentadienyl (tert-butylamido) (tetramethyl-? 5-cyclopentadienyl) dimethylsilane, titanium (II) 1, 4-d if in I-1, 3-butadienyl of (tert-butylamido) - (2-methylindenyl) dimethylsilane, titanium (II) 2,4-hexadienyl of (tert-butylamido) ) (2-methylindenyl) -dimethylsilane, titanium (IV) 2,3-dimethyl-1,3-butadienyl (tert-butylamido) - (2-methylindenyl) dimethylsilane, titanium (IV) isoprenyl (tert-butylamido) ( 2-Methylindenyl) -dimethylsilane, titanium (IV) 1,3-butadienyl (tert-butylamide) (2-methylindenyl) -dimethylsilane, titanium (IV) 2,3-dimethyl-1,3-butadienyl ester of (ter) -butylamido) - (2,3-dimethylindenyl) d -methylsilane, titanium (IV) isoprenyl (tert-butyl) amido) (2,3-dimethylindenyl) -dimethylsilane, titanium (IV) dimethyl (tert-butylamido) (2,3-dimethylindenyl) -dimethylsilane, titanium (IV) dibenzyl (tert-butylamido) (2,3-dimethylindenyl) -dimethylsilane, titanium (IV) 1 , 3-butadienyl (tert-butylamido) (2,3-dimethylindenyl) -dimethylsilane, titanium (II) 1, 3-pentadienyl (tert-butylamido) (2,3-dimethylindenyl) -dimethylsilane, titanium (II) 1 , 4-diphenyl-1,3-butadienyl (tert-butylamido) - (2,3-dimethylindenyl) dimethylsilane, titanium (II) 1, 3-pentadienyl (tert-butylamido) (2-methylindenyl) -dimethylsilane) , titanium (IV) dimethyl of (tert-butylamido) (2-methylindenyl) dimethylsilane, titanium (IV) dibenzyl of (tert-butylamido) (2-methylindenyl) -dimethylsilane, titanium (II) 1, 4-d if eni I - 1, 3-butadienyl (tert-butylamido) - (2-methyl-4-phenylindenyl) dimethylsilane, titanium (II) 1,3-pentadienyl (tert-butylamido) - (2-methyl-4-phen Linden il) dimethylsilane, titanium (II) 2,4-hexadienyl of (tert-butylamido) - (2-methyl-4-phenylindenyl) dimethylsilane, titanium (IV) 1, 3-Butadienyl (tert-butylamido) (tetramethyl-? 5-cyclopentadienyl) dimethylsilane, titanium (IV) 2,3-dimethyl-1,3-butadienyl (tert-butylamido) - (tetramethyl-? 5-cyclopentadienyl) ) dimetathylamine, (tert-butylamido) (tetramethyl-? 5-cyclopentadienyl) dimethylsilane, titanium (II) 1,4-dibenzyl-1,3-butadiene (tert-butylamido) - (tetramethyl) titanium (IV) isoprenyl ester -? 5-cyclopentadienyl) dimethylsilane, titanium (II) 2,4-hexadienyl (tert-butylamido) (tetramethyl-? 5- cyclopentadienyl) dimethylsilane, titanium (II) 3-methyl-1,3-pentadienyl ester (ter-butyl) butylamido) (tetramethyl-? 5-cyclopentadienyl) dimethylsilane, dimethyl (tert-butylamido) (2,4-dimethylpentadien-3-yl) -dimethylsilane, dimethyl (tert-butylamido) titanium (6,6-dimethylcyclohexadienil) ) -dimethylsilane, dimethyl titanium of (tert-butylamido) (1,1-dimethyl-2, 3,4,9, 10-α-1, 4,5, 6,7,8-hexahydronaphthalen-4-yl) dimethylsilane, dimethyl (tert-butylamido) titanium (1,1, 2,3-tetramethyl-2,3,4, 9,10 -? - 1,4,5,6,7,8-hexahydronaphthalen-4-yl) dimethylsilane, dimethyl (tert-butylamido) titanium (IV) (tetramethyl-? 5-cyclopentadienyl) methylphenylsilane, titanium (II ) 1, 4-diphenyl-1,3-butadienyl (tert-butylamido) (tetramethyl-? 5-cyclopentadienyl) methylphenylsilane, dimethyl (IV) titanium from 1 - (tert-butylamido) -2- (tetramethyl-? 5-) cyclopentadienyl) ethanediyl, and titanium (II) 1,4-diphenyl-1,3-butadienyl 1- (tert-butylamido) -2- (tetramethyl-? 5-cyclopentadienyl) ethanediyl. Complexes containing two Lp groups including complexes suitable bridge for use in the present invention include: dimethyl zirconium, bis (cyclopentadienyl) dibenzyl zirconium, bis (cyclopentadienyl) zirconium methyl benzyl, bis (cyclopentadienyl) zirconium methyl phenyl bis (cyclopentadienyl) diphenyl zirconium, bis (cyclopentadienyl) allyl titanium bis (cyclopentadienyl) methoxide methyl zirconium bis (cyclopentadienyl) methyl chloride zirconium bis (cyclopentadienyl) dimethyl zirconium, bis (pentamethylcyclopentadienyl) titanium dimethyl, bis (pentamethylcyclopentadienyl) zirconium dimethyl bis (indenyl) zirconium dimethyl indenilfluorenilo, methyl zirconium (2- (dimethylamino) benzyl), bis (indenyl) zirconium metiltrimetilsilílico bis (indenyl) zirconium bis metiltrimetilsilílico ( tetrahydroindenyl), bis (pentamethylcyclopentadiene) methylbenzyl zirconium, dibenzyl zirconium or of bis (pentamethylcyclopentadienyl), bis (pentamethylcyclopentadienyl) zirconium methyl methoxide, bis (pentamethylcyclopentadienyl) zirconium methyl ester, bis (methylethylcyclopentadienyl) dimethyl zirconium, bis (butylcyclopentadienyl) dibenzyl zirconium, bis (t-) dimethyl zirconium butylcyclopentadienyl), bis (ethyltetramethylcyclopentadienyl) dimethyl zirconium, bis (methylpropylcyclopentadienyl) dibenzyl zirconia, bis (trimethylsilylcyclopentadienyl) dibenzyl zirconium, dimethylsilyl-bis (cyclopentadienyl) dimethylsilyl zirconium, dimethylsilyl-bis allyl titanium (lll) (tetramethylcyclopentadienyl) zirconium dichloride dimethylsilyl-bis (t-butylcyclopentadienyl) zirconium dichloride dimethylsilyl-bis (n-butylcyclopentadienyl) titanium (lll) 2- (dimethylamino) benzyl (methylene-bis- (tetra methy I cyclopentadienyl), titanium (III) 2- (dimethylamino) benzyl (methylene-bis- (n-butylcyclopentadienyl), benzyl chloride zirconium dimethylsilyl-bis (indenyl) zirconium dimethyl dimethylsilyl-bis (2-methylindenyl) zirconium dimethyl dimethylsilyl-bis (2-methyl-4-phenylindenyl) zirconium-1,4-diphenyl-1,3-butadienílico of dim eti Is i I i-bis- (2-methylindenyl), zirconium (II) 1,4-diphenyl-1,3-butadienyl dimethylsilyl-bis- (2-methyl-4-phenylindenyl), zirconium (II ) 1, 4-diphenyl-1, 3-butadienílico dimethylsilyl-bis- (tetrahydroindenyl) zirconium methyl chloride dimethylsilyl-bis (fluorenyl) zirconium bis (trimethylsilyl) dimethylsilyl-bis (tetrahydrofluorenyl) zirconium dibenzyl of ( isopropylidene) (cyclopentadienyl) (fluorenyl), and dimethylsilyl (tetramethylcyclopentadienyl) - (fluorenyl) dimethyl zirconium. Other catalysts, especially catalysts containing Group 4 metals, will, of course, be apparent to those skilled in the art. The cocatalysts of the invention can also be used in combination with an oligomeric or polymeric alumoxane compound, a tri (hydrocarbyl) aluminum compound, a di (hydrocarbyl) (hydrocarbyloxy) aluminum compound, a di (hydrocarbyl) (dihydrocarbyl) compound. amido) aluminum, a bis (d i -hydrocarbyl amido) (hydrocarbyl) aluminum compound, a di (hydrocarbyl) amido (disilyl) aluminum compound, a di (hydrocarbyl) -amido (hydrocarbyl) (silyl) aluminum compound, a compound bis (dihydrocarbylamido) (silyl) aluminum, or a mixture of the above compounds, having from 1 to 20 non-hydrogen atoms in each hydrocarbyl group, hydrocarbyloxy or silyl, if desired. These aluminum compounds are usefully used for their beneficial ability to sweep impurities such as oxygen, water and aldehydes from the polymerization mixture. Preferred aluminum compounds include C2-6 aluminum trialkyl compounds, especially those wherein the alkyl groups are ethyl, propyl, isopropyl, n-butyl, isobutyl, pentyl, neopentyl or isopentyl, dialkyl (aryloxy) aluminum compounds containing 1-6 carbons in the alkyl group and from 6 to 18 carbons in the aryl group (especially (3,5-di (t-butyl) -4-methylphenoxy) dussobutylaluminum), methylalumoxane, modified methylalumoxane and diisobutylalumoxane. The molar ratio of the aluminum compound to the metal complex preferably is from 1: 10,000 to 1000: 1, preferably from 1: 5000 to 100: 1, most preferably from 1: 100 to 100: 1. The molar ratio of catalyst / cocatalyst employed preferably ranges from 1:10 to 10: 1, preferably from 1: 5 to 1: 1 and most preferably from 1: 1.5 to 1: 1. If desired, mixtures of the activating cocatalysts of the present invention may also be employed. Suitable polymerizable addition monomers include ethylenically unsaturated monomers, acetylenic compounds, conjugated and non-conjugated dienes, and polyenes. Preferred monomers include olefins, for example, alpha-olefins having from 2 to 20,000, preferably from 2 to 20, most preferably from 2 to 8 carbon atoms, and combinations of two or more of said alpha-olefins. Particularly suitable alpha-olefins include, for example, ethylene, propylene, 1-butene, 1-pentene, 4-methylpentene-1, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1 -undecene, 1-dodecene, 1-tridecene, 1-tetradecene, 1-pentadecene or combinations thereof, as well as oligomeric or polymeric reaction products terminated in long chain vinyl formed during polymerization, and α-olefins of C 10- 3o specifically added to the reaction mixture in order to produce relatively long chain branches in the resulting polymers. Preferably, the alpha-olefins are ethylene, propene, 1-butene, 4-methyl-pentene-1, 1-hexene, 1-octene and combinations of ethylene and / or propene with one or more other alpha-olefins. Other preferred monomers include styrene, halogen or substituted alkyl styrene, tetrafluoroethylene, vinylcyclobutene, 1,4-hexadiene, dicyclopentadiene, ethylidene norbornene and 1,7-octadiene, mixtures of the aforementioned monomers can also be used.

In general, polymerization can be achieved at conditions well known in the art for polymerization reactions of the Ziegler-Natta or Kaminsky-Sinn type. If desired, suspension, solution, slurry, gas phase or high pressure can be used, if it is used intermittently or continuously or other process conditions. Examples of such well known polymerization processes are described in WO 88/02009, US-A-5,084,534, US-A-5,405,922, US-A-4,588,790, US-A-5,032,652, US-A-4,543,399, US-A- 4,564,647, US-A-4,522,987, etc. The preferred polymerization temperatures are 0-250 ° C. The preferred polymerization pressures are atmospheric at 3000 atmospheres. Preferred processing conditions include solution polymerization, most preferably continuous solution polymerization processes, conducted in the presence of an aliphatic or alicyclic liquid diluent. By the term "continuous polymerization" it is meant that at least the products of the polymerization are continuously removed from the reaction mixture, such as, for example, by the devolatilization of a portion of the reaction mixture. Preferably, one or more reagents are also continuously added to the polymerization mixture during the polymerization. Examples of suitable aliphatic or alicyclic diluents include straight and branched chain hydrocarbons such as isobutane, butane, pentane, hexane, heptane, octane, and mixtures thereof; alicyclic hydrocarbons such as cyclohexane, cycloheptane, methylcyclohexane, methylcycloheptane, and mixtures thereof; and perfluorinated hydrocarbons such as perfluorinated C4-10 alkanes. Suitable diluents also include aromatic hydrocarbons (particularly for use with aromatic α-olefins such as styrene or ring-substituted alkyl styrenes) including toluene, ethylbenzene or xylene, as well as liquid olefins (which may act as monomers or comonomers) including ethylene, propylene, butadiene, cyclopentene, 1-hexene, 3-methyl-1-pentene, 4-methyl-1-pentene, 1,4-hexadiene, 1-octene, 1-decene, styrene, divinylbenzene, allylbenzene and vinyltoluene (including all the isomers alone or in combination). Mixtures of the above are also suitable. In most polymerization reactions, the molar ratio of catalyst: polymerizable compounds employed is 10"12: 1 to 10" 1: 1, most preferably 10 ~ 12: 1 to 10"5: 1. The catalyst of the invention can also be used in combination with at least one homogeneous or heterogeneous polymerization catalyst in separate reactors connected in series or in parallel to prepare polymer blends having desirable properties.An example of such a process is described in WO 94/00500 A more specific process is described in co-pending application WO 94/17112. Molecular weight control agents can be used in combination with the cocatalysts herein Examples of such molecular weight control agents include hydrogen, trialkylaluminum compounds or other known chain transfer agents A particular benefit of the use of the cocatalysts herein is the ability (depending on the reaction conditions) to produce narrow molecular weight α-olefin homopolymers and copolymers in greatly improved catalyst efficiencies. Preferred polymers have an Mw / Mn less than 2.5, most preferably less than 2.3. such narrow molecular weight distribution polymer products are highly desirable due to the improved tensile strength properties. The catalyst composition of the present invention can also be employed to have advantage in gas phase polymerization and olefin copolymerization. Gas phase processes for the polymerization of olefins, especially the homopolymerization and copolymerization of ethylene and propylene, are well known in the art., and the copolymerization of ethylene with higher alpha-olefins such as, for example, 1-butene, 1-hexene, 4-methyl-1-pentene. These processes are commercially used on a large scale for the manufacture of high density polyethylene (HDPE), medium density polyethylene (MDPE), linear low density polyethylene (LLDPE) and polypropylene. The gas phase process employed can be, for example, of the type employing a mechanically agitated bed or a fluidized gas bed as the polymerization reaction zone. The process is preferred in which the polymerization reaction is carried out in a vertical cylindrical polymerization reactor containing a fluidized bed of polymer particles supported above a perforated plate, the fluidization grid, through a gas flow of fluidization. The gas used to fluidize the bed comprises the monomer or monomers to be polymerized, and also serves as a heat exchange medium to remove the heat of reaction from the bed. Hot gases emerge from the upper part of the reactor, usually via a calming zone, also known as a velocity reduction zone, having a wider diameter than the fluidized bed, and where the fine particles entering the gas stream they have the opportunity to gravitate back to the bed. It can also be advantageous to use a cyclone to remove ultra-fine particles from the gas stream. The gas is then normally recirculated to the bed through a blower or compressor and one or more heat exchangers to separate the gas from the heat of the polymerization. A preferred method for cooling the bed, in addition to the cooling provided by the cold recirculating gas, is to feed a volatile liquid into the bed to provide an evaporative cooling effect. The volatile liquid used in this case can be, for example, a volatile inert liquid, for example, a saturated hydrocarbon having from 3 to 8, preferably from 4 to 6 carbon atoms. In the event that the monomer or comonomer itself is a volatile liquid, or can be condensed to provide such a liquid, it can be suitably fed into the bed to provide an evaporative cooling effect. Examples of olefin monomers which can be used in this manner include olefins containing from 3 to 8, preferably from 3 to 6, carbon atoms. The volatile liquid evaporates in the hot fluidized bed to form gas, which is mixed with the fluidizing gas. If the volatile liquid is a monomer or comonomer, it will experience some polymerization in the bed. The evaporated liquid then emerges from the reactor as part of the hot recirculation gas, and enters the compression / heat exchanger part of the recirculation loop. The recirculation gas is cooled in the heat exchanger and, if the temperature at which the gas is cooled is below the dew point, the liquid will precipitate out of the gas. This liquid is desirably recirculated continuously to the fluidized bed. It is possible to recirculate the precipitated liquid to the bed as droplets of liquid carried in the recirculation gas stream, as described, for example, in EP-A-89691, US-A-4543399, WO 94/225495 and US-A -5352749. A particularly preferred method for recirculating liquid to the bed is to separate the liquid from the recirculating gas stream and re-inject this liquid directly to the bed, preferably using a method that generates fine drops of the liquid within the bed. This type of process is described in WO 94/28032.

The polymerization reaction occurring in the gas fluidized bed is catalysed through the continuous or semi-continuous addition of catalyst. Said catalyst can be supported on an inorganic or organic support material, if desired. The catalyst can also be subjected to a pre-polymerization step, for example, by polymerizing a small amount of olefin monomer in a liquid inert diluent, to provide a catalyst composite comprising catalyst particles embedded in olefin polymer particles. The polymer is produced directly in the fluidized bed through catalysed (co) polymerization of monomer (s) on the fluidized particles of catalyst, supported catalyst or prepolymer within the bed. The start of the polymerization reaction is achieved using a bed of preformed polymer particles, which, preferably, is similar to the objective polyolefin, and conditioning the bed by drying with an inert gas or nitrogen before the introduction of the catalyst, the monomer (s) and any other gases that are desired to have in the recirculation gas stream, such as a diluent gas, a hydrogen chain transfer agent, or an inert condensable gas when operating in a gas phase condensation mode . The produced polymer is discharged continuously or discontinuously from the fluidized bed as desired, optionally exposed to a catalyst annihilator and optionally pelletized. It is understood that the present invention can be operated in the absence of any component that has not been specifically described.

Claims (11)

1. CLAIMS A zwitterionic compound that corresponds to the formula: R1 / | _ + - R -M "l - (Arf) 3, R22M1 M1R2 \ / ZR22 R1 / R22M1 M'R ^ \ / YR¿ L + is a protonated derivative of an element of Group 15 of the Periodic Table of the Elements, additionally carrying two hydrocarbyl substituents of 1 to 50 carbons each, or a positively charged derivative of an element of Group 14 of the Periodic Table of the Elements , said element of Group 14 being substituted with three hydrocarbyl substituents of 1 to 50 carbons each; R1 is a divalent linking group of 1 to 40 atoms that are not hydrogen; R2 independently of each occurrence is a ligand group of 1 to 50 atoms that are not hydrogen, provided that in a sufficient number of occurrences to balance the charge on the compound, R2 is L + -R1; R4 is a hydride or halide bridge group or a divalent linking group of 1 to 40 atoms that are not hydrogen; M1 is boron, aluminum or gallium; ArF independently of each occurrence in an organic, fluorinated, monovalent group, containing from 6 to 100 atoms that are not hydrogen; And it is an element of Group 15; and Z is an element of Group 14.
2. 2. A zwitterionic compound according to claim 1 corresponding to the formula: HL '+ -R * 1-B- (Arf); wherein: R1 is a hydrocarbylene group or a halogeno-, alkoxy-, N, N-dihydrocarbylamino-, silyl-, or germyl-substituted hydrocarbylene group, said R1 having from 1 to 40 atoms not representing hydrogen atoms; L 'is dihydrocarbyl substituted nitrogen or a phosphorus group, having from 1 to 50 carbons in each hydrocarbyl group; and Arf independently of each occurrence is a fluorinated, monovalent organic group, containing from 6 to 100 atoms not representing hydrogen atoms.
3. 3. A compound according to claim 1 corresponding to the formula: HN + (R5) 2-R -B "(Arf) 3 wherein: R1 is an alkylene group of C1-40 or an arylene group of C6 - or; R5 independently of each occurrence is a hydrocarbyl group of C? -50, and Arf in each occurrence is perfluorophenyl, perfluoronaphthyl or perfluorobiphenyl 4. A compound according to claim 1 corresponding to the formula: (C6H5) 2C + ~ B "C6F5 > 3» H (R5) 2N + ^^ _ B- (C10F7) 3 .H (C6H5) 2P + (H -B "(C.F5) 3 • H (R5) 2N + - C2H4- B- (C6F5) 3 H (R5) 2N + - ^ C2H4 - B- (C12F9) 3. H (R 55 &v) 2N M ++ - (C 2 H 4) - B- (C 6 F 5) 3, 0 H (R 5) 2N + -C 18 H 36 B * (C 12 F 9) 3 wherein R5 is methyl, phenyl or a mixture of C1 alkyl. 8. A catalyst system for the polymerization of α-olefins, which comprises, in combination, a metal complex of Group 4 and a compound according to any of claims 1 to 4, or the reaction product of the same. 6. - A supported catalyst system for the polymerization of α-olefins, which comprises, in combination, a metal complex of Group 4 and a compound according to any of claims 1 to 4, or the reaction product thereof and a support material. 7. A polymerization process comprising contacting one or more α-olefins under polymerization conditions with a catalyst system according to claim 5 or 6. 8. - A process according to claim 7, which is a solution polymerization. 9. A polymerization process according to claim 8, which is a continuous solution polymerization. 10. - A polymerization process according to claim 7, which is a slurry polymerization. 11. A polymerization process according to claim 7, which is a gas phase polymerization. SUMMARY A catalyst activator particularly suitable for use in the activation of metal complexes of metals of Group 3-10 is described for the polymerization of polymerizable, ethylenically unsaturated monomers, especially olefins, comprising a zwitterionic compound corresponding to the formula (I) or (II), wherein: L + is a protonated derivative of an element of Group 15 of the Periodic Table of the Elements, additionally carrying two hydrocarbyl substituents of 1 to 50 carbons each, or a positively charged derivative of an element of the Group 14 of the Periodic Table of the Elements, said element of Group 14 being replaced with three hydrocarbyl substituents of 1 to 50 carbons each; R1 is a divalent linking group of 1 to 40 atoms that are not hydrogen; R2 independently of each occurrence is a ligand group of 1 to 50 atoms that are not hydrogen, provided that in a sufficient number of occurrences to balance the charge in the compound, R2 is L + -R1-; R4 is a hydride or bridging halide group or a divalent linking group of 1 to 40 atoms which are not hydrogen; M is boron, aluminum or gallium; Arf independently of each occurrence is an organic, monovalent, fluorinated group containing from 6 to 100 atoms that are hydrogen; And it is an element of Group 15; and Z is an element of Group 14. R1 R1 / \ L + -Rl-Ml - (Arf) 3l R2M1 M1R22, 0 R2, 1 M1R2 \ / \ / ZR22 (I) YR2 (II)