EP1200488A1 - Procede de (co)polymerisation d'olefines - Google Patents

Procede de (co)polymerisation d'olefines

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Publication number
EP1200488A1
EP1200488A1 EP00945905A EP00945905A EP1200488A1 EP 1200488 A1 EP1200488 A1 EP 1200488A1 EP 00945905 A EP00945905 A EP 00945905A EP 00945905 A EP00945905 A EP 00945905A EP 1200488 A1 EP1200488 A1 EP 1200488A1
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European Patent Office
Prior art keywords
alkyl
aryl
atoms
cig
alkylaryl
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EP00945905A
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German (de)
English (en)
Inventor
Joachim Queisser
Michael GEPRÄGS
Gerrit Luinstra
Norbert Huber
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BASF SE
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BASF SE
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F4/00—Polymerisation catalysts
    • C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
    • C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
    • C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
    • C08F4/70—Iron group metals, platinum group metals or compounds thereof
    • C08F4/7001—Iron group metals, platinum group metals or compounds thereof the metallic compound containing a multidentate ligand, i.e. a ligand capable of donating two or more pairs of electrons to form a coordinate or ionic bond
    • C08F4/7003—Bidentate ligand
    • C08F4/7004—Neutral ligand
    • C08F4/7006—NN
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
    • C07F15/04—Nickel compounds
    • C07F15/045—Nickel compounds without a metal-carbon linkage
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
    • C07F15/0006—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table compounds of the platinum group
    • C07F15/006—Palladium compounds
    • C07F15/0066—Palladium compounds without a metal-carbon linkage
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/12—Esters of monohydric alcohols or phenols
    • C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
    • C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/42—Nitriles
    • C08F220/44—Acrylonitrile
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/52—Amides or imides
    • C08F220/54—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide
    • C08F220/56—Acrylamide; Methacrylamide
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F4/00—Polymerisation catalysts
    • C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
    • C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
    • C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
    • C08F4/70—Iron group metals, platinum group metals or compounds thereof
    • C08F4/7001—Iron group metals, platinum group metals or compounds thereof the metallic compound containing a multidentate ligand, i.e. a ligand capable of donating two or more pairs of electrons to form a coordinate or ionic bond
    • C08F4/7003—Bidentate ligand
    • C08F4/7019—Monoanionic ligand
    • C08F4/7021—NN
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F4/00—Polymerisation catalysts
    • C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
    • C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
    • C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
    • C08F4/70—Iron group metals, platinum group metals or compounds thereof
    • C08F4/7001—Iron group metals, platinum group metals or compounds thereof the metallic compound containing a multidentate ligand, i.e. a ligand capable of donating two or more pairs of electrons to form a coordinate or ionic bond
    • C08F4/7003—Bidentate ligand
    • C08F4/7032—Dianionic ligand
    • C08F4/7034—NN
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F110/00—Homopolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F110/02—Ethene

Definitions

  • the present invention relates to a process for the (co) polymerization of olefins with the aid of transition metal compounds. Furthermore, the invention relates to these transition metal compounds and a catalyst system containing the same. The invention also relates to the use of these transition metal compounds as catalysts for the (co) polymerization of non-polar olefins and, if appropriate, of ⁇ -olefins which have a functional group.
  • the invention was therefore based on the object of making available a process for the preparation of (co) polymers from olefinic monomers which is distinguished by high activities, requires little or no addition of cocatalyst and can also be used on an industrial scale without problems.
  • the invention was further based on the object of finding a transition metal compound which is insensitive and easy to handle and, in particular under the polymerization conditions, does not show any loss in the catalytic activity even with longer reaction times.
  • a process for the production of (co) polymers from non-polar olefinic monomers (I) and a process for the production of (co) polymers from non-polar olefinic monomers (I) and ⁇ -olefins (II) have at least one functional Have found group in which the starting monomer or monomers in the presence of a transition metal compound of the general formula
  • R 1 , R 3 are hydrogen, C 1 -C 1 to C 10 alkyl, C 3 to C 1 cycloalkyl, Cg to C 6 aryl, alkylaryl having 1 to 10 C atoms in the alkyl and 6 to 14 C atoms in the aryl part , Si (R 6 ) 3 , N (R 6 ) (R 7 ), OR 6 , SR 6 or R 1 and R 3 together with C a , C b and optionally C form a five, six or seven-wire aliphatic or aromatic, substituted or unsubstituted carbo- or heterocycle,
  • R 5 is hydrogen, C 1 -C 10 -alkyl, Cg- to Cig-aryl or alkylaryl with 1 to 10 C-atoms in the alkyl and 6 to 14 C-
  • M is a metal from Group VIIIB of the Periodic Table of the Elements
  • T, Q neutral or monoanionic monodentate ligands or T and Q together form a C 2 or C 3 alkylene unit with a methyl ketone, linear C 1 -C 4 -alkyl ester or nitrite end group,
  • transition metal compound (III) and a catalyst system containing the essential constituents of the transition metal compound (III) and a cocatalyst were a strong neutral Lewis acid, an ionic compound with a Lewis acid cation or an ionic compound with a Bronsted acid found as a cation.
  • the use of the transition metal compound (III) and the catalyst system comprising the transition metal compound (III) and a cocatalyst has been found as essential constituents in the production of olefin (co) polymers.
  • Compounds of the general formula (Ia) are suitable as non-polar olefinic monomers (I)
  • R 8 to R 10 are, independently of one another, hydrogen, C 1 -C 10 -alkyl, including linear and branched alkyl radicals, preferably C 1 -C 6 -alkyl such as methyl,
  • Ethyl, n-, i-propyl, n-, i- or t-butyl, Cg to Cig aryl, including one, two or more times with Ci to Cg alkyl groups such as methyl, ethyl or i-propyl substituted aryl groups such as tolyl are understood to be preferably 0 Cg aryl such as phenyl or naphthyl and C ⁇ , in particular phenyl, alkylaryl having from 1 to 10, preferably 1 to 6 carbon atoms in the alkyl and 6 to 14, preferably 6 to 10 C -Atoms in the aryl part, for example benzyl, or Si (R 1: L ) 3 with
  • R 11 Ci to Cio-alkyl, C 6 - to Cig-aryl or alkylaryl with 1 to 10 C atoms in the alkyl and 6 to 16 C atoms in the aryl part, these radicals preferred those given under R 8 to R 10 or can assume special meaning.
  • Suitable cyclic olefins (I) are, for example, cyclobutene, cyclopentene, cyclohexene or norbornene and substituted norbornenes. Preferred among these are cyclopentene and norbornene.
  • Suitable non-polar olefinic monomers can have one, two or more terminal or internal double bonds.
  • Olefinically unsaturated compounds with a terminal double bond such as ethene, propene, 1-butene, 1-pentene, 1-hexene or 1-octene, are preferably used.
  • perfluorinated olefins such as tetrafluoroethylene are also suitable nonpolar starting monomers (I).
  • any mixtures of starting monomers (I) can also be used in the process according to the invention.
  • ⁇ -olefins (II) which have at least one functional group in the molecule are used as further starting monomers.
  • Suitable functional groups are, for example, the carboxylic acid, carboxylic acid ester, carboxylic acid amide, carboxylic acid anhydride, hydroxy, epoxy, siloxy, ether, keto, aldehyde, amino, nitrile, oxazoline, sulfonic acid, sulfonic acid ester. or halogen functionalities.
  • Preferred functional groups are based, inter alia, on the carboxylic acid unit, on carboxylic ester, carboxylic acid amide or anhydride residues and on the ether or keto group.
  • R 12 is hydrogen, CN, CF 3 , C 1 ⁇ to Cio-alkyl, Cg to Cig-aryl or alkylaryl with 1 to 10 carbon atoms in the alkyl and 6 to 14 carbon atoms in the aryl part, pyrrolidonyl or carbazolyl,
  • R 13 CN, C (0) R 14 , C (0) OR 14 , C (0) N (R 14 ) (R 15 ), CH 2 Si (OR 16 ) 3 , C (O) -OC (O) R 14 , O-Ci to -O-C ⁇ 0 alkyl, O-Cg to - O-cig-aryl with
  • R 14 is hydrogen, Ci- to Cio-alkyl, C 2 - to C ⁇ 0 alkenyl, Cg to Cig aryl or alkylaryl having from 1 to 10 carbon atoms in the alkyl and 6 to 14 carbon atoms in the aryl part , an C - to Cio-alkyl group containing an epoxy group, a Cg to Cig-aryl group substituted by an epoxy group or Si (R 16 ) 3 and
  • R 16 Ci to Cio alkyl, Cg to Cig aryl or alkylaryl with 1 to 10 C atoms in the alkyl and 6 to 14 C atoms in the aryl part.
  • Functionalized olefinically unsaturated comonomers (II) have a terminal carbon / carbon double bond.
  • (meth) acrylic acid and the ester and amide derivatives of (meth) acrylic acid, preferably acrylic acid, and acrylonitrile or methacrylonitrile or mixtures thereof are particularly suitable.
  • C ⁇ to C ⁇ o ⁇ in particular the C ⁇ ⁇ to Cs alkyl esters of acrylic and methacrylic acid, ie for example the methyl, ethyl, n-, i-propyl, n-, i-, t- Butyl, hexyl, dicyclopentadienyl or 2-ethylhexyl (meth) crylate, where the alkyl radicals can be linear or branched.
  • (Meth) acrylates with a Epoxy group in the ester unit for example glycidyl (meth) acrylates, and with an alkenyl group such as ethylidene or propylidene as the ester unit.
  • Acrylates are particularly preferred. Examples of particularly suitable examples are methyl acrylate, ethyl acrylate, n-butyl acrylate, t-butyl acrylate, dicyclopentadienyl acrylate, glycidyl acrylate, 2-ethylhexyl acrylate and acrylic acid. Methyl acrylate and glycidyl acrylate are particularly preferred. Methacrylic or acrylonitrile can also be used. Any mixtures of comonomers (II) can of course also be used. The aforementioned monomers are known per se and are commercially available.
  • the starting concentration of the functionalized monomers (II) described can be varied over a wide range and, for example, easily assume values in the range from 3 to 6 mol / 1.
  • C 1 to C 1 alkyl radicals include, for example, the methyl, ethyl, n- or i-propyl, n-, i- or t-butyl group and the pentyl, hexyl or heptyl group in straight-chain and branched form.
  • C 1 ⁇ to C 1 ⁇ alkyl radicals, apart from monomer (I), also include those which are substituted by functional groups based on the elements of groups IVA, VA, VIA or VIIA of the periodic table, for example partially or perhalogenated alkyl radicals such as trichloromethyl , Trifluoromethyl, 2, 2, 2-trifluoroethyl, pentafluoroethyl or pentachloroethyl and alkyl radicals bearing one or more epoxy groups, for example propenoxy.
  • the C 1 -C 10 -alkyl radicals are preferred among the C 1 -C 1 -alkyl radicals.
  • Suitable C 3 - to Cio-cycloalkyl radicals include carbocycles and heterocycles, for example substituted and unsubstituted cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloctyl, pyrrolyl, pyrrolidonyl or piperidinyl.
  • Examples of the substituted cycloeopathic radicals are 1-methylcyclohexyl, 4-t-butylcyclohexyl and 2,3-dimethylcyclopropyl.
  • Suitable Cg to Cig aryl groups generally include substituted and unsubstituted aryl groups.
  • the C 1 -C 8 -aryl groups such as phenyl and naphthyl are preferred. Phenyl is particularly preferred.
  • Unsubstituted as well as substituted C 6 to cig aryl groups indicates the indication of the carbon atoms (eg Cg-, C ⁇ o ⁇ or Cig-) on the number of carbon atoms that form the aromatic system. Carbon atoms from possible alkyl and / or aryl substituents are not yet covered by this information.
  • Cg to Ci 6 ⁇ aryl is thus intended to include, for example, substituted Cg to Ci ⁇ aryl residues such as substituted anthracenyl.
  • Cg to Cig aryl fall, apart from monomer (I), including those radicals with functional groups based on the elements from Groups IVA, VA, VIA and VIIA of the Periodic Table of the Elements singly, multiply or persubsti ⁇ tuiert are.
  • Suitable functional groups are C ⁇ ⁇ to Cio-alkyl, preferably C ⁇ ⁇ to Cg-alkyl, Cg- to Cig-aryl, preferably Cg- to Cio-aryl, triorganosilyl such as trimethyl, triethyl, tri-phenyl or t-butyl diphenylsuyl and amino, for example NH 2 , dimethylamino, di-i-propylamino, di-n-butylamino, diphenylamino or dibenzylamino, Ci to Cio alkoxy, preferably Ci to Cg alkoxy, for example methoxy, ethoxy, n- or i-propoxy, n-, i- or t-butoxy, or halogen such as fluoride, chloride or bromide.
  • Suitable alkylaryl radicals include those having 1 to 10, preferably 1 to 6, carbon atoms in the alkyl and 6 to 14, preferably 6 to 10, carbon atoms in the aryl part, in particular the benzyl group.
  • the radicals R 2 and R 4 represent C 4 to Cig heteroaryl or Cg to C g aryl groups, each in their two ortho positions to the imine nitrogen atoms N a and N b , ie ortho-constant to the covalent Wear bond between the aryl group and the imine nitrogen electron-withdrawing groups such as halogeno, nitro, cyano, sulfonato or trihalomethyl.
  • the ortho positions in R 2 and R 4 can be substituted with identical as well as with different electron-withdrawing radicals.
  • SO 3 R 6 , S0 3 Si (R 6 ) 3 and S0 3 + (HN (R 5 ) 3 ) are particularly suitable.
  • S0 3 Me, S ⁇ 3 SiMe 3 and SO 3 " are particularly suitable among these. (HNEt 3 ) + .
  • trihalomethyl radicals trifluor, trichlor and tribromomethyl, in particular trifluoromethyl, are particularly suitable.
  • ortho substituents are halogen radicals such as the fluorine, chlorine, bromine or iodine radical. Chlorine or bromine radicals are preferably used as ortho substituents. Furthermore, the respective ortho positions are preferably occupied by identical residues.
  • the heteroaryl or aryl radicals R 2 and R 3 can have one or more further substituents in addition to the ortho radicals.
  • substituents are functional groups based on the elements from groups IVA, VA, VIA and VIIA of the Periodic Table of the Elements.
  • Suitable are, for example, linear or branched C 1 to C 10 alkyl, preferably C 1 to C 6 alkyl, such as methyl, ethyl, n- or i-propyl, n-, i- or t-butyl, partially or perhalogenated C 1 -C 10 -Alkyl, preferably -C ⁇ to Cg-alkyl, such as trifluoro or tri - chloromethyl or 2, 2, 2-trifluoroethyl, triorganosilyl, such as trimethyl, triethyl, tri-t-butyl, triphenyl or t- Butyl-di-phenylsüyl, the nitro, cyano or sulfonato group, amino, for example NH 2 , dirnethylamino, di-i-propylamino, di-n-butylamino, diphenylamino or dibenzylamino, C ⁇ ⁇ to Cio-
  • ortho-substituted aryl radicals are phenyl, naphthyl and anthracenyl groups, phenyl and naphthyl groups are particularly preferred and the phenyl group is particularly preferred.
  • These ortho-substituted aryl radicals can also be substituted in the positions which are not ortho-permanent with functional groups based on the elements from groups IVA, VA, VIA and VIIA of the periodic table of the elements, as described above.
  • An ortho-substituted phenyl radical R 2 , R 4 is preferably an additional substitution in the para position, for example with a methyl, t-butyl, chlorine or bromine radical.
  • Preferred aryl radicals R 2 , R 4 are 2,6-dibromo, 2,6-dichloro, 2,6-dibromo-4-methyl- or 2,6-dichloro-4-methylphenyl.
  • C 4 - to Cig heteroaryl radicals R 2 and R 4 in the context of the present invention are also to be understood as meaning substituted and unsubstituted heteroaryl radicals, for example C 4 - to C 3 -heteroaryl, preferably C 4 - bis
  • heteroaryl such as the pyrrolidyl group (linked to the imine nitrogen via a ring carbon atom) or the pyrrolid group (via linked the pyrrole nitrogen with the imine nitrogen) or the imidazolyl (CN linked), imidazolid (NN linked), benz - imidazolyl, benzimidazolid, pyrazolyl, pyrazolid, pyridinyl, pyrimidinyl, quinolyl or isoquinolyl group.
  • Preferred among the heteroaryl radicals is the ortho-substituted pyrrolidyl and, in particular, the pyrrod group.
  • This pyrrod group particularly preferably has halogen substituents such as fluorine, chlorine, bromine or iodine in the ortho position to the point of attachment to the imine nitrogen atoms N a or N b .
  • Preferred heteroaryl radicals R 2 , R 4 are 2, 5-dichloropyrrolid and 2, 5-dibrompyrrolid.
  • the radicals R 1 and R 3 in (III) are hydrogen, C 1 -C 1 -alkyl, C 3 -C 1 -cycloalkyl, C 1 -C 10 -aryl, alkylaryl having 1 to 10 carbon atoms in the alkyl and 6 to 14 carbon atoms in the aryl part, a silyl (Si (R 6 ) 3 ), an amino (N (R 6 ) (R 7 ), an ether
  • radicals R 1 and R 3 together with C a , C b and optionally C can form a five-, six- or seven-wire aliphatic or aromatic, substituted or unsubstituted carbo- or heterocycle.
  • radicals R 1 and R 3 are hydrogen, methyl, ethyl, i-propyl, t-butyl, methoxy, ethoxy, i-propoxy, t-butoxy, trifluoromethyl, phenyl, naphthyl, tolyl, 2-i-propylphenyl , 2-t-butylphenyl, 2, 6-di-i-propylphenyl, 2-trifluoromethylphenyl, 4-methoxyphenyl, pyridyl or benzyl and in particular hydrogen, methyl, ethyl, i-propyl or t-butyl are preferred.
  • Ligand compounds with these residues can be found in K. Vrieze and G.
  • cyclic systems preferably from R 1 , R 3 , C a and C b , aromatic systems, in particular phenanthrene and camphor systems, are preferred (see also J. Matei, T. Lixandru, Bul. Inst. PoÜteh. Isai, 1967, 13 , 245).
  • the radical R 5 preferably represents hydrogen or methyl, in particular hydrogen.
  • Suitable metals M in (III) are all elements of group VIIIB of the periodic table, ie iron, cobalt, nickel, ruthenium, rhodium, palladium, osmium, iridium or platinum. Nickel, rhodium, palladium or platinum are preferably used, nickel and palladium and in particular palladium being particularly preferred. In the metal compounds (III), iron and cobalt are generally two or three times positively charged, palladium, platinum and nickel are twice positively charged and rhodium is three times positively charged. In one embodiment, T and Q represent neutral and / or mono-anionic monodentate ligands.
  • Lewis bases are suitable as neutral ligands, for example acetonitrile, benzonitrile, diethyl ether, tetrahydrofuran, amines, ketones, phosphanes, ethyl acetate, dimethyl sulfoxide and dirnethyl formamide or hexamethylphosphoric triamide.
  • Ethene is also suitable as a Lewis basic neutral ligand.
  • Monoanionic ligands are, for example, carbanions based on substituted or unsubstituted alkyl, aryl or acyl radicals or halide ions.
  • T in (III) preferably denotes monoanionic radicals such as chloride, bromide or iodide, methyl, phenyl, benzyl or a C 1 -C 1 -alkyl which has no hydrogen atoms in the ⁇ position to the metal center M and has a C 1 -C 4 - Alkylester- or a Nitrüendelle has.
  • Chloride and bromide as halide residues and methyl as alkyl residue are particularly preferred as ligand T.
  • Q preferably represents ligand residues such as acetonitrile, benzonitrile, ethene, triphenylphosphine as monodentate phosphorus compound, pyridine as monodentate aromatic nitrogen compound, acetate, propionate or butyrate, in particular acetate as a suitable carboxylate, a linear alkyl ether, for example a linear di-C - to Cg- Alkyl ethers such as diethyl ether or di-i-propyl ether, preferably diethyl ether, a cyclic alkyl ether such as tetrahydrofuran or dioxane, preferably tetrahydrofuran, a linear C 1 -C 4 -alkyl ester, for example ethyl acetate, dimethyl sulfoxide, dimethylformamide, hexamethylphosphoric acid triamide or an halogenide
  • Ni nickel complexes
  • the radicals T and Q together can represent a C - or C 3 -alkylene unit with a methyl ketone, a linear Ci to C 4 -alkyl ester or a nitrite end group.
  • T and Q preferably together represent a - (CH 2 CH 2 CH 2 C (0) OCH 3 unit and in this way form a six-membered cycle together with M. While the terminal methylene unit forms a metal / carbon bond with M. , the carbonyl group interacts coordinatively with M.
  • T represents an alkyl radical, in particular methyl
  • Q represents a neutral one Lewis base ligands, especially diethyl ether, acetonitrile or ethene.
  • a non-coordinating or poorly coordinating anion A is understood to mean those anions whose charge density at the anionic center is reduced due to electronegative residues and / or whose residues sterically shield the anionic center.
  • Suitable anions A include antimonates, sulfates, sulfonates, borates, phosphates or perchlorates such as B [CgH 3 (CF 3 ) 2 ] 4 "(tetrakis (3, 5-bis- (trifluoromethyldphenyDborate), B [C 6 F 5 ] ⁇ or BF 4 - and SbFg " , A1F 4 _ , AsFg " , PFg “or trifluoroacetate (CF 3 SO 3 -).
  • B [CgH 3 (CF 3 )] 4 "" , SbFg " and PFg " are preferred.
  • Particularly preferred borates, in particular B [CgH 3 (CF 3 ) 2 ] 4 " are used.
  • Suitable non-coordinating or poorly coordinating anions and their preparation are described, for example, in SH Strauss, Chem. Rev. 1993, 93, 927-942, and in W Beck and K. Sünkel, Chem. Rev. 1988, 88, 1405-1421.
  • Preferred transition metal compounds (III) are, for example, bis-2,3- (2,6-dibromophenylimine) butane-palladium (methyl) chloride, bis-2,3- (2,6-dichlorophenylimine) butane-palladium (methyl) chloride, bis -2, 3- (2,6-dibromo-4-methylphenylimine) butane-palladium (methyl) chloride, bis-2,3, (2,6-dichloro-4-methylphenylimine) butane-podium (methyl) chloride .
  • preferred transition metal compounds (III) can also use tetrahis (3, 5-bis (trifluoromethylDphenyDborate (B [C 6 H 3 (CF 3 ) 2 ] 4 " ) or hexafluorophosphate (PFg ® ) become.
  • the transition metal compounds (III) can be used in the process according to the invention as a single compound or in the form of a mixture of several different transition metal compounds (III) as a catalyst.
  • the transition metal compounds (III) have a bidentate bisimine chelate ligand (in formula (III) the structural element which is obtained with the components M, T, Q and A omitted).
  • bidentate ligands can e.g. can be obtained from glyoxal or diacetyl by reaction with primary amines such as 2, 6-dibromomanine, 2, 6-dichloroanine, 2, 6-dibromo-4-methylphenylamine or 2, 6-dichloro-4-methylphenylamine (see also C. van Koten and K. Vriee, Adv. Organomet. Chem. 1982, Vol. 21, 152-234, Academic Press, New York).
  • these complexes are treated in the presence of acetonitrile, benzonitrile, dimethyl sulfoxide, dimethylformamide, hexamethylphosphoric triamide or a linear or cyclic ether such as diethyl ether with an alkali metal or silver salt (M 1 ) ⁇ - with A in the meaning of a non- or poorly coordinating anions and M 1, for example in the meaning of a sodium, potassium, lithium, cesium or silver cation, for example sodium (tetra (3, 5-bis (trifluoromethyl) phenyl) borate) or silver hexafluoroantimonate.
  • M 1 alkali metal or silver salt
  • M 1 alkali metal or silver salt
  • M 1 alkali metal or silver salt
  • M 1 alkali metal or silver salt
  • the starting compound in which Q represents a halide can be obtained by treating a corresponding cyclooctadiene complex with a bidentate bisimine chelate ligand in a non-coordinating solvent such as dichloromethane.
  • a non-coordinating solvent such as dichloromethane.
  • Such production processes are known to the person skilled in the art and are described, for example, by Johnson et al. , J. Am. Chem. Soc. 1995, 117, 6414 and JH Groen et al. , Organometallics, 1997, 17, 68.
  • For the preparation of the cyclooctadiene complexes see, for example, H. Tom Dieck et al. , Z. Naturforschung, 1981, 36b, 823 and D.
  • the (TMEDA) complexes are, for example, according to a specification by de Graaf et al. , Rec. Trav. Chim. Pay-Bas, 1988, 107, 299 accessible from the corresponding dichloride complexes.
  • transition metal complexes (III) can be obtained from Lewis base adducts of the metal salts such as palladium (II) bis (acetonitrile) chloride by treatment with a bidentate bisiminchelate ligand (see also GK Anderson, M. Lin, Inorg. Synth. 1990, 28, 61 and RR Thomas, A. Sen, Inorg. Synth. 1990, 28, 63).
  • the resulting halogen metal diimine complexes can be converted into the corresponding monoalkyl derivatives using alkylating reagents such as tin tetramethyl (SnMe 4 ) (see also EP-A 0 380 162).
  • the starting point for the preparation of the transition metal complexes (III) are suitable metal salts such as cobalt (II) chloride, cobalt (II) bromide, iron (III) chloride and in particular
  • a cocatalyst can be used in addition to the transition metal compound (III).
  • Suitable cocatalysts include strong neutral Lewis acids, ionic compounds with Lewis acid cations and ionic compounds with Bronsted acids as cations.
  • M 2 is an element of III.
  • Main group of the periodic table means, in particular B, Al or Ga, preferably B means and
  • X 1 , X 2 , X 3 independently of one another for hydrogen, linear or branched C ⁇ ⁇ to Cio-alkyl, preferably C ⁇ ⁇ bis
  • C ⁇ -alkyl such as methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, t-butyl or n-hexyl, one or more Substituted C - to Cio-alkyl, preferably Ci- to Cs-alkyl, for example with halogen atoms such as fluorine, chlorine, bromine or iodine, Cg to Cig-aryl, preferably Cg to Cio-aryl, for example phenyl, which is also a - Or can be substituted several times, for example with halogen atoms such as fluorine, chlorine, bromine or iodine, for example pentafluorophenyl, alkylaryl with 1 to 10 carbon atoms, preferably 1 to 6 carbon atoms in the alkyl radical and 6 to 14 carbon atoms, preferably 6 are up to 10 carbon atoms in the aryl radical, for example
  • radicals X 1 , X 2 , X 3 are those which have halogen substituents. Pentafluorophenyl should preferably be mentioned. Particularly preferred are compounds of the general formula (IVa) in which X 1 , X 2 and X 3 are identical, preferably tris (pentafluorophenyl) borane.
  • alumoxane compounds are further preferred among the cocatalysts.
  • those compounds which have an Al — C bond are suitable as alumoxane compounds.
  • Open-chain and / or cyclic alumoxane compounds of the general formula (IVb) or (IVc) are particularly suitable as cocatalysts.
  • R 17 independently of one another denotes a C 1 -C 4 -alkyl group, preferably a methyl or ethyl group, and k represents an integer from 5 to 30, preferably 10 to 25.
  • oligomeric alumoxane compounds are usually prepared by reacting a solution of trialkylaluminum with water and are described, inter alia, in EP-A 0 284 708 and US Pat. No. 4,794,096.
  • the oligomeric alumoxane compounds obtained are mixtures of both linear and cyclic chain molecules of different lengths, so that m is to be regarded as the mean.
  • the alumoxane compounds can also be present in a mixture with other metal alkyls, preferably with aluminum alkyls, such as triisobutyl aluminum or triethyl aluminum.
  • Methylalumoxane (MAO) is preferably used, in particular in the form of a solution in toluene.
  • the production of methylalumoxane can be found e.g. described in detail in EP-A 284 708.
  • Aryloxyalumoxanes as described in US Pat. No. 5,391,793, amidoaluminoxanes, as described in US Pat. No. 5,371,260, aminoaluminoxane hydrochlorides, as described in EP-A 0 633 264, and siloxyaluminoxanes, as in EP-A 0 621 279, can also be used as cocatalysts described, or alumoxane mixtures are used.
  • alumoxanes described are used either as such or in the form of a solution or suspension, for example in aliphatic or aromatic hydrocarbons, such as toluene or xylene, or mixtures thereof.
  • Q is an element of main group I or II of the Periodic Table of the Elements, such as lithium, sodium, potassium, rubidium, cesium, magnesium, calcium, strontium or barium, in particular lithium or sodium, or a silver, carbonium, oxonium, Ammonium, sulfonium or 1,1 '-dimethylferrocenyl cation,
  • Main group of the periodic table of the elements means, in particular boron, aluminum or galium, preferably boron,
  • Ci to CiQ alkyl independently of one another for hydrogen, linear or branched Ci to CiQ alkyl, preferably Ci to Cs-alkyl, such as methyl " , ethyl, n-propyl, i-propyl, n-butyl, i-butyl, t-butyl or n-hexyl, mono- or polysubstituted C ⁇ ⁇ to Cio-alkyl, preferably C ⁇ ⁇ bis Cs-alkyl, for example with halogen atoms such as fluorine, chlorine, bromine or iodine, Cg to Cig aryl, preferably Cg to
  • Cio-aryl for example phenyl, which can also be substituted one or more times, for example with halogen atoms such as fluorine, chlorine, bromine or iodine, for example pentafluorophenyl, alkylaryl with 1 to 10 C atoms, preferably 1 to 6 C atoms in the alkyl radical and 6 to 14 carbon atoms, preferably 6 to 10 carbon atoms in the aryl radical, for example benzyl, fluorine, chlorine, bromine, iodine, C 1 -C 10 -alkoxy, preferably C 1 -C 8 -alkoxy, such as methoxy, ethoxy or i-propoxy, or Cg to C g aryloxy, preferably Cg to Cio aryloxy, for example phenoxy, and
  • the anion (TX 4 X 5 X 6 X 7 ) - in a compound of the general formula (IVd) - is preferably a non-coordinating counterion.
  • Boron compounds such as those in WO 91/09882, to which reference is expressly made here, should be emphasized will be called.
  • Particularly suitable cations G are based on the sodium or triphenylmethyl cation and on tetraalkylammonium cations, such as tetramethyl, tetraethyl or tetra-n-butylammonium, or tetraalkylphosphonium cations such as tetramethyl, tetraethyl or tetra-n-butylphosphonium.
  • Preferred compounds (IVd) are, for example, sodium tetrakis (pentafluorophenyl) borate or sodium tetrakis [bis (trifluoromethyl) phenyl] borate
  • Ionic compounds with Bronsted acids as cations and preferably also non-coordinating counterions are mentioned in WO 91/09882, to which reference is expressly made here.
  • Preferred as a cation is e.g. N, N-Dimethylaniünium.
  • Aromatic monohydroxy compounds shielded with sterically demanding groups preferably phenols, come as radical inhibitors. who have at least one sterically demanding group vicmal to the OH group.
  • Suitable phenolic compounds can be found in the classes of compounds of alkylphenols, hydroxyphenol propionates, ammophenols, bisphenols or alkylidene bisphenols.
  • Another group of suitable phenols is derived from substituted benzoecarboxylic acids, in particular from substituted benzoepropionic acids.
  • Examples of the compound class of sterically hindered phenols are bis (2, 6-tert-butyl) -4-methylphenol (BHT), 4-methoxymethyl-2, 6-di-tert-butylphenol, 2, 6-D-tert- butyl-4-hydroxymethylphenol, 1,3, 5-tr ⁇ methyl-2, 4, 6-tr ⁇ s- (3, 5-d ⁇ -tert-butyl-4-hydroxybenzyl) -benzene, 4,4 '-methylene-bis- ( 2, 6-di-tert-butylphenol), 3, 5-di-tert-butyl-4-hydroxybenzoic acid 2, 4-di-tert-butylphenyl ester, 2, 2-B ⁇ - (4-hydroxyphenyl) propane (bisphenol A ), 4, 4 '-dihydroxybiphenyl (DOD), 2, 2' -methylene-bis (4-methyl-6-tert-butylphenol), 1, 6-hexanediol-b ⁇ s-3- (3, 5-d ⁇ -tert
  • B ⁇ s (2,6- (C ⁇ - to Cio-alkyl) -4- (Ci- to C ⁇ o-alkyl) phenols in particular bis (2, 6-tert-butyl) -4-methylphenol and Bis (2,6-methyl) -4-methylphenol is preferred, and bis (2,6-tert-butyl) -4-methylphenol is particularly preferred.
  • tetraalkylpiperidm-N-oxyl radicals can be used as radical inhibitors instead of the sterically hindered phenols or also as an additive to these.
  • Suitable are e.g. 2,2,6, 6-tetramethyl-l-p ⁇ per ⁇ dmyloxy (TEMPO), 4-oxo-2,2, 6, 6-tetramethyl-l-p ⁇ pe ⁇ dmyloxy (4-0xo-TEMP0), 4-hydroxy-2, 2, 6, 6-tetramethyl-1-p ⁇ pe ⁇ dmyloxy, 2,2,5, 5-tetra-methyl-1-pyrrole-dmyloxy, 3-carboxy-2, 2,5, 5-tetramethyl-pyrrole-dmyloxy or di-tert-butylnitroxide.
  • TEMPO 2,2,6, 6-tetramethyl-l-p ⁇ per ⁇ dmyloxy
  • 4-oxo-2,2, 6, 6-tetramethyl-l-p ⁇ pe ⁇ dmyloxy 4-hydroxy-2, 2, 6, 6-tetramethyl-1-p ⁇ pe ⁇
  • amounts of an aromatic monohydroxy compound shielded with sterically demanding groups or an N-oxyl radical compound shielded with sterically demanding groups of less than 200, less than 100 or even less than 20 ppm are sufficient, based on the starting amount of functionalized olefinically unsaturated monomers in order to ensure that the process according to the invention runs smoothly. This is also possible with amounts of less than 10, 5 and even 2 ppm.
  • concentrations of radical inhibitor are also permissible which exceed the concentration of the transition metal compound in the reaction mixture by double, triple or even four times.
  • the preparation of the (co) polymers according to the process according to the invention can be carried out in an aliphatic or aromatic aprotic solvent, e.g. in heptane, i-butane, toluene or benzene, as well as in a polar aprotic solvent.
  • Suitable polar aprotic solvents are e.g. Halogenated hydrocarbons such as dichloromethane, chloroform, carbon tetrachloride or chlorobenzene, linear or cyclic ethers such as diethyl ether or tetrahydrofuran, furthermore acetone, dimethyl sulfoxide, dimethylformamide, hexamethylphosphoric acid triamide or acetonitrile.
  • any, preferably homogeneous, mixtures of the abovementioned solvents can also be used.
  • Dichloromethane, chloroform, toluene, chlorobenzene and acetonitrile and mixtures thereof are particularly preferred.
  • the amount of solvent is usually determined so that the starting compounds are in dissolved form at the start of the reaction.
  • the transition metal-catalyzed polymerization process can also be carried out in bulk or in the gas phase.
  • the transition metal compounds (III) can also be used in supported form in the polymerization in the gas phase.
  • Inorganic and organic materials can be used as carrier materials. Suitable inorganic carrier materials are, for example, silica gel, aluminum, magnesium, titanium, zirconium, boron, calcium or zinc oxides, aluminosilicates, polysiloxanes, talc, layered silicates, zeolites or metal halides such as MgCl 2 .
  • Organic carrier materials are based, for example, on prepolymers of olefin (co) polymers, as are obtained, for example, using the processes according to the invention.
  • Suitable transfer methods are known to the person skilled in the art and can be found among others for supported ones Ziegler-Natta catalysts in Makromol. Chem. Phys. 1994, 195, 3347, Macromol. Rapid Commun. 1994, 15, 139-143 and Angew. Chem. Int. Ed. Engl. 1995, 34, 1143-1170) and for supported metal ocene catalysts in EP-A-0 308 177 and in US 4,897,455, US 4,912,075 and US 5,240,894.
  • the copolymerization is usually carried out at temperatures in the range from -40 to 160 ° C., preferably in the range from -20 to 100 ° C. and particularly preferably from 0 to 80 ° C. Depending on the reaction conditions chosen, the reaction times are generally between 1 and 2 hours and several days. Gaseous reaction components such as ethene are pressed onto the reaction mixture.
  • the copolymerization generally takes place at a pressure in the range from 0.1 to 200 bar, preferably from 0.5 to 100 bar and particularly preferably from 1 to 80 bar.
  • the concentration of transition metal compound (III) is generally set to values in the range from 10 ⁇ 6 to 0.1, preferably in the range from 10 ⁇ 5 to 10 ⁇ 2 and particularly preferably in the range from 5 x 10 ⁇ 5 to 5 x 10 ⁇ 2 mol / 1 set.
  • the initial concentration of nonpolar olefin (I) is generally in the range from 10 ⁇ 3 to 10 mol / 1, preferably in the range from 10 ⁇ 2 to 5 mol / 1.
  • the starting concentration of a functional tional group-substituted ⁇ -olefin (II) is generally in the range of 10 -5 to 8 mol / 1, preferably of 10 "3 to 7 and particularly preferably from 10 to 6.8 mol _1 /1.
  • the molar ratio of functionalized to non-polar monomer in the starting mixture is usually in the range from 10 -3 : 1 to 1000: 1, preferably in the range from 10 "1 : 1 to 100: 1, particularly preferably from 0.1: 1 to 20 : 1.
  • the molar initial ratio of radical inhibitors to functionalized monomer (II) is generally in the range from 10 ⁇ 8 : 1 to 10 "1 : 1, preferably from 10 ⁇ 7 : 1 to 10 ⁇ 2 : 1 and particularly preferably from 5 x 10 ⁇ 7 : 1 to 10 ⁇ 4 : 1.
  • the polymerization can be terminated by adding a deactivation reagent such as triphenylphosphine or by adding a low molecular weight alcohol such as methanol or ethanol.
  • a deactivation reagent such as triphenylphosphine
  • a low molecular weight alcohol such as methanol or ethanol.
  • the (co) polymers obtained by the process according to the invention have molecular weight distributions M w / M n in the range from 1.1 to 2.5, preferably from 1.1 to 1.8, and glass transition temperature values of regularly ⁇ -40 ° C., preferably ⁇ -50 ° C and regularly ⁇ -20 ° C in the case of the nickel transition metal compounds (III).
  • M Pd in (III)
  • (co) polymers, for example polyethylene are obtained with a very high degree of linearity.
  • homopolymers and copolymers of monomers (I) and copolymers of monomers (I) and (II) can be obtained.
  • the process can be carried out either continuously or batchwise.
  • the transition metal compounds (III) are notable for their high activity, and also have no loss of activity even in the case of prolonged polymerization, and thus ensure high productivity.
  • the 13 C-NMR spectra were recorded on a device from Bruker (ARX 300) with CDC1 3 or CDC1 4 as solvent.
  • the 1 H-NMR spectra were recorded on a device from Bruker (ARX 300) with CDCI 3 or CDC1 4 as solvent.
  • the DSC spectra were recorded on a device from Perkin-Elmer (Series 7) at a heating rate of 20 K / min.
  • Glycidyl acrylate was purchased from Polysciences Inc. and distilled before addition to the reaction mixture.
  • Catalyst F was prepared analogously to catalyst E), with the difference that the bidentate chelate ligand
  • the polymer formed separated out in the form of a highly viscous oil or in the form of a fine powder and could be obtained by decanting or filtering.
  • the polymer obtained was washed several times with ethanol. The last solvent residues were removed in a high vacuum.

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Abstract

L'invention concerne un procédé pour préparer des (co)polymères, selon lequel on fait réagir des monomères oléfiniques non polaires et éventuellement des alpha -oléfines, présentant un groupe fonctionnel, en présence d'un ou de plusieurs composés de métaux de transition de formule générale (III), et éventuellement en présence d'un cocatalyseur. Dans la formule (III), les substituants et les indices ont la signification suivante : R<1>, R<3> représentent hydrogène, alkyle C1 à C10, cycloalkyle C3 à C10, aryle C6 à C16, alkylaryle comportant 1 à 10 atomes de C dans la partie alkyle et 6 à 14 atomes de C dans la partie aryle, Si(R<6>)3, N(R<6>)(R<7>), OR<6>, SR<6>, ou R<1> et R<3> forment avec C<a>, C<b> et éventuellement C' un carbocycle ou un hétérocycle à cinq, six ou sept chaînons, aliphatique ou aromatique, substitué ou non ; R<2>, R<4> représentent hétéroaryle C4 à C16 ou aryle C6 à C16 comportant des substituants halogéno, nitro, cyano, sulfonato ou triahalogénure de méthyle, au deux positions ortho par rapport à N<a> et N<b> ; R<5> représente hydrogène, alkyle C1 à C10, aryle C6 à C16 ou alkylaryle comportant 1 à 10 atomes de C dans la partie alkyle et 6 à 14 atomes de C dans la partie aryle ; R<6>, R<7> représentent alkyle C1 à C10, aryle C6 à C16 ou alkylaryle comportant 1 à 10 atomes de C dans la partie alkyle et 6 à 14 atomes de C dans la partie aryle ; m vaut 0 ou 1 ; M représente un métal du groupe VIIIB de la classification périodique des éléments ; T, Q représentent des ligands neutres ou mono-anioniques monodentates, ou T et Q forment ensemble un motif alkyle C2 ou C3 avec un groupe terminal méthylcétone, ester d'alkyle C1 à C4 linéaire ou nitrile ; A représente un anion ne provoquant pas ou provoquant difficilement la formation d'une liaison de coordination ; x, p valent 0, 1, 2 ou 3 ; q, n valent 1, 2 ou 3.
EP00945905A 1999-07-27 2000-07-11 Procede de (co)polymerisation d'olefines Withdrawn EP1200488A1 (fr)

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US6545108B1 (en) 1999-02-22 2003-04-08 Eastman Chemical Company Catalysts containing N-pyrrolyl substituted nitrogen donors
US6605677B2 (en) 2000-02-18 2003-08-12 Eastman Chemical Company Olefin polymerization processes using supported catalysts
US6579823B2 (en) 2000-02-18 2003-06-17 Eastman Chemical Company Catalysts containing per-ortho aryl substituted aryl or heteroaryl substituted nitrogen donors
US7056996B2 (en) 2000-02-18 2006-06-06 E. I. Du Pont De Nemours And Company Productivity catalysts and microstructure control
US6706891B2 (en) 2000-11-06 2004-03-16 Eastman Chemical Company Process for the preparation of ligands for olefin polymerization catalysts
US6903169B1 (en) * 2003-12-30 2005-06-07 Equistar Chemicals, Lp LTMC polymerization of unsaturated monomers

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