Classifications

• • 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
  • C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
  • C08F10/14—Monomers containing five or more carbon atoms
• • 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
  • C08F4/62—Refractory metals or compounds thereof
  • C08F4/64—Titanium, zirconium, hafnium or compounds thereof
  • C08F4/659—Component covered by group C08F4/64 containing a transition metal-carbon bond
  • C08F4/65908—Component covered by group C08F4/64 containing a transition metal-carbon bond in combination with an ionising compound other than alumoxane, e.g. (C6F5)4B-X+
• • 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
  • C08F4/62—Refractory metals or compounds thereof
  • C08F4/64—Titanium, zirconium, hafnium or compounds thereof
  • C08F4/659—Component covered by group C08F4/64 containing a transition metal-carbon bond
  • C08F4/6592—Component covered by group C08F4/64 containing a transition metal-carbon bond containing at least one cyclopentadienyl ring, condensed or not, e.g. an indenyl or a fluorenyl ring

Definitions

• This invention relates to a process for preparing certain catalytically active metal complexes. More particularly, this invention relates to such a process involving oxidation of the metal center of a complex to form active catalyst compositions useful for polymerizing olefins, diolefins and/or acetylenically unsaturated monomers.
• homogeneous Ziegler-Natta type catalysts in the polymerization of addition polymerizable monomers is, of course, well known in the prior art.
• these o soluble systems comprise a Group 4 or Lanthanide metal compound and a metal alkyl cocatalyst, particularly an aluminum alkyl cocatalyst.
• Several preparations for homogeneous olefin polymerization catalysts are known. These involve reacting a transition metal chloride with an aluminum alkyl, reacting a transition metal alkyl and a aluminum alkyl, reacting a transition metal alkyl with a proton source, or reacting a transition metal alkyl with a cationic 5 oxidant. In these examples the oxidation state of the transition metal remains unchanged or may actually be reduced.
• the present invention lies in the discovery of a novel technique for preparing 0 certain metal complexes involving both metal center oxidation and cation complex formation via electron transfer in a single step by use of a neutral organic oxidant.
• a neutral organic oxidant permits the synthesisto be performed in hydrocarbon solvents normally employed for olefin polymerizations instead of polar or oxygenated solvents. Consequently, in the present invention contamination with deactivating substances is reduced and the need to 5 substitute solvents prior to use of the resulting complexes is omitted, thereby simplifying the synthesis and use of the complexes as catalysts.
• the reduced remnant of the oxidizing agent comprises an anion able to ligate the metal complex.
• a Lewis acid mitigator is additionally added to the reaction mixture.
• Cp independently each occurrence is a cyclopentadienyl group ⁇ -bound to M, or a hydrocarbyl, silyl, halo, halohydrocarbyl, hydrocarbylmetalloid or halohydrocarbyl metalloid substituted derivative of said cyclopentadienyl group, said Cp containing up to 50 nonhydrogen atoms, and, when a is 2, optionally both Cp groups may be joined together by a bridging group; a is 1 or 2; b is O or l; c is 1 or 2; the sum of a, b and c is 3;
• Z is a divalent moiety comprising oxygen, nitrogen, phosphorous, boron, or a member of Group 14 of the Periodic Table of the Elements, said moiety having up to 30 nonhydrogen atoms;
• Y is a linking group comprising nitrogen, phosphorus, oxygen or sulfur covalently bonded to M and Z through said nitrogen, phosphorus, oxygen or sulfur atom;
• L independently each occurrence is hydride, halo, or a monovalent anionic iigand selected from covalently bonded hydrocarbyl, silyl, amido, phosphido, alkoxy, aryloxy, and sulfido groups optionally being further substituted with one or more amino, phosphino, ether, or thioether groups, said Iigand having up to 50 nonhydrogen atoms; M is titanium or zirconium in the +4 oxidation state; p is an integer from 0 to 4; q is 1 or 2;
• A is a reduced remnant of a neutral organic oxidizing agent and may be ligating or nonligating, the steps of the process comprising contacting under conditions to form the oxidized metal complex:
• metal includes Group 13 - 15 elements which exhibit semi-metallic characteristics especially boron, silicon, germanium, and phosphorus.
• M is titanium in the + 4 oxidation state and M * is titanium in the + 3 oxidation state.
• L preferably is a monovalent anionic stabilizing Iigand selected from the group consisting of:
• stabilizing Iigand is meant that the Iigand group stabilizes the metal complex, and especially the reduced metal precursor complex, through either: 1 ) a nitrogen, phosphorus, oxygen or sulfur chelating bond, or
• stabilizing ligands L of group 1) include silyl, hydrocarbyl, amido or phosphido ligands substituted with one or more aliphatic or aromatic ether, thioether, amino or phosphino groups, especially such amino or phosphino groups that are tertiary substituted, said stabilizing Iigand having from 3 to 30 nonhydrogen atoms.
• Most preferred group 1) stabilizing ligands L are 2-(dialkylamino)benzyl, 2-(dialkylaminomethyl)phenyl, 2- (dialkylphosphino)benzyl or 2-(dialkylphosphinomethyl)phenyl groups containing from 1 to 4 carbons in the alkyl groups.
• Examples of stabilizing ligands L of group 2) for use according to the present invention include C3.10 hydrocarbyl groups containing ethylenic unsaturation, such as allyl, 1- methylallyl- 2-methylallyl, 1,1-dimethylallyl, or 1,2,3-trimethylallyl groups.
• Highly preferred Group 4 metal complexes formed according to the present invention are monocyclopentadienyl metal complexes corresponding to the formula: Cp M+ or Cp [J2A"] "2 ⁇ ⁇ L L 2
• M is titanium
• L independently each occurrence is a covalently bonded hydrocarbyl group substituted with an amino, phosphino, ether, or thioether containing substituent able to form a coordinate-covalent bond or chelating bond with M, said Iigand having up to 50 nonhydrogen atoms, or a C3.40 hydrocarbyl radical comprising an ethylenic unsaturation able to form an ⁇ 3 bond with M;
• A' is a nonligating form of A
• A" is a ligating form of A
• Cp is a cyclopentadienyl or substituted cyclopentadienyl group bound in an ⁇ 5 bonding mode to M;
• Z is a divalent moiety comprising carbon or silicon
• Y is a divalent linking group comprising nitrogen or phosphorus.
• the monocyclopentadienyi metal complex starting reactant for preparation of the above metal complexes is
• Each carbon atom in the cyclopentadienyl radical may be unsubstituted or substituted with the same or a different radical selected from the group consisting of hydrocarbyl radicals, substituted-hydrocarbyl radicals wherein one or more hydrogen atoms is replaced by a halogen atom, hydrocarbyl-substituted metalloid radicals wherein the metalloid is selected from Group 14 of the Periodic Table of the Elements, and halogen radicals.
• two or more such substituents may together form a fused ring system.
• Preferred hydrocarbyl and substituted-hydrocarbyl radicals contain from 1 to 20 carbon atoms and include straight and branched alkyl radicals, cyclic hydrocarbon radicals, alkyl-substituted cyclic hydrocarbon radicals, aromatic radicals and alkyl-substituted aromatic radicals-
• Suitable organometailoid radicals include mono-, di- and tri-substituted organometailoid radicals of Group 14 elements, preferably silicon or germanium, wherein each of the hydrocarbyl groups contains from 1 to 20 carbon atoms.
• suitable organometailoid radicals include trimethylsilyl, triethylsilyl, ethyldi methylsi I yl , methyldiethylsilyl, triphenylgermyl, and trimethylgermyl.
• Most highly preferred Cp groups are cyclopentadienyl, tetramethylcyclopentadienyl, indenyl, tetrahydroindenyl, fluorenyl and octahydrofluorenyl.
• Group 4 metal complexes formed according to the present invention are amidosilane- or amidoalkanediyl-compounds corresponding to the formula:
• L independently each occurrence is a covalently bonded hydrocarbyl group substituted with an amino, phosphino, ether, or thioether containing substituent able to form a coordinate-covalent bond or chelating bond with M, said Iigand having up to 50 nonhydrogen atoms, or a C3.40 hydrocarbyl radical comprising an ethylenic unsaturation able to form an ⁇ 3 bond with M, and
• R' independently each occurrence is selected from the group consisting of hydrogen, silyl, alkyl, aryl and combinations thereof having up to 10 carbon or silicon atoms, or two such R' groups together are a C 4 hydrocarbylene moiety forming a fused ring with adjacent carbons of the cyclopentadienyl group;
• E is silicon or carbon; and a is 1 or 2.
• R' on the foregoing cyclopentadienyl groups each occurrence is hydrogen, methyl, ethyl, propyl, butyl, pentyl, hexyl, including isomers of these radicals, norbornyl, benzyl, phenyl, or two or more such R' groups together form an indenyl, tetrahydroindenyl, fluorenyl or octahydrofluorenyl group.
• Group 4 metal complexes examples include compounds wherein the R' on the amido group is methyl, ethyl, propyl, butyl, pentyl, hexyl, including isomers of these radicals, norbornyl, benzyl, phenyl, etc.; the cyclopentadienyl group (including R' substituents) is cyclopentadienyl, tetramethylcyclopentadienyl, indenyl,
• L is methyl, neopentyl, trimethylsilyl, norbornyl, benzyl, methylbenzyl, phenyl, 2-(N,N-dialkylamino)benzyl or 2-(N,N- dialkylaminomethy phenyl wherein the alkyl substituents are preferably methyl radicals, and allyl.
• titanium(lll) precursor complexes include: (tert-butylamido)( ⁇ 5 - cyclopentadienyl)-1,2-ethanediyltitanium 2-(N,N-dimethylamino)benzyl, (tert-
• organic oxidizing agent refers to an organic compound having a reduction potential sufficient to cause oxidation of the metal, M*, to the + 4 oxidation
• Preferred organic oxidizers possess an electrochemical reduction potential from 0.30 volts more negative than the electrochemical oxidation potential of the desired oxidation to any value more positive than the electrochemical oxidation potential of the desired oxidation. More preferably, the electrochemical reduction potential for such oxidizing agent is in a range the lower endpoint of which is equal to the electrochemical oxidation potential of the desired
• Suitable neutral, organic oxidizing agents for use according to the present invention are organic compounds containing quinone functionality containing up to
• Fullerene oxidizing agents do not form ligating reduction species that interfere with the operation of the metal complex.
• Preferred are Ceo fullerene and C 70 fullerene.
• Preferred quinone functional organic oxidizing agents are benzoquinone, diphenoquinone, anthroquinone, and Ci-4 alkyl substituted derivatives thereof.
• Highly preferred organic oxidizing agents are 2,3,5,6-tetramethylbenzoquinone, 2,3,5,6-tetratert-butylbenzoquinone, 2,2', 6,6'- tetramethyldiphenoquinone, 2,2',6,6'-tetratert-butyldiphenoquinone.
• a most preferred quinone functional organic oxidizing agent is 2,2',6,6'-tetratert-butyldiphenoquinone.
• the above quinone functional oxidizing agents form an organic anion remnant which may coordinate to (ligate) the metal complex.
• the mitigating agent is an electron pair acceptor, the organic anion and one or more Lewis acid mitigating agents together form the noncoordinating, noninterfering, complex counter ion, JpA-q.
• Preferred Lewis acid mitigating agents are C ⁇ - ⁇ o trialkylaluminum compounds,
• Lewis acid mitigating agents are trimethylaluminum, triethyl- aluminum, trimethylboron, tri ethyl boron, tris(pentafluorophenyl)borane, tris (2,3,5,6-tetra- fluorophenyl)borane, tris(2,3,4,5-tetrafluorophenyl)borane, tris(3,4,5-trifluorophenyl)borane, tris(1,2,2-trifluoroethenyl)borane, phenylbis(perfluorophenyl)borane, and tris(perfluorophenyl) borate.
• the above Lewis acid mitigating agents may be prepared according to known techniques such as those of Marks, et al. J. Am. Chem. Soc. 1991 , 113, 3623-3625, or J. Pohlman, et al., Naturforschq. 1965.20b, 5-11.
• the preferred technique is to combine a boron or aluminum halide compound such as boron trichloride or boron trifluoride with an alkali metal or alkaline earth derivative of the desired substituent or substituents.
• borate esters such astris(perfluorophenyl) borate may be prepared by the reaction of pentafluorophenyl phenol and borane-methyl sulfide complex according to the method of 1 Orq.
• the complexes can be prepared by combining the components in a suitable noninterfering, noncoordinating solvent at a temperature from -100°C to 300°C, preferably from 0 to 200°C.
• suitable solvents are noncoordinating, inert liquids.
• Examples include straight and branched-chain hydrocarbons such as isobutane, butane, pentane, hexane, heptane, octane, and mixtures thereof; cyclic and alicyclic hydrocarbons such as cyclohexane, cycloheptane, methylcyclohexane, methylcycloheptane, and mixtures thereof; perfiuorinated hydrocarbons such as perfluorinated C 4 10 alkanes, and the like, and aromatic, or alkyl-substituted aromatic compounds such as benzene, toluene and xylene.
• straight and branched-chain hydrocarbons such as isobutane, butane, pentane, hexane, heptane, octane, and mixtures thereof
• cyclic and alicyclic hydrocarbons such as cyclohexane, cycloheptane, methylcyclo
• Suitable solvents also include liquid olefins which may act as monomers or comonomers including ethylene, propylene, butadiene, cyclopentene, 1-hexane, 3-methyl-1 -pentene, 4-methyl-1- pentene, 1,4-hexadiene, 1-octene, 1-decene, styrene, divinylbenzene, allylbenzene, 4-vinyl- cyclohexene, and vinyltoluene (including all isomers alone or in admixture). Mixtures of the foregoing are also suitable.
• the catalyst formed by the method of this invention may be retained in solution or separated from the sol vent, isolated, and stored for subsequent use. As previously indicated supra, the catalyst may also be prepared in situ during a polymerization reaction by passing the separate components into the polymerization vessel where the components will contact and react to produce the improved catalyst of this invention.
• the equivalent ratio of reduced metal precursor complex to oxidizing agent employed in the process is preferably in a range from 0.1 : 1 to 10: 1 , more preferably from 0.75: 1 to 5: 1 , most preferably 1 : 1 to 2: 1.
• the equivalent ratio of Lewis acid mitigating agent to oxidizing agent employed in the process is preferably in a range from 0: 1 to 50: 1, more preferably from 0.75:1 to 10: 1 , most preferably 1 : 1 to 2.5: 1.
• the complexes may be used to polymerize ethylenically and/or acetylenically unsaturated monomers having from 2 to 18 carbon atoms either alone or in combination. Preferably they are used to polymerize C 2 . ⁇ o ⁇ -olefins, especially ethylene, propylene, isobutylene, 1-butene, 1-hexene, 4-methyl-1 -pentene, and 1-octene, including mixtures thereof.
• Other suitable monomers include vinyl aromatic monomers such as styrene which may advantageously be interpolymerized with one or more ⁇ -olefins.
• the polymerization may be accomplished at conditions well known in the prior art for Ziegler-Natta or Kaminsky-Sinn type polymerization reactions that is, temperatures from 0-250°C and pressures from atmospheric to 1000 atmospheres. Suspension, solution, slurry, gas-phase or other process conditions may be employed. A support may be employed but preferably the catalysts are used in a homogeneous manner. In most polymerization reactions the equivalent ratio of complex:poiymerizable monomer employed is from 10 '12 : 1 to 10 " ':1, more preferably from 10 "8 : 1 to 10 "5 :1. The complexes generally need no activating agent in order to be catalytically effective.
• L is 2-(N,N-dimethylamino)benzyl
• Example 2 The polymerization conditions of Example 2 were repeated excepting that 4 mL of a 0.0050 M solution of triethylborane mitigating agent in Isopar'" E was substituted for the tris(perfluorophenyl)borane solution of Example 2. Polymer yield was 13.8 g. of ethylene/1-
• a two liter stirred reactor was charged with 660 g of Isopar-E ® and the quantity of 1-octene specified in Table I. Hydrogen was added by differential pressure expansion from a 75 m L addition tank from 2070 Kpa to 1929 Kpa. The contents of the reactor were heated to

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• 1993
  • 1993-03-19 US US08/034,434 patent/US5347024A/en not_active Expired - Fee Related
• 1994
  • 1994-02-10 WO PCT/US1994/001647 patent/WO1994021693A1/en not_active Ceased
  • 1994-02-10 FI FI945435A patent/FI945435A7/fi unknown
  • 1994-02-10 KR KR1019940704130A patent/KR950701651A/ko not_active Withdrawn
  • 1994-02-10 ES ES94911386T patent/ES2107201T3/es not_active Expired - Lifetime
  • 1994-02-10 DE DE69405952T patent/DE69405952T2/de not_active Expired - Fee Related
  • 1994-02-10 CA CA002134890A patent/CA2134890A1/en not_active Abandoned
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