WO2001083569A1 - Composes catalytiques, systemes catalytiques et leur utilisation dans un procede de polymerisation - Google Patents

Composes catalytiques, systemes catalytiques et leur utilisation dans un procede de polymerisation Download PDF

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WO2001083569A1
WO2001083569A1 PCT/US2001/010070 US0110070W WO0183569A1 WO 2001083569 A1 WO2001083569 A1 WO 2001083569A1 US 0110070 W US0110070 W US 0110070W WO 0183569 A1 WO0183569 A1 WO 0183569A1
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carbon atoms
unsubstituted
substituted
ruthenium
iso
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PCT/US2001/010070
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English (en)
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Matthew W. Holtcamp
Timothy T. Wenzel
Gregory T. Whiteker
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Univation Technologies, Llc
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Priority to AU2001253005A priority Critical patent/AU2001253005A1/en
Publication of WO2001083569A1 publication Critical patent/WO2001083569A1/fr

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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
    • 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
    • C08F110/00—Homopolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F110/02—Ethene

Definitions

  • the present invention relates to polymerization catalyst systems including a ruthenium complex and a phosphorous containing ligand or alternately, a phosphorus containing ruthenium complex, and to their use in the polymerization of olefin(s).
  • Ruthenium complexes have been reported in the prior art to catalyze olefin dimerization and polymerization.
  • EP 0 188 830 Bl discloses ruthenium complexes, in the presence of monodendate phosphine and sulfonic acid, to catalyze olefin dimerization.
  • WO 99/12981 disclose ruthenium complexes of tridentate diiminopyridine ligands to catalyze olefin polymerization.
  • Komiya, et al., Bulletin of the Chemical Society of Japan 1975, A8, 101 disclose (PPh 3 ) 4 RuH 2 as initiating polymerization of functionalized olefins (acrylonitrile, methyl acrylate) without activating cocatalysts.
  • This invention provides for an improved catalyst compound, a catalyst system and for its use in a polymerizing process.
  • the invention is directed to a catalyst composition including a ruthenium complex and a phosphorous containing ligand, a catalyst system including the catalyst composition, and to its use in the polymerization of olefin(s).
  • the invention is directed to a catalyst composition including a phosphorus containing ruthenium complex, a catalyst system including the catalyst composition, and to its use in the polymerization of olefin(s).
  • the invention is directed to a method for supporting the ruthenium complex and/or the phosphorous containing ligand catalyst compounds, to the supported catalyst system itself; and to its use in the polymerization of olefin(s).
  • the invention is directed to a method for supporting the phosphorus containing ruthenium complex catalyst compounds, to the supported catalyst system itself; and to their use in the polymerization of olef ⁇ n(s).
  • the invention is directed to a process for polymerizing olefm(s), utilizing a ruthenium complex and a phosphorous containing ligand catalyst system or the supported catalyst system described above. In still yet another embodiment, the invention is directed to a process for polymerizing olefm(s), utilizing a phosphorus contaimng ruthenium complex catalyst system or the supported catalyst system described above.
  • the present invention relates to polymerization catalysts and catalyst systems which include a ruthenium complex and at least one phosphorous containing ligand, or alternately, a phosphorus containing ruthenium complex.
  • the ruthenium complexes may be represented by the following formula
  • Ru is ruthenium, preferably in an oxidation state of 0, +2, +3 or +4; n is an integer 0 or 1, but if n is zero then m cannot be 0; m is an integer from 0 to 8, and preferably m is an integer from 1 to 4, but if m is 0 then n cannot be zero.
  • each X is independently a leaving group, preferably hydrogen, an alkyl group, defined below, a heteroatom or a halogen, more preferably X is hydrogen or a halogen and most preferably a halogen; and each L is a donor ligand, preferably, each L is independently ⁇ 6 -benzene, ⁇ 6 - cumene, ⁇ 6 -toluene or cyclooctadiene.
  • An alkyl group may be a linear, branched alkyl radicals, or alkenyl radicals, alkynyl radicals, cycloalkyl radicals or aryl radicals, acyl radicals, aroyl radicals, alkoxy radicals, aryloxy radicals, alkylthio radicals, dialkylamino radicals, alkoxycarbonyl radicals, aryloxycarbonyl radicals, carbomoyl radicals, alkyl- or dialkyl- carbamoyl radicals, acyloxy radicals, acylamino radicals, aroylamino radicals, straight, branched or cyclic, alkylene radicals, or combination thereof.
  • suitable ruthenium complexes include ruthenium (III) chloride, ruthenium (IN) chloride, ruthenium (III) chloride trihydrate.
  • Other specific examples of suitable ruthenium complexes include ( ⁇ 6 -benzene) ruthenium dichloride dimer, ( ⁇ 6 -toluene) ruthenium dichloride dimer, ( ⁇ 6 -cymeme) ruthenium dichloride dimer, and (cyclooctadiene)ruthenium (II) chloride.
  • the phosphorous containing ligand may include phosphines, phosphites, phosphinites and phosphonites.
  • the phosphorous containing ligand is a tertiary phosphine or phosphite, or a di-tertiary diphosphine or diphosphite which may be represented by the following formulae:
  • each R 1 , R 2 and R 3 is independently an alkyl having 1 to 20 carbon atoms, a cycloalkyl having 3 to 12 carbon atoms, a heterocycloalkyl having 2 to 11 carbon atoms, an aryl having 6 to 16 carbon atoms, a heteroaryl having 2 to 15 carbon atoms, or an arylalkyl having 7 to 16 carbon atoms.
  • the alkyl, cycloalkyl, heterocycloalkyl, aryl, heteroaryl and arylalkyl may independently be unsubstituted, or substituted by an alkyl having 1 to 6 carbon atoms, an alkoxy having 1 to 6 carbon atoms, a haloalkyl having 1 to 6 carbon atoms, an aryl having 6 to 16 carbon atoms, a non- hydrogen containing group having from 1 to 50 atoms, -NO 2 , SO 3 " , ammonium, halogen or a combination thereof.
  • R 1 and R 2 together may be tetra- or penta- methylene which maybe unsubstituted, or substituted by an alkyl having 1 to 6 carbon atoms, a haloalkyl having 1 to 6 carbon atoms, -NO 2 , or by an alkoxy having 1 to 6 carbon atoms, or may be tetra or penta methylene which is unsubstituted or substituted by an alkyl having 1 to 6 carbon atoms, a haloalkyl having 1 to 6 carbon atoms, -NO 2 , or by an alkoxy having 1 to 6 carbon atoms, and condensed with one or two l,2-phenylene(s), and R 3 is as defined above.
  • Z is a linear or branched, alkylene having 2 to 12 carbon atoms, which may be unsubstituted, or substituted by an alkyl or alkoxy having 1 to 4 carbon atoms; a 1,2- or
  • 1,3-cycloalkylene having 4 to 8 carbon atoms which may be unsubstituted, or substituted by an alkyl having 1 to 4 carbon atoms or an alkoxy having 1 to 4 carbon atoms
  • a 1,2- or 1,3-heterocycloalkylene having 5 or 6 ring members which may be unsubstituted, or substituted preferably by an alkyl having 1 to 4 carbon atoms or an alkoxy having 1 to 4 carbon atoms
  • 1,2-phenylene which may be unsubstituted, or substituted by an alkyl having 1 to 4 carbon atoms or an alkoxy having 1 to 4 carbon atoms
  • l-methylene-phen-2- yl 1,2 dimethylenebenzene
  • 2,2-diphenlyene which may be unsubstituted or substituted by an alkyl having 1 to 4 carbon atoms or an alkoxy having 1 to 4 carbon atoms.
  • alkyl examples include methyl, ethyl and the isomers of propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl and dodecyl.
  • alkoxy examples include methoxy, ethoxy and the isomers of propoxy and butoxy.
  • An example of aryl substituted alkyl is benzyl.
  • alkylene examples include methylene, ethylene and the isomers of propylene, butylene, pentylene, hexylene, heptylene, octylene, nonylene, decylene, undecylene and dodecylene.
  • cycloalkyl examples include cyclobutyl, cycloheptyl, cyclooctyl and especially cyclopentyl and cyclohexyl.
  • substituted cycloalkyl examples include methyl-, dimethyl-, trimethyl-, methoxy-, dimethozy-, trimethoxy-, trofluoromethyl-, bistriflurormethyl-, and tristrifluoromethyl-cylcopentyl and -cyclohexyl.
  • cycloalkylene examples include 1,2- and 1,3-cyclopentylene and 1,2- and 1,3- cyclohexylene.
  • heterocycloalkyl examples include tetrahydiOfuranyl, pyrrolidinyl, piperazinyl and tetrahydrothiophenyl.
  • heterocycloalkylene examples include 1,2- and 1,3-pyrrolidine, 1,2- and 1,3- piperidine and 1,2- and 1,3-tetrahydrofuran.
  • aryl examples include phenyl and naphthyl.
  • aryloxy examples include phenyloxy and naphthyloxy.
  • substituted aryls are methyl-, dimethyl-, trimethyl-, ethoxy-, dimethoxy-, trimethoxy-, trifluoromethyl-, bistrifluoromethyl- and tristrifluormethyl-phenyl.
  • An example of aralkyl is benzyl. Examples of substituted aralkyl are methyl-, dimethyl-, trimethyl-, methoxy-, dimethoxy-, trimethoxy-, trifluoromethyl-, bistrifluoromethyl-, and tris trifluoromethyl-benzyl.
  • heteroaryl examples include furanyl, thiophenyl, pyrrolyl, pryidinyl and pyrimidinyl.
  • the phosphine ligand is a tertiary phosphine of formula Ha wherein each R 1 , R 2 and R 3 is independently an alkyl having 1 to 20 carbon atoms, a cycloalky having 4 to 12 carbon atoms, a heterocycloalkyl having 2 to 11 carbon atoms, an aryl having 6 to 16 carbon atoms, a heteroaryl having 2 to 15 carbon atoms, or an arylalkyl having 7 to 16 carbon atoms.
  • alkyl, cycloalky, heterocycloalkyl, aryl, heteroaryl or arylalkyl may be unsubstituted, or substituted by an alkyl having 1 to 6 carbon atoms, an alkoxy having 1 to 6 carbon atoms, a haloalkyl having 1 to 6 carbon atoms, an aryl having
  • the tertiary phosphines and phosphites and the ditertiary diphosphines and diphosphites contain from 3 to 40 carbon atoms, more preferably from 3 to 30 carbon atoms and most preferably from 3 to 24 carbon atoms.
  • Preferred examples of tertiary phosphines of formula Ila are
  • Preferred examples of phosphites of formula lie include (CH 3 O) 3 P, (C 2 H 5 O) 3 P, (n-C 3 H 7 O) 3 P, (iso-C 3 H 7 O) 3 P, (n-C 4 H 9 O) 3 P, (2,6-di-tert-C 4 H 9 - C 6 H 3 O) 3 P, (2,3-di-tert-C 4 H 9 -C 6 H 3 O) 3 P, (2,4-di-tert-C 4 H 9 -C 6 H 3 O) 3 P, (iso-C 4 H 9 O) 3 P, (4-
  • phosphorus containing ligand include triphenylphosphine, trimethylphosphine, tricyclohexylphosphine, methyl diphenylphosphine, dimethyl phenylphosphine, cyclohexyldiphenylphosphine, tri-t- butylphosphine, tri-o-tolylphosphine, trimethylphospliite, triphenylphosphite, triethylphosphite and triisopropylphosphite.
  • a phosphorus containing ruthenium complex may be utilized as an olefin(s) polymerization catalyst.
  • the phosphorous containing ruthenium complexes may be represented by the following formulae:
  • Ru, P, L, R 1 , R 2 , R 3 , X, n and m are defined as above, and p is an integer, preferably an integer from 1 to 3.
  • Preferred examples of the phosphorous containing ruthenium complex include tris(triphenylphosphine)ruthenium(II)dichloride, fris(triphenylphosphine)ruthenium(II)hydrido chloride, ( ⁇ 6 -cymene)ruthenium(II)(trimethylphosphine) dichloride,
  • Examples of preferred additional phosphorous ligands include triphenylphosphine, trimethylphosphine, tricyclohexylphosphine, methyl diphenylphosphine, dimethyl phenylphosphine, cyclohexyldiphenylphosphine, tri-t-butylphosphine, tri-o-tolyl ⁇ hosphine, trimethylphosphite, triphenylphosphite, triethylphosphite and tri-isopropylphosphite.
  • catalyst compounds and compositions may be combined with the ruthenium complex and a phosphorous containing ligand catalyst compositions and/or with the phosphorus containing ruthenium complex catalyst compositions of this invention.
  • the catalyst compounds of the invention may be combined with a traditional Zieglar-Natta catalysts and or with a bulky ligand metallocene catalysts and/or with a Group 15 metal containing polymerization catalyst.
  • bulky ligand metallocene catalysts compounds include half and full sandwich compounds having one or more bulky ligands bonded to at least one metal atom.
  • Typical bulky ligand metallocene compounds are described as containing one or more bulky ligand(s) and one or more leaving group(s) bonded to at least one metal atom.
  • at least one bulky ligand is ⁇ -bonded to the metal atom and most preferably ⁇ 5 -bonded to a transition metal atom.
  • the bulky ligands may be represented by one or more open, acyclic, or fused ring(s) or ring system(s) or a combination thereof.
  • the ring(s) or ring system(s) of these bulky ligands are typically composed of atoms selected from Groups 13 to 16 atoms of the Periodic Table of Elements.
  • the atoms are selected from the group consisting of carbon, nitrogen, oxygen, silicon, sulfur, phosphorous, germanium, boron and aluminum or a combination thereof.
  • the ring(s) or ring system(s) are composed of carbon atoms such as but not limited to those cyclopentadienyl ligands or cyclopentadienyl-type ligand structures or other similar functioning ligand structure such as a pentadiene, a cyclooctatetraendiyl or an imide ligand.
  • the metal atom is preferably a transition metal selected from Groups 4 through 12 of the Periodic Table of the Elements, more preferably Groups 4, 5 and 6, and most preferably the transition metal is from Group 4.
  • Group 15 metal containing polymerization catalysts include a Group 3 to 14 metal atom, preferably a Group 3 to 7, more preferably a Group 4 to 6, and even more preferably a Group 4 metal atom, bound to at least one leaving group and also bound to at least two Group 15 atoms, at least one of which is also bound to a Group 15 or 16 atom through another group.
  • At least one of the Group 15 atoms is also bound to a Group 15 or 16 atom through another group which may be a hydrocarbon group having from 1 to 20 carbon atoms, a heteroatom containing group, silicon, germanium, tin, lead, or phosphorus, wherein the Group 15 or 16 atom may also be bound to nothing or a hydrogen, a Group 14 atom contaimng group, a halogen, or a heteroatom contaimng group, and wherein each of the two Group 15 atoms are also bound to a cyclic group and may optionally be bound to hydrogen, a halogen, a heteroatom or a hydrocarbyl group, or a heteroatom containing group.
  • ruthenium complex and phosphorous containing ligand catalyst compositions and the phosphorus containing ruthenium complex catalyst compositions are typically activated in various ways to yield catalyst compounds having a vacant coordination site that will coordinate, insert, and polymerize olefin(s).
  • activator is defined to be any compound or component or method which can activate any of the catalyst compounds or composition of the invention as described above.
  • Non- limiting activators may include a Lewis acid or a non-coordinating ionic activator or ionizing activator or any other compound including Lewis bases, aluminum alkyls, conventional-type cocatalysts and combinations thereof that can convert a neutral ruthenium complex and a phosphorous containing ligand catalyst composition and/or a neutral phosphorus containing ruthemum complex catalyst compound to a catalytically active ruthenium complex and phosphorous containing ligand catalyst composition and/or to a catalytically active phosphorus containing ruthenium complex catalyst compound.
  • aluminoxanes or modified alumoxanes are combined with catalyst compound(s) of the invention.
  • MMAO3A modified methyl alumoxane in heptane, commercially available from Akzo Chemicals, Inc., Holland, under the trade name Modified Methylalumoxane type 3A, see for example those aluminoxanes disclosed in U.S. Patent No. 5,041,584, which is herein incorporated by reference
  • Modified Methylalumoxane type 3A see for example those aluminoxanes disclosed in U.S. Patent No. 5,041,584, which is herein incorporated by reference
  • Organoaluminum compounds useful as activators include trimethylaluminum, triethylaluminum, trusobutylalummum, tri-n-hexylaluminum, tri-n-octylaluminum and the like.
  • an ionizing or stoichiometric activator such as tri (n-butyl) ammonium tetrakis (pentafluorophenyl) boron, a trisperfluorophenyl boron metalloid precursor or a trisperfluoronaphtyl boron metalloid precursor, polyhalogenated heteroborane anions (WO 98/43983) or a combination thereof, that would ionize the neutral ruthenium complex and phosphorous containing ligand catalyst composition and/or the neutral phosphorus containing ruthenium complex catalyst compositions of the invention.
  • neutral or ionic such as tri (n-butyl) ammonium tetrakis (pentafluorophenyl) boron, a trisperfluorophenyl boron metalloid precursor or a trisperfluoronaphtyl boron metalloid precursor, polyhalogenated heteroborane anions (WO 98/43983) or
  • neutral stoichiometric activator examples include tri-substituted boron, tellurium, aluminum, gallium and indium or mixtures thereof.
  • the three substituent groups are each independently selected from alkyls, alkenyls, halogen, substituted alkyls, aryls, arylhalides, alkoxy and halides.
  • the three groups are independently selected from halogen, mono or multicyclic (including halosubstituted) aryls, alkyls, and alkenyl compounds and mixtures thereof, preferred are alkenyl groups having 1 to 20 carbon atoms, alkyl groups having 1 to 20 carbon atoms, alkoxy groups having 1 to 20 carbon atoms and aryl groups having 3 to 20 carbon atoms (including substituted aryls). More preferably, the three groups are alkyls having 1 to 4 carbon groups, phenyl, napthyl or mixtures thereof. Most preferably, the neutral stoichiometric activator is trisperfluorophenyl boron or trisperfmoronapthyl boron.
  • the catalyst system of the invention includes an ionic stoichiometric activator.
  • Ionizing activator compounds may contain an active proton, or some other cation associated with but not coordinated to or only loosely coordinated to the remaining ion of the ionizing compound.
  • Such compounds and the like are described in European publications EP-A-0 570 982, EP-A-0 520 732, EP-A-0 495 375, EP-Bl-0 500 944, EP-A-0 277 003 and EP-A-0 277 004, and U.S. Patent Nos. 5,153,157, 5,198,401, 5,066,741, 5,206,197, 5,241,025, 5,384,299 and 5,502,124 and U.S. Patent Application Serial No. 08/285,380, filed August 3, 1994, all of which are herein fully incorporated by reference.
  • the stoichiometric activators include a cation and an anion component, and may be represented by the following formula:
  • L is an neutral Lewis base
  • H is hydrogen
  • (L-H) + is aBronsted acid
  • a d ⁇ is a non-coordinating anion having the charge d-; and d is an integer from 1 to 3.
  • the cation component, (L-H) d + may include Bronsted acids such as protons or protonated Lewis bases or reducible Lewis acids capable of protonating or abstracting a moiety, such as an alkyl or aryl, from the ruthenium complex and a phosphorous containing ligand catalyst precursor or from the phosphorus containing ruthenium complex catalyst precursor, resulting in a cationic transition metal species.
  • the activating cation (L-H) d + may be a Bronsted acid, capable of donating a proton to the transition metal catalytic precursor resulting in a transition metal cation, including ammoniums, oxoniums, phosphoniums, silyliums and mixtures thereof, preferably ammoniums of methylamine, aniline, dimethylamine, diethylamine, N-methylaniline, diphenylamine, trimethylamine, triethylamine, N,N- dimethylaniline, methyldiphenylamine, pyridine, p-bromo N,N-dimethylaniline, p-nitro-N,N- dimethylaniline, phosphoniums from triethylphosphine, triphenylphosphine, and diphenylphosphine, oxomiuns from ethers such as dimethyl ether diethyl ether, tetrahydrofuran and dioxane, s
  • the activating cation (L-H) d + may also be an abstracting moiety such as silver, carboniums, tropylium, carbeniums, ferroceniums and mixtures, preferably carboniums and ferroceniums. Most preferably (L-H) d + is triphenyl carbonium.
  • each Q is a fluorinated hydrocarbyl group having 1 to 20 carbon atoms, more preferably each Q is a fluorinated aryl group, and most preferably each Q is a pentafluoryl aryl group.
  • the ionic stoichiometric activator (L-H) d + (A d" ) is N,N-dimethylanilinium tetra(perfluorophenyl)borate or triphenylcarbenium tetra(perfluorophenyl)borate.
  • suitable A also include diboron compounds as disclosed in U.S. Patent No. 5,447,895, which is fully incorporated herein by reference.
  • an activation method using ionizing ionic compounds not containing an active proton but capable of producing both a catalyst cation and a non- coordinating anion are also contemplated, and are described in EP-A- 0 426 637, EP-A- 0 573 403 and U.S. Patent No. 5,387,568, which are all herein incorporated by reference.
  • Other activators include those described in PCT publication WO 98/07515 such as tris (2, 2', 2"- nonafluorobiphenyl) fluoroaluminate, which publication is fully incorporated herein by reference.
  • activators are also contemplated by the invention, for example, alumoxanes and ionizing activators in combinations, see for example, EP-B1 0 573 120, PCT publications WO 94/07928 and WO 95/14044 and U.S.
  • Patent Nos. 5,153,157 and 5,453,410 all of which are herein fully incorporated by reference.
  • methods of activation such as using radiation (see EP-Bl-0 615 981 herein incorporated by reference), electrochemical oxidation, and the like are also contemplated as activating methods for the purposes of rendering the neutral bulky ligand metallocene catalyst compound or precursor to a bulky ligand metallocene cation capable of polymerizing olefins.
  • Other activators or methods for activating a bulky ligand metallocene catalyst compound which may be utilized for the catalyst compositions of this invention, are described in for example, U.S. Patent Nos.
  • the above described ruthenium complex, phosphorous containing ligand and/or the phosphorus containing ruthenium complex may optionally be combined with one or more support materials or carriers using one of the support methods well known in the art or as described below.
  • the catalyst system of the invention is in a supported form, for example deposited on, contacted with, vaporized with, bonded to, or incorporated within, adsorbed or absorbed in, or on, a support or carrier.
  • support or “carrier” are used interchangeably and are any support material, preferably a porous support material, including inorganic or organic support materials.
  • inorganic support materials include inorganic oxides and inorganic chlorides.
  • Other carriers include resinous support materials such as polystyrene, functionalized or crosslinked organic supports, such as polystyrene divinyl benzene polyolefins or polymeric compounds or any other organic or inorganic support material and the like, or mixtures thereof.
  • resinous support materials such as polystyrene, functionalized or crosslinked organic supports, such as polystyrene divinyl benzene polyolefins or polymeric compounds or any other organic or inorganic support material and the like, or mixtures thereof.
  • the preferred carriers are inorganic oxides that include those Group 2, 3, 4, 5, 13 or 14 metal oxides.
  • the preferred supports include silica, alumina, silica-alumina, and mixtures thereof.
  • Other useful supports include magnesia, titania, zirconia, magnesium chloride, montmorillonite (EP-B1 0 511 665), phyllosilicate, zeolites, talc, clays and the like.
  • combinations of these support materials may be used, for example, silica- chromium, silica-alumina, silica-titania and the like.
  • Additional support materials may include those porous acrylic polymers described in EP 0 767 184 Bl, which is incorporated herein by reference.
  • the carrier most preferably an inorganic oxide, has a surface area in the range of from about 10 to about 100 rn ⁇ /g, pore volume in the range of from about 0.1 to about 4.0 cc/g and average particle size in the range of from about 5 to about 500 ⁇ m. More preferably, the surface area of the carrier is in the range of from about 50 to about 500 m.2/g, pore volume of from about 0.5 to about 3.5 cc/g and average particle size of from about 10 to about 200 ⁇ m. Most preferably the surface area of the carrier is in the range is from about 100 to about 400 m2/g, pore volume from about 0.8 to about 5.0 cc/g and average particle size is from about 5 to about 100 ⁇ m.
  • the average pore size of the carrier of the invention typically has pore size in the range of from 10 to 1000 A, preferably 50 to about 500A, and most preferably 75 to about 45 ⁇ A. Examples of supporting the catalysts of the invention are described in U.S. Patent Nos.
  • the ruthenium complex, the phosphorous containing ligand, and/or the phosphorus containing ruthenium complex catalyst compounds of the invention may be spray dried as described in U.S. Patent No. 5,648,310, which is herein fully incorporated by reference;
  • the support used with the ruthenium complex, the phosphorous containing ligand, and/or the phosphorus containing ruthenium complex catalyst compounds of the invention is functionalized as described in European publication EP-A-0 802 203, which is herein fully incorporated by reference, or at least one substituent or leaving group is selected as described in U.S. Patent No. 5,688,880, which is herein fully incorporated by reference.
  • the invention provides for the ruthenium complex, the phosphorous containing ligand, and/or the phosphorus containing ruthenium complex to include a surface modifier that is used in the preparation of the supported catalyst system as described in PCT publication WO 96/11960, which is herein fully incorporated by reference.
  • the catalyst systems of the invention can be prepared in the presence of an olefin, for example hexene-1.
  • the ruthenium complex, the phosphorous containing ligand, and or the phosphorus containing ruthenium complex can be combined with a carboxylic acid salt of a metal ester, for example aluminum carboxylates such as aluminum mono, di- and tri- stearates, aluminum octoates, oleates and cyclohexylbutyrates, as described in U.S. Application Serial No. 09/113,216, filed July 10,
  • a supported ruthenium complex, phosphorous containing ligand, and/or the phosphorus containing ruthenium complex is produced as described below and as described in U.S. Application Serial Nos. 265,533, filed June 24, 1994 and 265,532, filed June 24, 1994 and PCT publications WO 96/00245 and WO 96/00243 both published January 4, 1996, all of which are herein fully incorporated by reference. This procedure is used with the ruthenium complex, the phosphorous containing ligand, and/or the phosphorus containing ruthenium complex together or separately.
  • the catalyst ligands and/or complexes are slurried in a liquid to form a solution and a separate solution is formed containing an activator and a liquid.
  • the liquid may be any compatible solvent or other liquid capable of forming a solution or the like with the catalyst compound or compounds and/or activator of the invention.
  • the liquid is a cyclic aliphatic or aromatic hydrocarbon, most preferably toluene.
  • the catalyst compound or compounds and activator solutions are mixed together and added to a porous support such that the total volume of the catalyst compound or compounds solution and the activator solution is less than four times the pore volume of the porous support, more preferably less than three times, even more preferably less than two times; preferred ranges being from 1.1 times to 3.5 times range and most preferably in the 1.2 to 3 times range.
  • the loading of the total of ruthenium complex and the phosphorous containing ligand, and/or the phosphorus containing ruthenium complex in ⁇ mmol per gram (g) of finished supported catalyst is about 40 ⁇ mmol per gram, preferably about 38 ⁇ mmol/g.
  • the loading of the total of ruthenium complex, the phosphorous containing ligand, and/or the phosphorus containing ruthenium complex in ⁇ mmol per gram of finished supported catalyst is less than
  • olefin(s) preferably C2 to C30 olefin(s) or more particularly, alpha-olefin(s), preferably ethylene or propylene or combinations thereof, are prepolymerized in the presence of a supported ruthenium complex, phosphorous containing ligand, and/or the phosphorus contaimng ruthenium complex.
  • the prepolymerization can be carried out batchwise or continuously in gas, solution or slurry phase including at elevated pressures.
  • the prepolymerization can take place with any olefin monomer or combination and/or in the presence of any molecular weight controlling agent such as hydrogen.
  • any molecular weight controlling agent such as hydrogen.
  • the catalyst systems, supported catalyst systems or compositions of the invention described above are suitable for use in any prepolymerization and/or polymerization process over a wide range of temperatures and pressures.
  • the temperatures may be in the range of from -60°C to about 280°C, preferably from 50°C to about 200°C, and the pressures employed may be in the range from 1 atmosphere to about 500 atmospheres or higher.
  • Polymerization processes include solution, gas phase, slurry phase and a high pressure process or a combination thereof. Particularly preferred is a gas phase or slurry phase polymerization of one or more olefins at least one of which is ethylene or propylene.
  • the process of this invention is directed toward a solution, high pressure, slurry or gas phase polymerization process of one or more olefin monomers having from 2 to 30 carbon atoms, preferably 2 to 12 carbon atoms, and more preferably 2 to 8 carbon atoms.
  • the invention is particularly well suited to the polymerization of two or more olefin monomers of ethylene, propylene, butene- 1 , pentene- 1 , 4-methyl-pentene- 1 , hexene-1, octene-1 and decene-1.
  • monomers useful in the process of the invention include ethylenically unsaturated monomers, diolefins having 4 to 18 carbon atoms, conjugated or nonconjugated dienes, polyenes, vinyl monomers and cyclic olefins.
  • Non-limiting monomers useful in the invention may include norbornene, norbornadiene, isobutylene, vinyl acetate, isoprene, vinylbenzocyclobutane, styrenes, alkyl substituted styrene, ethylidene norbornene, dicyclopentadiene and cyclopentene.
  • a copolymer of ethylene is produced, where with ethylene, a comonomer having at least one alpha-olefin having from 4 to 15 carbon atoms, preferably from 4 to 12 carbon atoms, and most preferably from 4 to 8 carbon atoms, is polymerized in a gas phase process.
  • ethylene or propylene is polymerized with at least two different comonomers, optionally one of which may be a diene, to form a terpolymer.
  • the invention is directed to a polymerization process, particularly a gas phase or slurry phase process, for polymerizing propylene alone or with one or more other monomers including ethylene, and/or other olefins having from 4 to 12 carbon atoms.
  • a continuous cycle is employed where in one part of the cycle of a reactor system, a cycling gas stream, otherwise known as a recycle stream or fluidizing medium, is heated in the reactor by the heat of polymerization.
  • This heat is removed from the recycle composition in another part of the cycle by a cooling system external to the reactor.
  • a gas fluidized bed process for producing polymers a gaseous stream containing one or more monomers is continuously cycled through a fluidized bed in the presence of a catalyst under reactive conditions. The gaseous stream is withdrawn from the fluidized bed and recycled back into the reactor. Simultaneously, polymer product is withdrawn from the reactor and fresh monomer is added to replace the polymerized monomer.
  • the reactor pressure in a gas phase process may vary from about 100 psig (690 kPa) to about 500 psig (3448 kPa), preferably in the range of from about 200 psig (1379 kPa) to about 400 psig (2759 kPa), more preferably in the range of from about 250 psig
  • the reactor temperature in a gas phase process may vary from about 30°C to about 120°C, preferably from about 60°C to about 115°C, more preferably in the range of from about 70°C to 110°C, and most preferably in the range of from about 70°C to about 95°C.
  • Other gas phase processes contemplated by the process of the invention include series or multistage polymerization processes.
  • gas phase processes contemplated by the invention include those described in U.S. Patent Nos. 5,627,242, 5,665,818 and 5,677,375, and European publications EP-A- 0 794 200 EP-Bl-0 649 992, EP-A- 0 802 202 and EP-B- 634 421 all of which are herein fully incorporated by reference.
  • the reactor utilized in the present invention is capable and the process of the invention is producing greater than 500 lbs of polymer per hour (227 Kg/hr) to about 200,000 lbs/hr (90,900 Kg/hr) or higher of polymer, preferably greater than 1000 lbs/hr (455 Kg/hr), more preferably greater than 10,000 lbs/hr (4540 Kg/hr), even more preferably greater than 25,000 lbs/hr (11,300 Kg/hr), still more preferably greater than 35,000 lbs/hr (15,900 Kg/hr), still even more preferably greater than 50,000 lbs/hr (22,700 Kg/hr) and most preferably greater than 65,000 lbs/hr (29,000 Kg hr) to greater than 100,000 lbs/hr (45,500 Kg hr).
  • a slurry polymerization process generally uses pressures in the range of from about 1 to about 50 atmospheres and even greater and temperatures in the range of 0°C to about 120°C.
  • a suspension of solid, particulate polymer is formed in a liquid polymerization diluent medium to which ethylene and comonomers and often hydrogen along with catalyst are added.
  • the suspension including diluent is intermittently or continuously removed from the reactor where the volatile components are separated from the polymer and recycled, optionally after a distillation, to the reactor.
  • the liquid diluent employed in the polymerization medium is typically an alkane having from 3 to 7 carbon atoms, preferably a branched alkane.
  • the medium employed should be liquid under the conditions of polymerization and relatively inert.
  • a propane medium When used the process must be operated above the reaction diluent critical temperature and pressure.
  • a hexane or an isobutane medium is employed.
  • a preferred polymerization technique of the invention is referred to as a particle form polymerization, or a slurry process where the temperature is kept below the temperature at which the polymer goes into solution.
  • a particle form polymerization or a slurry process where the temperature is kept below the temperature at which the polymer goes into solution.
  • Such technique is well known in the art, and described in for instance U.S. Patent No. 3,248,179 which is fully incorporated herein by reference.
  • Other slurry processes include those employing a loop reactor and those utilizing a plurality of stirred reactors in series, parallel, or combinations thereof.
  • Non-limiting examples of slurry processes include continuous loop or stirred tank processes.
  • other examples of slurry processes are described in U.S. Patent No. 4,613,484, which is herein fully incorporated by reference.
  • the reactor used in the slurry process of the invention is capable of and the process of the invention is producing greater than 2000 lbs of polymer per hour (907 Kg/hr), more preferably greater than 5000 lbs/hr (2268 Kg/hr), and most preferably greater than 10,000 lbs/hr (4540 Kg/hr). In another embodiment the slurry reactor used in the process of the invention is producing greater than 15,000 lbs of polymer per hour
  • a preferred process of the invention is where the process, preferably a slurry or gas phase process is operated in the presence a catalyst system of the invention and in the absence of or essentially free of any scavengers, such as triethylaluminum, trimethylaluminum, tri-isobutylaluminum and tri-n-hexylaluminum and diethyl aluminum chloride, dibutyl zinc and the like.
  • any scavengers such as triethylaluminum, trimethylaluminum, tri-isobutylaluminum and tri-n-hexylaluminum and diethyl aluminum chloride, dibutyl zinc and the like.
  • a method of the invention provides for injecting an unsupported catalyst complex, ligand, or system of the invention into a reactor, particularly a gas phase reactor.
  • the polymerization catalysts of the invention are used in the unsupported form, preferably in a liquid form such as described in U.S. Patent Nos. 5,317,036 and 5,693,727 and European publication EP-A-0 593 083, all of which are herein incorporated by reference.
  • the polymerization catalyst or catalyst(s) of the invention, in liquid form may be fed with an activator together or separately to a reactor using the injection methods described in PCT publication WO 97/46599, which is fully incorporated herein by reference.
  • the hydrogen concentration in the reactor is from about 100 to 5000 ppm, and preferably from about 200 to 2000 ppm.
  • the hydrogen concentration in the reactor being inversely proportional to the polymer's weight average molecular weight (M w ).
  • the polymers produced by the process of the invention can be used in a wide variety of products and end-use applications.
  • the polymers produced by the process of the invention include linear low density polyethylene, elastomers, plastomers, high density polyethylenes, medium density polyethylenes, low density polyethylenes, polypropylene and polypropylene copolymers.
  • the new polymers include polyethylene
  • the polyolefms particularly polyethylenes, produced by the present invention, have a density of 0.89 to 0.97g/cm 3 .
  • polyethylenes having a density of 0.910 to 0.965g/cm 3 , more preferably 0.915 to 0.960 g/cm 3 , and even more preferably 0.920 to
  • 0.955 g/cm 3 can be produced.
  • a density of 0.915 to 0.940 g/cm 3 would be preferred, in other embodiments densities of 0.930 to 0.970 g/cm 3 are preferred. Density is measured in accordance with ASTM-D-1238.
  • the polymers produced by the process of the invention typically have a molecular weight distribution, a weight average molecular weight to number average molecular weight (M M ⁇ ) of greater than 2, particularly greater than 3.
  • the polymers of the invention typically have a narrow composition distribution as measured by Composition Distribution Breadth Index (CDBI). Further details of determining the CDBI of a copolymer are known to those skilled in the art. See, for example, PCT Patent Application WO 93/03093, published February 18, 1993, which is fully incorporated herein by reference.
  • CDBI Composition Distribution Breadth Index
  • polymers produced using a catalyst system of the invention have a CDBI less than 50%, more preferably less than 40%, and most preferably less than 30%.
  • the polyolef ⁇ n recovered typically has a melt index I 2
  • the polyolefin is ethylene homopolymer or copolymer.
  • a melt index of lOdg/min or less is preferred.
  • a melt index of ldg/min or less is preferred.
  • Polyethylene having a I 2 between 0.01 and lOdg/min is preferred.
  • the polymer produced herein has an I 21 (as measured by ASTM-D-1238-F, at 190 °C) of 0.1 to 100 dg/min, preferably 0.5 dg/min to 50 dg/min, more preferably 2 dg/min to 20 dg/min (especially for pipe applications), and most preferably for film applications from 5 dg/min to 10 dg/min.
  • I 21 as measured by ASTM-D-1238-F, at 190 °C
  • the polymers of the invention in a preferred embodiment have a melt index ratio (I 21 /I 2 ) ( I 21 is measured by ASTM-D-1238-F) of from preferably greater than 80, more preferably greater than 90, even more preferably greater that 100, still even more preferably greater than 110 and most preferably greater than 120.
  • the catalyst composition described above is used to make a polyethylene having a density of between 0.940 and 0.970 g/cm 3 (as measured by ASTM D 2839) and an I 2 of 0.5 or less g/lOmin or less.
  • the catalyst composition described above is used to make a polyethylene having an I 21 of less than 10 and a density of between about 0.940 and 0.950g/cm 3 or an I 21 of less than 20 and a density of about 0.945g/cm 3 or less.
  • the polymers of the invention may be blended and/or coextruded with any other polymer.
  • Non-limiting examples of other polymers include linear low density polyethylenes, elastomers, plastomers, high pressure low density polyethylene, high density polyethylenes, polypropylenes and the like.
  • Polymers produced by the process of the invention and blends thereof are useful in such forming operations as film, sheet, and fiber extrusion and co-extrusion as well as blow molding, injection molding and rotary molding.
  • Films include blown or cast films formed by coextrusion or by lamination useful as shrink film, cling film, stretch film, sealing films, oriented films, snack packaging, heavy duty bags, grocery sacks, baked and frozen food packaging, medical packaging, industrial liners, membranes, etc. in food- contact and non-food contact applications.
  • Fibers include melt spinning, solution spinning and melt blown fiber operations for use in woven or non-woven form to make filters, diaper fabrics, medical garments, geotextiles, etc.
  • Extruded articles include medical tubing, wire and cable coatings, pipe, geomembranes, and pond liners. Molded articles include single and multi-layered constructions in the form of bottles, tanks, large hollow articles, rigid food containers and toys, etc.

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Abstract

L'invention concerne une composition catalytique contenant un complexe de ruthénium et un ligand phosphoreux ou éventuellement un complexe de ruthénium phosphoreux. L'invention concerne en outre des systèmes catalytiques non supportés et supportés de ces derniers, ainsi qu'un procédé de polymérisation d'oléfines au moyen desdits systèmes.
PCT/US2001/010070 2000-05-03 2001-03-29 Composes catalytiques, systemes catalytiques et leur utilisation dans un procede de polymerisation WO2001083569A1 (fr)

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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0970972A1 (fr) * 1998-07-10 2000-01-12 Ciba SC Holding AG Compositions polymérisables contenant Ru(II)- ou Os(II) complexe comme catalysateurs
WO2000069959A2 (fr) * 1999-05-19 2000-11-23 National Institute Of Standards & Technology Nanocomposites inorganiques a couches polymeres

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0970972A1 (fr) * 1998-07-10 2000-01-12 Ciba SC Holding AG Compositions polymérisables contenant Ru(II)- ou Os(II) complexe comme catalysateurs
WO2000069959A2 (fr) * 1999-05-19 2000-11-23 National Institute Of Standards & Technology Nanocomposites inorganiques a couches polymeres

Non-Patent Citations (6)

* Cited by examiner, † Cited by third party
Title
BOUACHIR, FAOUZI ET AL: "Cationic allylmetal complexes. Part 11. Cationic allylruthenium complexes by allyl group exchange", ANGEW. CHEM. (1985), 97(4), 347-8, XP000984338 *
BOUACHIR, FAOUZI ET AL: "Preparation and stoichiometric and catalytic reactivity of hydrido organometallic ruthenium complexes. X-ray crystal structure of [RuH(.eta.5-C8H11)2]BF4", ORGANOMETALLICS (1991), 10(2), 455-62, XP000984345 *
GUSEV, O. V. ET AL: "Ruthenium phosphine complexes as catalysts of alternating copolymerization of ethylene and carbon monoxide", RUSS. CHEM. BULL. (2000), 49(6), 1113-1115, XP001015614 *
JAMES B R ET AL: "KINETICS OF ETHYLENE POLYMERIZATION AND BUTADIENE POLYMERIZATION CATALYZED BY SOLUTIONS OF HYDRIDOCHLOROTRIS(TRIPHENYLPHOSPHINE)RUTHEN IUM(II)", JOURNAL OF CATALYSIS, ACADEMIC PRESS, NEW YORK, NY, US, vol. 27, 1972, pages 442 - 451, XP000984339, ISSN: 0021-9517 *
KOMIYA S ET AL: "POLYMERIZATIONN OF VINYL COMPOUNDS BY DIHYDRIDOTETRAKIS-(TRIPHENYLPHO SPHINE)RUTHENIUM(II)", BULLETIN OF THE CHEMICAL SOCIETY OF JAPAN, JAPAN PUBLICATIONS TRADING CO. TOKYO, JP, vol. 48, no. 1, January 1975 (1975-01-01), pages 101 - 107, XP001015423, ISSN: 0009-2673 *
NOMURA, KOTOHIRO ET AL: "Olefin polymerization by the (pybox)RuX2(ethylene)-MAO catalyst system", MACROMOLECULES (1999), 32(14), 4732-4734, XP000984320 *

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