WO2004108775A1 - Compositions catalytiques activees a base de metal de transition multinucleaire - Google Patents

Compositions catalytiques activees a base de metal de transition multinucleaire Download PDF

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WO2004108775A1
WO2004108775A1 PCT/US2004/013976 US2004013976W WO2004108775A1 WO 2004108775 A1 WO2004108775 A1 WO 2004108775A1 US 2004013976 W US2004013976 W US 2004013976W WO 2004108775 A1 WO2004108775 A1 WO 2004108775A1
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hydrocarbyl
group
independently
occurrence
catalyst composition
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PCT/US2004/013976
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English (en)
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Jürgen SCHELLENBERG
Silke Wichmann
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Dow Global Technologies Inc.
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Publication of WO2004108775A1 publication Critical patent/WO2004108775A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F17/00—Metallocenes
    • 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
    • C08F12/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
    • C08F12/02—Monomers containing only one unsaturated aliphatic radical
    • C08F12/04—Monomers containing only one unsaturated aliphatic radical containing one ring
    • C08F12/06—Hydrocarbons
    • C08F12/08—Styrene
    • 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
    • C08F2410/00—Features related to the catalyst preparation, the catalyst use or to the deactivation of the catalyst
    • C08F2410/03—Multinuclear procatalyst, i.e. containing two or more metals, being different or not
    • 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
    • C08F2410/00—Features related to the catalyst preparation, the catalyst use or to the deactivation of the catalyst
    • C08F2410/04—Dual catalyst, i.e. use of two different catalysts, where none of the catalysts is a metallocene
    • 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
    • C08F4/65912—Component covered by group C08F4/64 containing a transition metal-carbon bond in combination with an organoaluminium compound
    • 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

  • the present invention relates to activated multinuclear transition metal catalyst compositions and their use in polymerization reactions. More particularly, this invention relates to improved activated catalyst compositions comprising a Group 4 metal complex containing multiple transition metals.
  • Group 4 metal compounds containing one or more cyclopentadienyl ligands or multi-ring derivatives of such cyclopentadienyl ligands also known as metallocenes
  • their preparation, methods of activation, active catalysts formed therefrom including cationic catalysts, and methods of use are previously known in the art.
  • Such compounds are capable of preparing polymers of addition polymerizable monomers, especially olefins, including vinylaromatic monomers in high yields and/or narrow molecular weight distributions.
  • Examples include United States Patents (US-A-) 5,045,517, 5,196,490 and 5,536,797 wherein titanium containing compounds that are highly selective for the production of syndiotactic polymers of vinyl aromatic monomers are disclosed. Multinuclear, especially binuclear, transition metal compounds useful as catalyst components are disclosed in US-A-5,892,079.
  • US-A-5 ,045,517 and US-A-5, 196,490 disclose a process for preparing syndiotactic polymers of vinyl aromatic monomers using, as a catalyst, the reaction product of polymethylalurninoxane and a titanium (IV) complex corresponding to the formula CPT1X3.
  • Cp and X are defined at column 1, lines 32-45.
  • Illustrative CpTiX3 complexes include cyclopentadienyltitanium tris(phenoxide), cyclopentadienyltitanium tris(ethoxide), indenyltitanium tris(dimethylamide), cyclopentadienyltitanium tris(dimethylamide), pentamethylcyclopenta- dienyltitanium tris(phenoxide) and cyclopentadienyltitanium phenoxy dichloride.
  • US-A-5,536,797 teaches preparation of polymers of prochiral olefin monomers having high stereo-regularity (for example, high syndiotactic polymers) and a molecular weight less than 500,000 using an octahydrofluorenyltitanium metal complex or a ring substituted octahydrofluorenyltitanium metal complex in the +2, +3 or +4 formal oxidation state and an activating cocatalyst or activating technique.
  • high stereo-regularity for example, high syndiotactic polymers
  • metal complexes examples include octahydrofluorenyltitanium (TV) trichloride; octahydrofluorenyltitanium (TV) trimethoxide; octahydrofluorenyltitanium (TV) triphenoxide; octahydrofluorenyltitanium (TV) dichloride phenoxide; octahydrofluorenyltitanium (HI) dimethoxide; octahydrofluorenyltitanium (IE) methyl (2-dimethylaminobenzyl); octahydrofluorenyltitanium (TJ) allyl (s-cis-l,4-diphenylbutadiene); octahydrofluorenyltitanium (TT) 2,4-dimethylpentadienyl. Additional complexes that are variously substituted as herein
  • US-A-5,892,079 provides a number of novel metallocene catalysts at column 4, line 20 through column 5, line 20.
  • Specific metallocene catalyst examples include those found in columns 10-16.
  • the present invention is an activated catalyst composition produced by contacting A) a multinuclear transition metal compound with B) a mononuclear transition metal compound.
  • This activated catalyst composition can be used in polymerization reactions to enable higher polymerization conversions when compared to the use of multinuclear transition metal compounds alone.
  • compositions claimed herein through use of the term “comprising” may include any additional additive, adjuvant, or compound whether polymeric or otherwise, unless stated to the contrary.
  • polymer includes both homopolymers, that is, polymers prepared from a single reactive compound, and copolymers, that is, polymers prepared by reaction of at least two polymer forming reactive, monomeric compounds.
  • copolymers that is, polymers prepared by reaction of at least two polymer forming reactive, monomeric compounds.
  • synthetic means a polymer of one or more monomers capable of forming enantiomers wherein the syndiotacticity at a racemic diad in the 13 C nuclear magnetic resonance spectrum thereof is at least seventy five percent, or the syndiotacticity at a racemic pentad in the 13 C nuclear magnetic resonance spectrum thereof is at least thirty percent.
  • the multinuclear transition metal compound used in the catalyst composition of the present invention is any compound described by Formula (I). wherein:
  • M is independently a metal of Group 4 or the Lanthanide Series of the Periodic Table and is preferably titanium (Ti), zirconium (Zr) or hafnium (Hf);
  • R 1 is independently in each occurrence a C 1-5 o(l to 50 carbon atoms, "C” representing carbon and the subscript showing the range of atoms of the element so modified) hydrocarbon group, ⁇ -coordinated hydrocarbyl Hgand, or a boron (B), silicon (Si), nitrogen (N), phosphorus (P), or oxygen (O) substituted derivative thereof, wherein any R 1 group may optionally contain one or more halo-, halocarbyl-, halohydrocarbyl-, tri(hydrocarbyl)silyl-, or tri(hydrocarbyl)silylhydrocarbyl-, substituents.
  • R 1 is a cyclopentadienyl, pentamethylcyclopentadienyl, indenyl, benzindenyl, fluorenyl, or octahydrofluorenyl group; or substituted groups thereof; and more preferably R 1 contains no metal atoms;
  • R 2 is independently in each occurrence R 1 , a hydride, or a hydrocarbyl, hydrocarbyloxy, di(hydrocarbyl)amido, trihydrocarbylsilyl, or halo group of up to 20 nonhydrogen atoms;
  • R a is independently in each occurrence R 1 , R 2 , or a divalent ligand group selected from O, NR 5 , PR 5 , 0-R 4 -0, NR 5 -R 4 -NR 5 , and PR 5 -R 4 -PR 5 , which is shared by two metal centers, M, in the form of a ⁇ -bridged structure;
  • R 4 is a divalent ligand group of up to 30 atoms, not counting hydrogen, preferably C ⁇ -]0 alkylene;
  • R 5 is an anionic ligand group of up to 30 atoms, not counting hydrogen, preferably C ⁇ -6 alkyl; and m is 1, 2, or 3; n is an integer greater than or equal to (>) 1; p is equal to 4-m; q is an integer >1 ; and r is an integer >1.
  • n is >1, but less than ( ⁇ ) 100
  • q is >1, but ⁇ 100
  • r is >1, but ⁇ 100.
  • the multinuclear transition metal compound may be of the formula:
  • R 1 , R 2 , R 3 , and n are as defined previously or when n is >2, two R 2 groups on different metal centers may together form an R 3 group;
  • M is independently in each occurrence a group 4 metal, preferably Ti;
  • the metal compounds preferably are Group 4 metalloxanes having an "adamantane like'' structure corresponding to the formula:
  • M and R 1 are as previously defined with respect to compounds of formula (I).
  • Preferred metal complexes are those complexes of formula (HI) wherein M in each occurrence is Ti, and R 1 independently in each occurrence is ⁇ 5 -pentamethylcyclopentadienyl or ⁇ 5 octahydrofluorenyl.
  • Additional multinuclear transition metal compounds useful in the catalyst composition of the present invention include the following:
  • the foregoing metal complexes are conveniently prepared by standard metallation and ligand exchange procedures involving a source of the transition metal and the various ligand sources.
  • the metalloxanes in particular are prepared by reaction of the corresponding monocyclopentadienyl metal trialkoxide with water.
  • the complexes may be prepared using standard dry box synthetic techniques.
  • the multinuclear transition metal compounds may also be supported on a support material and used in olefin polymerization processes in a slurry or in the gas phase upon activation.
  • the catalyst composition of the present invention additionally comprises a mononuclear transition metal compound of formula VIE:
  • M' is independently a metal of Group 4 or the Lanthanide Series of the Periodic Table, or a mixture thereof; preferably Ti, Zr, or Hf;
  • X is independently a halide (that is, bromine, fluorine, chlorine, or iodine), preferably chlorine; and s is 2, 3 or 4, preferably 4.
  • the mononuclear transition metal compound is titanium tetrachloride.
  • Mononuclear transition metal compounds are well known by those skilled in the art and are typically commercially available. Methods of making such compounds are also well known by those skilled in the art.
  • the multinuclear transition metal compound of A) and mononuclear transition metal compound of B) are typically used in molar ratios (B:A) of from (5n):l to (0.05n):l, and preferably from (4n):l to (0.1n):l.; wherein n is as defined in Formula I.
  • the two components used to produce the activated catalyst composition of the present invention can be combined prior to use, or can be added independently within a reaction process.
  • the activated catalyst composition of the present invention can be used in polymerization processes with polymerizable monomers or mixtures thereof by contacting said monomer or mixture of monomers with the activated catalyst composition under polymerization conditions.
  • Preferred polymerizable monomers are C 8-2 o vinylaromatic monomers, especially styrene, o-, m- or p- C M alkyl- substituted styrenes, and mixtures thereof, which form highly syndiotactic polymers.
  • Polymers prepared by the foregoing invented process are usefully employed for injection molding and other applications.
  • the activated catalyst composition of the present invention can also be used in combination with other components which are beneficial to the polymer product being produced.
  • Such compounds include additional cocatalysts useful in polymerization reactions.
  • Suitable cocatalysts useful in combination with the present activated catalyst composition of the present invention are those compounds capable of abstraction of a substituent therefrom to form an inert, non-interfering counter ion, or that form a zwitterionic or other catalytically active derivative of the metal complex.
  • Suitable cocatalysts for use herein include Lewis acids, such as alumoxanes, including trialkylaluminum, tris(fluoroaryl)aluminum and tris(fluoroaryl)boron modified alumoxanes, or perfluorinated tri(aryl)boron compounds, and most especially methylalumoxane (MAO) or tris(pentafluorophenyl)borane; nonpolymeric, compatible, noncoordinating, ion forming compounds (including the use of such compounds under oxidizing conditions), especially ammonium-, phosphonium-, oxonium-, carbonium-, silylium-, sulfonium-, or ferrocenium- salts of compatible, noncoordinating anions.
  • a combination of the foregoing cocatalysts may be employed as well.
  • suitable ion forming compounds useful as cocatalysts in one embodiment of the present invention comprise a cation which is a Bronsted acid capable of donating a proton, and a compatible, noncoordinating anion, A " .
  • Preferred anions are those containing a single coordination complex comprising a charge-bearing metal or metalloid core which anion is capable of balancing the charge of the active catalyst species (the metal cation) which may be formed when the two components are combined.
  • said anion should be sufficiently labile to be displaced by olefinic, diolefinic and acetylenically unsaturated compounds or other neutral Lewis bases such as ethers or nitriles.
  • Suitable metals include, but are not limited to, aluminum (Al), gold and platinum.
  • Suitable metalloids include, but are not limited to, B, P, and Si.
  • Compounds containing anions which comprise coordination complexes containing a single metal or metalloid atom are, of course, well known and many, particularly such compounds containing a single boron atom in the anion portion, are available commercially.
  • cocatalysts may be represented by the following general formula: (L*-H) + d (A) d - n (X) wherein:
  • L* is a neutral Lewis base
  • (L*-H) + is a Bronsted acid
  • a d" is a noncoordinating, compatible anion having a charge of d-, and d is an integer from 1 to 3.
  • a d" corresponds to the formula: [M'Q ] " ; (XI)- wherein:
  • M' is B or Al in the +3 formal oxidation state
  • Q independently each occurrence is selected from hydride, dialkylamido, halide, hydrocarbyl, hydrocarbyloxide, halosubstituted-hydrocarbyl, hydroxy- substituted hydrocarbyl, halosubstituted hydrocarbyloxy, and halo- substituted silylhydrocarbyl radicals (including perhalogenated hydrocarbyl- perhalogenated hydrocarbyloxy- and perhalogenated silylhydrocarbyl radicals), said Q having up to 20 carbons with the proviso that in not more than one occurrence is Q halide.
  • suitable hydrocarbyloxide Q groups are disclosed in US-A-5,296,433.
  • d is one, that is, the counter ion has a single negative charge and is A " .
  • Cocatalysts comprising B which are particularly useful in the preparation of catalysts of this invention may be represented by the following general formula: (L*-H) + (BQ 4 )-; (XE) wherein: L* is as previously defined;
  • B is boron in a formal oxidation state of 3
  • Q is a hydrocarbyl-, hydrocarbyloxy-, fluorinated hydrocarbyl-, fluorinated hydrocarbyloxy- , or fluorinated silylhydrocarbyl- group of up to 20 nonhydrogen atoms, with the proviso that in not more than one occasion is Q hydrocarbyl.
  • Q is each occurrence a fluorinated aryl group, especially, a pentafluorophenyl group.
  • B compounds which may be used as an cocatalyst in the preparation of the improved catalysts of this invention are tri-substituted ammonium salts such as: trimethylammonium tetrakis(pentafluorophenyl) borate, triethylammonium tetrakis(pentafluorophenyl) borate, tripropylammonium tetrakis(pentafluorophenyl) borate, tri(n-butyl)ammonium tetrakis(pentafluorophenyl) borate, tri(sec-butyl)ammonium tetrakis(pentafluorophenyl) borate, N,N-dimethyl-N-dodecylammonium tetrakis(pentafluorophenyl) borate,
  • N,N-dimethyl-2,4,6-trimethylanilinium tetrakis(pentafluorophenyl) borate trimethylammonium tetrakis(2,3 ,4,6-tetrafluorophenyl)borate, triethylammonium tetrakis(2,3,4,6-tetrafluorophenyl) borate, tripropylammonium tetrakis(2,3,4,6-tetrafluorophenyl) borate, tri(n-butyl)ammonium tetrakis(2,3,4,6-tetrafluorophenyl) borate, dimethyl(t-butyl)ammonium tetrakis(2,3,4,6-tetrafluorophenyl) borate,
  • Preferred (L*-H) + cations are N,N-dimethylanilinium, tributylammonium, N-methyl-N,N- di(dodecyl)ammonium, N-methyl-N,N-di(tetradecyl)ammonium, N-methyl-N,N- di(hexadecyl)ammonium, N-methyl-N,N-di(octadecyl)ammonium, and mixtures thereof.
  • the latter three cations are the primary ammonium cations derived from a commercially available mixture of tallow amines, and are collectively referred to as bis-hydrogenated tallowalkyl methylammonium cation.
  • Another suitable ion forming, cocatalyst comprises a salt of a cationic oxidizing agent and a noncoordinating, compatible anion represented by the formula: (Ox ) d (A d % (XTTT) wherein:
  • Ox 6-1" is a cationic oxidizing agent having a charge of e+; e is an integer from 1 to 3; and A d" and d are as previously defined.
  • cationic oxidizing agents include: ferrocenium, hydrocarbyl-substituted ferrocenium, Ag + or Pb + 2.
  • Preferred embodiments of A d" are those anions previously defined with respect to the Bronsted acid containing cocatalysts, especially tetrakis(pentafluorophenyl)borate.
  • Another suitable ion forming, cocatalyst comprises a compound which is a salt of a carbenium ion and a noncoordinating, compatible anion represented by the formula: ⁇ + A ' (XIV) wherein:
  • ⁇ + is a C1. 20 carbenium ion;
  • a " is as previously defined.
  • a preferred carbenium ion is the trityl cation,that is, triphenylmethylium.
  • a further suitable ion forming, cocatalyst comprises a compound which is a salt of a silylium ion and a noncoordinating, compatible anion represented by the formula: R * 3 Si + A- (XV) wherein: R"is Ci.io hydrocarbyl, and A " are as previously defined.
  • Preferred silylium salt cocatalysts are trimethylsilylium tetrakispentafluorophenylborate, triethylsilylium tetrakispentafluorophenylborate and ether substituted adducts thereof.
  • a 1 is a cation of charge ⁇ a 1 ,
  • Z 1 is an anion group of from 1 to 50, preferably 1 to 30 atoms, not counting hydrogen atoms, further containing two or more Lewis base sites;
  • J 1 independently each occurrence is a Lewis acid coordinated to at least one Lewis base site of Z 1 , and optionally two or more such J 1 groups may be joined together in a moiety having multiple Lewis acidic functionality
  • j 1 is a number from 2 to 12 and a 1 , b', c 1 , and d 1 are integers from 1 to 3, with the proviso that a 1 x b 1 is equal to c 1 x d 1 .
  • a 1+ is a monovalent cation as previously defined, and preferably is a trihydrocarbyl ammonium cation, containing one or two C ⁇ 0-4 o alkyl groups, especially the methylbis(tetradecyl)ammonium- or methylbis(octadecyl)ammonium- cation, R 8 , independently each occurrence, is hydrogen or a halo, hydrocarbyl, halocarbyl, halohydrocarbyl, silylhydrocarbyl, or silyl, (including mono-, di- and tri(hydrocarbyl)silyl) group of up to 30 atoms not counting hydrogen, preferably C ⁇ -20 alkyl, and
  • J 1 is tris(pentafluorophenyl)borane or tris(pentafluorophenyl)aluminane.
  • these catalyst activators include the trihydrocarbylammonium-, especially, methylbis(tetradecyl)ammonium- or methylbis(octadecyl)ammonium- salts of: bis(tris(pentafluorophenyl)borane)imidazolide, bis(tris(pentafluorophenyl)borane)-2-undecylimidazolide, bis(tris(pentafluorophenyl)borane)-2- heptadecylimidazolide, bis(tris(pentafluorophenyl)borane)-4,5-bis(undecyl)imidazolide, bis(tris(pentafluorophenyl)borane)-4,5-bis(heptadecy
  • a further class of additional suitable activating cocatalysts which may be used in the composition of the present invention include cationic Group 13 salts corresponding to the formula: [M"Q 1 2 L' r ] + (Ar f 3 M'Q 2 )- (XX) wherein:
  • M" is Al, gallium, or indium; M' is B or Al;
  • Q 1 is C ⁇ -20 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 1 groups may be covalently linked with each other to form one or more fused rings or ring systems;
  • Q 2 is an alkyl group, optionally substituted with one or more cycloalkyl or aryl groups, said Q 2 having from 1 to 30 carbons;
  • L' is a monodentate or polydentate Lewis base, preferably L' is reversibly coordinated to the metal complex such that it may be displaced by an olefin monomer, more preferably L' is a monodentate Lewis base;
  • P is a number greater than zero indicating the number of Lewis base moieties, L', and Ar f independently each occurrence is an anionic ligand group; preferably Ar f is selected from the group consisting of halide, C 1-20 halohydrocarbyl, and Q 1 ligand groups, more preferably Ar f is a fluorinated hydrocarbyl moiety of from 1 to 30 carbon atoms, most preferably Ar f is a fluorinated aromatic hydrocarbyl moiety of from 6 to 30 carbon atoms, and most highly preferably Ar f is a perfluorinated aromatic hydrocarbyl moiety of from 6 to 30 carbon atoms.
  • Group 13 metal salts are aluminium tris(fluoroaryl)borates or gallicinium tris(fluoroaryl)borates corresponding to the formula: wherein M" is aluminum or gallium; Q 1 is C ⁇ -20 hydrocarbyl, preferably C ⁇ . 8 alkyl; Ar f is perfluoroaryl, preferably pentafluorophenyl; and Q 2 is C ⁇ -8 alkyl, preferably d -8 alkyl. More preferably, Q 1 and Q 2 are identical C 1-8 alkyl groups, most preferably, methyl, ethyl or octyl.
  • the foregoing activating cocatalysts may also be used in any combination.
  • An especially preferred combination is a mixture of a tri(hydrocarbyl)aluminum or tri(hydrocarbyl)borane compound having from 1 to 4 carbons in each hydrocarbyl group or an ammonium borate with an oligomeric or polymeric alumoxane compound.
  • the molar ratio of the amount of metal in the activated catalyst composition of the present invention to additional cocatalyst, if employed, preferably ranges from 1:10,000 to 100:1, more preferably from 1:5000 to 10:1, most preferably from 1:1000 to 1:1.
  • Alumoxane when used by itself as an activating cocatalyst, is employed in large quantity, generally at least 50 times the quantity of the amount of metal in the activated catalyst composition on a molar basis.
  • Tris(pentafluorophenyl)-borane, where used as an additional activating cocatalyst is employed in a molar ratio to the amount of metal in the activated catalyst composition of from 0.5:1 to 10:1, more preferably from 1 : 1 to 6 : 1 most preferably from 1 : 1 to 5 : 1.
  • the remaining activating cocatalysts are, if used, generally employed in approximately equimolar quantity to the amount of metal in the activated catalyst composition.
  • the most preferred activating cocatalysts are methylalumoxanes, including tri(C 3- ⁇ 2 alkyl)aluminum modified alumoxanes, trispentafluorophenylborane and a mixture of long chain ammonium salts of tetrakis(pentafluorophenyl)borate, especially N,N-dioctadecyl-N- methylammonium tetrakpentafluorophenylborate, N-methyl-N,N-di(hexadecyl)ammonium tetrakpentafluorophenylborate and N,N-ditetradecyl-N-methylammonium tetrakpentafluorophenylborate.
  • the latter mixture of borate salts is derived from hydrogenated tallow amine, and is referred to as bis-hydrogenated tallowalkyl methylammonium tetraki
  • Additional components such as scavengers, especially trialkylaluminum compounds, dialkylaluminum alkoxides, dialkylaluminum N,N-di(hydrocarbyl)amides, alkylaluminum dialkoxide compounds and hydroxyl containing compounds, especially triphenylmethanol, and the reaction products of such hydroxyl containing compounds with alkylaluminum compounds, may be included in the catalyst composition of the invention if desired.
  • a particularly preferred scavenger is triisobutylaluminum (TIBA).
  • TIBA triisobutylaluminum
  • additional components are present in the reaction mixture in molar ratios from 1 : 1 to 500: 1 based on the amount of metal in the activated catalyst composition, preferably from 10:1 to 100:1.
  • the activated catalyst composition of the present invention may be used in the polymerization of ethylenically unsaturated monomers having from 2 to 20 carbon atoms either alone or in combination.
  • Preferred monomers include monovinylidene aromatic monomers, 4- vinylcyclohexene, vinylcyclohexane, norbornadiene and C 2- ⁇ o aliphatic ⁇ -olefins (especially ethylene, propylene, isobutylene, 1-butene, 1-hexene, 3-methyl-l-pentene, 4-methyl-l-pentene, and 1-octene), Guo dienes, and mixtures thereof.
  • the particularly preferred dienes are 1,4- hexadiene (HD), 5-ethylidene-2-norbornene (ENB), 5-vinylidene-2-norbornene (VNB), 5- methylene-2-norbornene (MNB), and dicyclopentadiene (DCPD).
  • the especially preferred dienes are 5-ethylidene-2-norbornene (ENB) and 1,4-hexadiene (HD).
  • Most preferred monomers are ethylene, mixtures of ethylene, propylene and ethylidenenorbornene, mixtures of ethylene and a G ⁇ s ⁇ -olefin, especially 1-butene, 1-hexene or 1-octene, styrene, and mixtures of styrene and p- methylstyrene.
  • 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 to 250 degrees centigrade (°C), preferably 30 to 200 °C and pressures from atmospheric to >30,000 atmospheres.
  • a support for the multinuclear transition metal compound of the activated catalyst composition especially silica, alumina, or a polymer (especially poly(tetrafluoroethylene) or a polyolefin) may be employed, and desirably is employed when the activated multinuclear transition metal catalyst composition is used in a gas phase polymerization process.
  • the support is preferably employed in an amount to provide a weight ratio of the multinuclear transition metal catalyst composition to support from 1 : 100,000 to 1 : 10, more preferably from 1 :50,000 to 1 :20, and most preferably from 1 : 10,000 to 1 :30.
  • the molar ratio of the amount of metal in the activated catalyst composition to polymerizable compounds employed is from 10 "12 :1 to 10 -1 :1, more preferably from 10 "9 :1 to 10 "5 :1.
  • Suitable solvents for polymerization are 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; perfluorinated hydrocarbons such as perfluorinated C 4- ⁇ 0 alkanes, and the like and aromatic and alkyl-substiruted aromatic compounds such as benzene, toluene, xylene, ethylbenzene and the like.
  • Suitable solvents also include liquid olefins which may act as monomers or comonomers including ethylene, propylene, butadiene, cyclopentene, 1-hexene, 1-hexane, 4-vinylcyclohexene, vinylcyclohexane, 3-methyl-l-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.
  • the activated catalyst composition of the present invention may be utilized in combination with at least one additional homogeneous or heterogeneous polymerization catalyst in the same or separate reactors connected in series or in parallel to prepare polymer blends having desirable properties.
  • the activated catalyst composition may be prepared as a homogeneous catalyst by addition of the requisite components to a solvent.
  • the activated catalyst composition may also be prepared and employed as a heterogeneous catalyst by adsorbing the requisite components on a catalyst support material such as silica gel, alumina or other suitable inorganic support material.
  • a catalyst support material such as silica gel, alumina or other suitable inorganic support material.
  • silica When prepared in heterogeneous or supported form, it is preferred to use silica as the support material.
  • the heterogeneous form of the catalyst system is desirably employed in a slurry or gas phase polymerization. As a practical limitation, slurry polymerization takes place in liquid diluents in which the polymer product is substantially insoluble.
  • the diluent for slurry polymerization is one or more hydrocarbons with ⁇ 5 carbon atoms.
  • saturated hydrocarbons such as ethane, propane or butane may be used in whole or part as the diluent.
  • ⁇ -olef ⁇ n monomer or a mixture of different ⁇ -olefm monomers may be used in whole or part as the diluent.
  • the diluent comprises in at least major part the ⁇ -olefin monomer or monomers to be polymerized.
  • solution polymerization conditions utilize a solvent for the respective components of the reaction, particularly the resulting polymer, at the temperature of operation.
  • Preferred solvents include mineral oils and the various hydrocarbons which are liquid at reaction temperatures.
  • Illustrative examples of useful solvents include alkanes such as pentane, iso-pentane, hexane, heptane, octane and nonane, as well as mixtures of alkanes including kerosene and Isopar ETM, available from Exxon Chemicals Inc.; cycloalkanes such as cyclopentane and cyclohexane; and aromatics such as benzene, toluene, xylenes, ethylbenzene and diethylbenzene.
  • the individual ingredients as well as the recovered activated catalyst components must be protected from oxygen and moisture. Therefore, the activated catalyst components and activated catalyst composition must be prepared and recovered in an oxygen and moisture free environment.
  • the syntheses are performed in the presence of a dry, inert gas such as, for example, nitrogen.
  • a dry, inert gas such as, for example, nitrogen.
  • the polymerization of olefin monomers is carried out with a differential pressure from 10 to 1000 pounds per square in (psi) (70 to 7000 kilopascals (kPa)), most preferably from 40 to 400 psi (30 to 300 kPa).
  • the polymerization is generally conducted at a temperature of from 25 to 200 °C, preferably from 75 to 170 °C, and most preferably from greater than 95 to 160 °C.
  • Generally polymerization of vinylaromatic monomers is conducted in a solid, powder bed polymerization reactor at temperatures from 25 to 120°C, preferably from 50 to 90 °C under conditions to avoid substantial formation of atactic vinylaromatic polymer.
  • the polymerization may be carried out as a batchwise or a continuous polymerization process.
  • a continuous process is preferred, in which event the catalyst composition or the individual components thereof, monomer(s), and optionally solvent are continuously supplied to the reaction zone and polymer product continuously or semi-continuously removed therefrom.
  • Catalyst premix solutions are prepared in a 10 ml glass flask by combining 3.59 ml of 1.52 Molar methylalumoxane (MAO) solution in toluene, 3.00 ml of a 1 Molar solution of triisobutylaluminum (TIBA) in toluene, and the corresponding amount of the titanium compound:
  • MAO Molar methylalumoxane
  • TIBA triisobutylaluminum
  • Styrene polymerizations are conducted in glass ampoules charged with 10 ml of deoxygenated styrene that had been passed through activated alumina and hydrogenated using palladium (Pd) on alumina to remove impurities.
  • the flasks are capped with a septum, crimp sealed and placed in a water bath at the desired temperature for 10 minutes to equilibrate.
  • Polymerization is initiated by addition of 145.5 microliters ( ⁇ l) the desired catalyst premix solution via microliter syringe. After polymerization for the desired time, the reaction is quenched by addition of methanol. The resulting polymer is isolated and dried under vacuum for 30 minutes at 150 °C followed by 35 minutes at 250 °C. Results are contained in Table 1.
  • Tg Glass transition temperature
  • Mw weight average molecular weight
  • SEC size-exclusion chromatography

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Abstract

L'invention concerne une composition catalytique activée obtenue par mise en contact : A) d'un composé de métal de transition multinucléaire avec B) un composé de métal de transition mononucléaire. Cette composition catalytique activée peut être utilisée dans des réactions de polymérisation pour permettre des conversions de polymérisation supérieures en comparaison avec des composés de métaux de transition multinucléaires utilisés seuls.
PCT/US2004/013976 2003-06-05 2004-05-05 Compositions catalytiques activees a base de metal de transition multinucleaire WO2004108775A1 (fr)

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WO2011119116A1 (fr) * 2010-03-25 2011-09-29 Agency For Science, Technology And Research Catalyseur multinucléaire auto-assemblé pour la polymérisation d'oléfines
US8431661B2 (en) 2010-10-21 2013-04-30 Exxonmobil Chemical Patents Inc. Polyethylene and process for production thereof
US8507103B2 (en) 2007-12-18 2013-08-13 Exxonmobil Chemical Patents Inc. Polyethylene and process for production thereof
US8829138B2 (en) 2010-10-21 2014-09-09 Exxonmobil Chemical Patents Inc. Polyethylene and process for production thereof
EP2915826A1 (fr) 2010-10-21 2015-09-09 Univation Technologies, LLC Polyéthylène et son procédé de fabrication
CN112745422A (zh) * 2019-10-31 2021-05-04 中国石油化工股份有限公司 一种用于制备烯烃-烯烃醇共聚物的方法
CN112745429A (zh) * 2019-10-31 2021-05-04 中国石油化工股份有限公司 用于制备烯烃-不饱和羧酸共聚物的方法

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Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8507103B2 (en) 2007-12-18 2013-08-13 Exxonmobil Chemical Patents Inc. Polyethylene and process for production thereof
WO2011119116A1 (fr) * 2010-03-25 2011-09-29 Agency For Science, Technology And Research Catalyseur multinucléaire auto-assemblé pour la polymérisation d'oléfines
US8431661B2 (en) 2010-10-21 2013-04-30 Exxonmobil Chemical Patents Inc. Polyethylene and process for production thereof
US8829138B2 (en) 2010-10-21 2014-09-09 Exxonmobil Chemical Patents Inc. Polyethylene and process for production thereof
US8865849B2 (en) 2010-10-21 2014-10-21 Exxonmobil Chemical Patents Inc. Polyethylene and process for production thereof
EP2915826A1 (fr) 2010-10-21 2015-09-09 Univation Technologies, LLC Polyéthylène et son procédé de fabrication
CN112745422A (zh) * 2019-10-31 2021-05-04 中国石油化工股份有限公司 一种用于制备烯烃-烯烃醇共聚物的方法
CN112745429A (zh) * 2019-10-31 2021-05-04 中国石油化工股份有限公司 用于制备烯烃-不饱和羧酸共聚物的方法
CN112745429B (zh) * 2019-10-31 2022-03-15 中国石油化工股份有限公司 用于制备烯烃-不饱和羧酸共聚物的方法
CN112745422B (zh) * 2019-10-31 2022-03-15 中国石油化工股份有限公司 一种用于制备烯烃-烯烃醇共聚物的方法

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