EP1222025A2 - Complexes metalliques du groupe 4 non metallocenes et dicationiques - Google Patents

Complexes metalliques du groupe 4 non metallocenes et dicationiques

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Publication number
EP1222025A2
EP1222025A2 EP00975243A EP00975243A EP1222025A2 EP 1222025 A2 EP1222025 A2 EP 1222025A2 EP 00975243 A EP00975243 A EP 00975243A EP 00975243 A EP00975243 A EP 00975243A EP 1222025 A2 EP1222025 A2 EP 1222025A2
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Prior art keywords
group
metal
groups
lewis
atoms
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German (de)
English (en)
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Eugene Y. Chen
William J. Kruper, Jr.
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Dow Global Technologies LLC
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Dow Global Technologies LLC
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    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/22Organic complexes
    • B01J31/2204Organic complexes the ligands containing oxygen or sulfur as complexing atoms
    • B01J31/2208Oxygen, e.g. acetylacetonates
    • B01J31/2226Anionic ligands, i.e. the overall ligand carries at least one formal negative charge
    • B01J31/2243At least one oxygen and one nitrogen atom present as complexing atoms in an at least bidentate or bridging ligand
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/02Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • B01J31/0201Oxygen-containing compounds
    • B01J31/0211Oxygen-containing compounds with a metal-oxygen link
    • B01J31/0214Aryloxylates, e.g. phenolates
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/02Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • B01J31/0234Nitrogen-, phosphorus-, arsenic- or antimony-containing compounds
    • B01J31/0235Nitrogen containing compounds
    • B01J31/0252Nitrogen containing compounds with a metal-nitrogen link, e.g. metal amides, metal guanidides
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/02Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • B01J31/0234Nitrogen-, phosphorus-, arsenic- or antimony-containing compounds
    • B01J31/0271Nitrogen-, phosphorus-, arsenic- or antimony-containing compounds also containing elements or functional groups covered by B01J31/0201 - B01J31/0231
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/02Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • B01J31/12Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides
    • B01J31/14Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides of aluminium or boron
    • B01J31/143Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides of aluminium or boron of aluminium
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/18Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
    • B01J31/1805Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing nitrogen
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07FACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F7/00Compounds containing elements of Groups 4 or 14 of the Periodic Table
    • C07F7/003Compounds containing elements of Groups 4 or 14 of the Periodic Table without C-Metal linkages
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07FACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F7/00Compounds containing elements of Groups 4 or 14 of the Periodic Table
    • C07F7/02Silicon compounds
    • C07F7/08Compounds having one or more C—Si linkages
    • C07F7/10Compounds having one or more C—Si linkages containing nitrogen having a Si-N linkage
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F210/00Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F210/16Copolymers of ethene with alpha-alkenes, e.g. EP rubbers
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2531/00Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/02Compositional aspects of complexes used, e.g. polynuclearity
    • B01J2531/0238Complexes comprising multidentate ligands, i.e. more than 2 ionic or coordinative bonds from the central metal to the ligand, the latter having at least two donor atoms, e.g. N, O, S, P
    • B01J2531/0258Flexible ligands, e.g. mainly sp3-carbon framework as exemplified by the "tedicyp" ligand, i.e. cis-cis-cis-1,2,3,4-tetrakis(diphenylphosphinomethyl)cyclopentane
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2531/00Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/40Complexes comprising metals of Group IV (IVA or IVB) as the central metal
    • B01J2531/46Titanium
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F4/00Polymerisation catalysts
    • C08F4/42Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
    • C08F4/44Metals; 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
    • C08F4/60Metals; 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
    • C08F4/62Refractory metals or compounds thereof
    • C08F4/64Titanium, zirconium, hafnium or compounds thereof
    • C08F4/659Component covered by group C08F4/64 containing a transition metal-carbon bond
    • C08F4/65912Component covered by group C08F4/64 containing a transition metal-carbon bond in combination with an organoaluminium compound

Definitions

  • the present invention relates to compounds that are useful, inter alia, as catalysts or catalyst components. More particularly, the present invention relates to dicationic compounds comprising a Group 4 metal atom (Ti, Zr, Hf) that are particularly adapted for use in the coordination polymerization of unsaturated compounds. Such compounds are particularly advantageous for use in a polymerization process wherein at least one polymerizable monomer is combined under polymerization conditions with a catalyst or catalyst composition to form a polymeric product.
  • dicationic compounds comprising a Group 4 metal atom (Ti, Zr, Hf) that are particularly adapted for use in the coordination polymerization of unsaturated compounds.
  • Such compounds are particularly advantageous for use in a polymerization process wherein at least one polymerizable monomer is combined under polymerization conditions with a catalyst or catalyst composition to form a polymeric product.
  • certain specifically substituted bis-Cp zirconocenedimethyl complexes may be converted to a dicationic derivative at -60°C using multiple equivalents of trispentafiuorophenylborane.
  • the resulting metallocenes required the presence of either pendant phosphine moieties or benzyl groups on the cyclopentadienyl ring system and two equivalents of the methyltris(pentafluorophenyl)borate anion for charge balance.
  • Y 1 and Y 2 independently each occurrence is an anionic ligand group that is covalently bonded to M by means of a sigma bond through an oxygen, phosphorus or nitrogen atom, and containing up to 50 atoms, not counting hydrogen, said Y 1 and Y 2 optionally being joined through bridging group, J, and further optionally, Y 1 and Y 2 may also contain a coordinate/covalent bound to M;
  • J is an optional divalent bridging group having up to 20 atoms not counting hydrogen; j is 0 or 1 ;
  • M is a Group 4 metal
  • X 1 independently each occurrence is a Lewis base; x 1 is 0, 1 or 2; and A " independently each occurrence is an anion of up to 50 atoms other than hydrogen, derived or derivable from a Lewis acid, said A " optionally forming an adduct with the metal complex by means of a ⁇ -bridging group, and further optionally two A " groups may be joined together thereby forming a single dianion, optionally containing one or more ⁇ -bridging groups.
  • the compounds of the invention may be formed by contacting a charge-neutral
  • Group 4 metal coordination complex having two monovalent, anionic ligand groups, X (or optionally the two X groups together form a single divalent, anionic ligand group), or precursor(s) thereof (catalyst) with at least 2 molar equivalents of a charge-neutral, Lewis acid compound (activator), A, or a mixture thereof, such that the X groups of the Group 4 metal coordination complex are abstracted or partially abstracted, thereby forming a charge separated cation/anion pair, a zwitterionic metal complex, or a complex having both cation/anion and zwitterion functionality.
  • the molar ratio of catalyst:activator employed in the foregoing process is from 1 :2 to 1 :10, more preferably the ratio is from 1 :2 to 1 :3, and most preferably from 1 :2 to 1 :2.5.
  • Y 1 , Y 2 , M, J, j, X, X 1 , x 1 , A, and A " are as previously defined.
  • the present invented compounds are stable at elevated temperatures of at least 0°C, preferably at least 20°C up to as high as 150°C or higher and are usefully employed in a process for polymerization of ethylenically unsaturated monomers under solution, slurry, high pressure, or gas phase polymerization conditions. Relatively high molecular weight polymers may be readily obtained by use of the present metal complexes in the foregoing polymerization processes.
  • metal complexes are suitably employed as initiators or catalysts for cationic polymerizations, such as the cationic polymerization of styrene or isobutylene, ring opening polymerizations, such as the polymerization of oxiranes or epoxides, especially propylene oxide, and the copolymerization of an olefin, especially ethylene, with a ring openable monomer.
  • cationic polymerizations such as the cationic polymerization of styrene or isobutylene
  • ring opening polymerizations such as the polymerization of oxiranes or epoxides, especially propylene oxide
  • copolymerization of an olefin, especially ethylene especially ethylene
  • the present invention additionally provides a process for the polymerization of one or more ethylenically unsaturated, addition polymerizable monomers comprising contacting the same, optionally in the presence of an inert aliphatic, alicyclic or aromatic hydrocarbon, under polymerization conditions with the above metal complex, or alternatively, forming the above metal complex in situ in the presence of or prior to addition to, a reaction mixture comprising one or more ethylenically unsaturated, polymerizable compounds.
  • Lewis acid in reference to activator compounds herein, is meant compounds that are sufficiently electrophilic, such that a fully charge separated cation/anion pair, a ⁇ - bridged complex or a zwiterionic complex is formed upon combination of the respective catalyst and activators.
  • Preferred anionic ligand groups, X are hydrocarbyl, silyl, N,N- dialkylamido and alkanediylamido groups of up to 20 atoms not counting hydrogen, or two such X groups together are an alkanediyl or alkenediyl group which together with M form a metallocycloalkane or metallocycloalkene.
  • partially dicationic is meant that at least one A " group (or the entity formed from two A " groups collectively) is not fully charge separated from the metal center, M, or that at least one A " group (or the entity formed from two A " groups collectively) form a zwitterionic complex.
  • Preferred activators, A are aluminum compounds containing at least one halohydrocarbyl ligand, preferably a fluoroaryl ligand. More preferred are tri(halohydrocarbyl)aluminum compounds having up to 50 atoms other than hydrogen, especially tri(fluoroaryl) aluminum compounds, most preferably tris(perfluoroaryl)aluminum compounds, and most highly preferably tris(pentafluorophenyl)aluminum.
  • the activator compound may be used in pure form or in the form of an adduct with a Lewis base such as an ether.
  • Suitable Lewis acidic activators may be prepared by exchange between tris(pentafluorophenyl)boron and alkylaluminum- or alkyaluminumoxy- compounds such as alumoxanes or diisobutyl(2,6-di-t-butyl-4-methylphenoxy)aluminum, as disclosed in Biagini et.al., US-A-5,602,269, and pending application USSN 09/330673 (WO00/09515).
  • the aluminum containing Lewis acids may be previously prepared and used in a relatively pure state or generated in situ by any of the foregoing techniques in the presence of the metal complex.
  • tris(perfluoroaryl)borane compounds especially tris(pentafluoro-phenyl)boron
  • MAO methylalumoxane
  • MMAO triisobutylaluminum- modified methylalumoxane
  • This reaction product of tris(perfluoroaryl)boron with an alumoxane comprises a tris(fluoraryl)aluminum component of high Lewis acidity and a form of alumoxane which is rendered more Lewis acidic by the inherent removal of trimethylaluminum (TMA) via exchange to form trimethylborane.
  • TMA trimethylaluminum
  • Ar f is a fluorinated aromatic hydrocarbyl moiety of from 6 to 30 carbon atoms; preferably fluoroaryl, more preferably perfluoroaryl, and most preferably pentafluorophenyl;
  • Q 1 is d- 20 alkyl, preferably methyl;
  • Q 2 is C ⁇ - 2 o hydrocarbyl, optionally substituted with one or more groups which independently each occurrence are hydrocarbyloxy, hydrocarbylsiloxy, hydrocarbylsilylamino, di(hydrocarbylsilyl)amino, hydrocarbylamino, di(hydrocarbyl)amino, di(hydrocarbyl)phosphino, or hydrocarbylsulfido groups having from 1 to 20 atoms other than hydrogen, or, optionally, two or more Q 2 groups may be covalently linked with each other to form one or more fused rings or ring systems; w' is a number from 0 to 3; w is a number from 0 to 1.0; preferably from 0.5 to 1.0, more preferably from 0.8 to 1.0; x' is a number from 0 to 3; x is a number from 1.0 to 0; preferably from 0.5 to 0, more preferably from 0.2 to 0; y' is a number from
  • the moieties may exist as discrete entities or as dynamic exchange products. That is, the foregoing formula is an idealized representation of the composition, which may actually exist in equilibrium with additional exchange products.
  • An additional suitable Lewis acid activator may be formed in situ by reaction of residual or excess Lewis acid activator, prefearbly, tris(pentaflurophenyl)aluminum, with the anion resulting from initial abstraction of an X group from the metal complex.
  • anions resulting from the foregoing reaction are of the formula: [A- ⁇ X-A] ' , where, A- is the monovalent ligand derivative of A, preferably -AI(C 6 F 5 ) 3 , and ⁇ X is the ⁇ - bridged derivative of X, preferably a ⁇ -methyl group.
  • An example of such an anion is [(C 6 F 5 ) 3 AI- ⁇ -CH 3 -AI(C 6 F 5 ) 3 ] ' .
  • the group 4 metal complex and originally formed anion form a rather stable coordination pair under normal reaction conditions, the formation of the foregoing ⁇ -methyl bridged anion is likely observed only under reaction conditions that would favor destabilization of the previously disclosed coordination pair.
  • anion A are ligands of the formula: [M 1 Q 4 ] ⁇ where M 1 is a Group 13 metal or metalloid, preferably Al, and Q independently each occurrence is an anionic ligand group, preferably an alkyl, aryl, aralkyl, or fluorinated aromatic ligand, that optionally may form a ⁇ -bridge to the metal, M.
  • M 1 is a Group 13 metal or metalloid, preferably Al
  • Q independently each occurrence is an anionic ligand group, preferably an alkyl, aryl, aralkyl, or fluorinated aromatic ligand, that optionally may form a ⁇ -bridge to the metal, M.
  • Most preferred examples of this type of A " anion are is [CH 3 AI(C 6 F5)3] " and [ ⁇ -CH 3 AI(C 6 F5)3] ⁇ .
  • Exemplary J groups include O, as well as groups corresponding to the formula: (ER * 2 ) e , (BNR * 2 ) e , or PR * 2 BR 6 2 , wherein,
  • R 6 independently each occurrence is halide, or C M2 hydrocarbyl.
  • Suitable compounds according to the present invention include compounds having the following structures: where M, R 1 , and A " are as previously defined, and
  • R 2 independently each occurrence is H or a hydrocarbyl, silyl, or trihydrocarbylsilyl- substituted hydrocarbyl group, said group having up to 20 atoms not counting hydrogen.
  • some or all of the bonds between M, Y 1 and Y 2 may possess partial bond characteristics.
  • R 1 is a primary alkyl group
  • an electronic interaction between the nitrogen and either one or both of the anionic moieties, A " may occur.
  • the process for preparing the dicationic complexes of the invention is conducted at temperatures from -80 to 220°C, preferably from 25 to 50°C, and preferably in a hydrocarbon diluent or solvent, especially C 4 . 12 aliphatic, cycloaliphatic or aromatic hydrocarbons or a mixture thereof.
  • Suitable addition polymerizable monomers for use with the foregoing novel catalyst compositions include ethylenically unsaturated monomers, acetylenic compounds, conjugated or non-conjugated dienes, and polyenes.
  • Preferred monomers include olefins, for example alpha-olefins having from 2 to 20,000, preferably from 2 to 20, more preferably from 2 to 8 carbon atoms and combinations of two or more of such alpha-olefins.
  • alpha-olefins include, for example, ethylene, propylene, 1 -butene, isobutylene, 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 long chain vinyl terminated oligomeric or polymeric reaction products formed during the polymerization, and C 10 - 30 ⁇ -olefins specifically added to the reaction mixture in order to produce relatively long chain branches in the resulting polymers.
  • the alpha-olefins are ethylene, propylene, 1-butene, 1-pentene, 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, halo- or alkyl substituted styrenes, vinylbenzocyclobutene, 1 ,4-hexadiene, dicyclopentadiene, ethylidene norbornene, and 1 ,7-octadiene. Mixtures of the above-mentioned monomers may also be employed.
  • the polymerization may be accomplished under conditions well known in the prior art for Ziegler-Natta or Kaminsky-Sinn type polymerization reactions. Suspension, solution, slurry, gas phase or high pressure, whether employed in batch or continuous form or other process conditions, may be employed if desired. Examples of such well known polymerization processes are depicted in U.S. Patent Nos. 5,084,534, 5,405,922, 4,588,790, 5,032,652, 4,543,399, 4,564,647, 4,522,987, and elsewhere. Preferred polymerization temperatures are from 0-250°C. Preferred polymerization pressures are from atmospheric to 3000 atmospheres (100 kPa to 300 Pma).
  • Preferred processing conditions include solution polymerization, more preferably continuous solution polymerization processes, conducted in the presence of an aliphatic or alicyclic liquid diluent.
  • continuous polymerization is meant that at least the products of the polymerization are continuously removed from the reaction mixture.
  • one or more reactants are also continuously added to the polymerization mixture during the polymerization.
  • Suitable aliphatic or alicyclic liquid diluents include straight and branched-chain C4.12 hydrocarbons and mixtures thereof; alicyclic hydrocarbons such as cyclohexane, cycloheptane, methylcyciohexane, methylcycloheptane, and mixtures thereof; and perfluorinated hydrocarbons such as perfluorinated C 4 . 10 alkanes, and the like.
  • Suitable diluents also include aromatic hydrocarbons (particularly for use with aromatic ⁇ -olefins such as styrene or ring alkyl- substituted styrenes) including toluene, ethylbenzene or xylene, as well as liquid olefins (which may act as monomers or comonomers) including ethylene, propylene, 1-butene, isobutylene, butadiene, 1-pentene, cyclopentene, 1-hexene, cyclohexene, 3-methyl-1- pentene, 4-methyl-1-pentene, 1 ,4-hexadiene, 1 -octene, 1 -decene, styrene, divinylbenzene, allylbenzene, vinyltoluene (including all isomers alone or in admixture), and the like. Mixtures of the foregoing are also suitable.
  • aromatic hydrocarbons particularly for use
  • the molar ratio of catalyst:polymerizable compounds employed is from 10 "12 :1 to 10 "1 :1 , more preferably from 10 "12 :1 to 10 "5 :1.
  • Molecular weight control agents may be used in combination with the present cocatalysts. Examples of such molecular weight control agents include hydrogen, trialkyl aluminum compounds or other known chain transfer agents.
  • a particular benefit of the use of the present cocatalysts is the ability (depending on reaction conditions) to produce narrow molecular weight distribution ⁇ -olefin homopolymers and copolymers in greatly improved catalyst efficiencies.
  • Preferred polymers have Mw/Mn of less than 2.5, more preferably less than 2.3. Such narrow molecular weight distribution polymer products are highly desirable due to improved tensile strength properties.
  • the catalyst composition of the present invention can also be employed to advantage in the gas phase polymerization and copolymerization of olefins, preferably by supporting the catalyst composition by any suitable technique.
  • Gas phase processes for the polymerization of olefins, especially the homopolymerization and copolymerization of ethylene and propylene, and the copolymerization of ethylene with higher alpha olefins such as, for example, 1-butene, 1 -hexene, 4-methyl-1-pentene are well known in the art. Such processes are used commercially on a large scale for the manufacture of high density polyethylene (HDPE), medium density polyethylene (MDPE), linear low density polyethylene (LLDPE) and polypropylene.
  • HDPE high density polyethylene
  • MDPE medium density polyethylene
  • LLDPE linear low density polyethylene
  • the gas phase process employed can be, for example, of the type that employs a mechanically stirred bed or a gas fluidized bed as the polymerization reaction zone.
  • Preferred is the process wherein 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, by a flow of fluidization gas.
  • the gas employed 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.
  • the gas is then normally recycled to the bed by means of a blower or compressor and one or more heat exchangers to strip the gas of the heat of polymerization.
  • a preferred method of cooling of the bed, in addition to the cooling provided by the cooled recycle gas, is to feed a volatile liquid to the bed to provide an evaporative cooling effect.
  • the volatile liquid employed in this case can be, for example, a volatile inert liquid, for example, a saturated hydrocarbon having about 3 to about 8, preferably 4 to 6, carbon atoms.
  • a volatile inert liquid for example, a saturated hydrocarbon having about 3 to about 8, preferably 4 to 6, carbon atoms.
  • the monomer or comonomer itself is a volatile liquid or can be condensed to provide such a liquid, this can be suitably be fed to the bed to provide an evaporative cooling effect.
  • olefin monomers which can be employed in this manner are olefins containing from about 3 to about eight, preferably from 3 to six carbon atoms.
  • the volatile liquid evaporates in the hot fluidized bed to form gas which mixes with the fluidizing gas. If the volatile liquid is a monomer or comonomer, it may undergo some polymerization in the bed.
  • the evaporated liquid then emerges from the reactor as part of the hot recycle gas, and enters the compression/heat exchange part of the recycle loop.
  • the recycle gas is cooled in the heat exchanger and, if the temperature to which the gas is cooled is below the dew point, liquid will precipitate from the gas.
  • This liquid is desirably recycled continuously to the fluidized bed. It is possible to recycle the precipitated liquid to the bed as liquid droplets carried in the recycle gas stream, as described, for example, in EP-A-89691 , US-A-4543399, WO 94/25495 and US-A-5352749.
  • a particularly preferred method of recycling the liquid to the bed is to separate the liquid from the recycle gas stream and to reinject this liquid directly into the bed, preferably using a method that generates fine droplets 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 catalyzed by the continuous or semi-continuous addition of catalyst.
  • catalyst can be supported on an inorganic or organic support material if desired.
  • the catalyst can also be subjected to a prepolymerization step, for example, by polymerizing a small quantity 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 by catalyzed (co)polymerization of the monomer(s) on the fluidized particles of catalyst, supported catalyst or prepolymer within the bed.
  • Start-up of the polymerization reaction is achieved using a bed of preformed polymer particles, which, preferably, is similar to the target polyolefin, and conditioning the bed by drying with a dry inert gas such as nitrogen prior to introducing the catalyst, the monomer(s) and any other gases which it is desired to have in the recycle gas stream, such as a diluent gas, hydrogen chain transfer agent, or an inert condensable gas when operating in gas phase condensing mode.
  • a dry inert gas such as nitrogen prior to introducing the catalyst, the monomer(s) and any other gases which it is desired to have in the recycle gas stream, such as a diluent gas, hydrogen chain transfer agent, or an inert condensable gas when operating in gas phase condensing mode.
  • the produced polymer is discharged continuously or discontinuously from the fluidized bed as desired, optionally exposed to a catalyst kill and optionally pelletized.
  • Lithium dimethylamide (10.70 g, 210.0 mmol) was added slowly as a solid to a solution of bis(catecholato)diboron (10.00 g, 42.00 mmol) in diethylether (200 mL) at — 20 ° C. This mixture was then allowed to stir for an additional 40 hours at room temperature. After the reaction period, the ether was removed under vacuum and the residue extracted and filtered using hexane. Removal of hexane resulted in the isolation of a yellow oil. Fractional vacuum distillation resulted in the isolation of the desired compound as a pale yellow liquid (5.493 g, 66.0 percent yield).
  • Tetrakis(dimethylamido)diborane (7.756 g, 39.19 mmol) was stirred in diethylether (100 mL) at -78°C as HCI (156.75 mmol, 156.75 mL of 1.0 M solution in diethylether) was added dropwise. This mixture was then allowed to stir for six hours at room temperature. After the reaction period the volatiles were removed and the residue extracted and filtered using hexane. Removal of the hexane resulted in the isolation of a yellow oil.
  • the contents of the reactor was then heated to the desired run temperature under 500 psig (3.4 Mpa) of ethylene pressure.
  • the catalyst composition (as a 0.0050 M solution in toluene) and cocatalyst (tris(pentafluorophenyl)aluminum, FAAL) were combined in the desired ratio in the glove box and transferred from the glove box to the catalyst shot tank through 1/16 in (0.16 cm) tubing using toluene to aid in the transfer.
  • the catalyst tank was then pressurized to 700 psig (4.8 Mpa) using nitrogen. After the contents of the reactor had stabilized at the desired run temperature of 140°C, the catalyst was injected into the reactor via a dip tube.
  • the temperature was maintained by allowing cold ethylene glycol to pass through the internal cooling coils.
  • the reaction was allowed to proceed for 15 minutes with ethylene provided on demand.
  • the contents of the reactor were expelled into a 4 liter nitrogen purged vessel and quenched with isopropyl alcohol.
  • a toluene solution containing approximately 67 mg of a hindered phenol antioxidant (IrganoxTM 1010 from Ciba Geigy Corporation) and 133 mg of a phosphorus stabilizer (IrgafosTM 168 from Ciba Geigy Corporation) were added.
  • a hindered phenol antioxidant IrganoxTM 1010 from Ciba Geigy Corporation
  • a phosphorus stabilizer IrgafosTM 168 from Ciba Geigy Corporation
  • Volatile materials were removed from the polymers in a vacuum oven that gradually heated the polymer to 140°C overnight and cooled to at least 50°C prior to removal from the oven. After completion of the polymerization, the reactor was washed with 1200 ml of mixed hexanes solvent at 150°C before reuse.

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Abstract

L'invention concerne des composés métalliques du groupe 4, dicationiques ou partiellement dicationiques, que l'on utilise, entre autres, en tant que catalyseurs supplémentaires de polymérisation. L'invention concerne encore un procédé de préparation de ces composés.
EP00975243A 1999-10-12 2000-10-12 Complexes metalliques du groupe 4 non metallocenes et dicationiques Ceased EP1222025A2 (fr)

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US6960635B2 (en) * 2001-11-06 2005-11-01 Dow Global Technologies Inc. Isotactic propylene copolymers, their preparation and use
US7910760B2 (en) 2008-04-15 2011-03-22 Exxonmobil Chemical Patents Inc. Semi-rigid linked diamines, precursors therefor, and transition metal diamido complexes as catalysts for olefin polymerization processes

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EP0694548A1 (fr) * 1994-07-29 1996-01-31 ENICHEM ELASTOMERI S.r.l. Dérivés organométalliques du groupe III A et procédé pour leur préparation

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JP3541485B2 (ja) * 1995-03-08 2004-07-14 住友化学工業株式会社 オレフィン重合用触媒及びエチレン−α−オレフィン共重合体の製造方法
US5889128A (en) * 1997-04-11 1999-03-30 Massachusetts Institute Of Technology Living olefin polymerization processes

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0694548A1 (fr) * 1994-07-29 1996-01-31 ENICHEM ELASTOMERI S.r.l. Dérivés organométalliques du groupe III A et procédé pour leur préparation

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
Booth C.; Price C. (eds.): Comprehensive Polymer Science, 1st. ed., vol. 1, Pergamon Press, 1989, pages 16-19 *
Falbe J.; Regitz M. (eds.): 'Polyreaktionen', Römpp's Chemie Lexikon, 9th ed., vol. 5, 1992, pages 3568-9 *
See also references of WO0126806A3 *

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WO2001026806A2 (fr) 2001-04-19

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