EP0825897A1 - Catalyseur a support polymere pour la polymerisation d'olefines - Google Patents

Catalyseur a support polymere pour la polymerisation d'olefines

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Publication number
EP0825897A1
EP0825897A1 EP96911489A EP96911489A EP0825897A1 EP 0825897 A1 EP0825897 A1 EP 0825897A1 EP 96911489 A EP96911489 A EP 96911489A EP 96911489 A EP96911489 A EP 96911489A EP 0825897 A1 EP0825897 A1 EP 0825897A1
Authority
EP
European Patent Office
Prior art keywords
catalyst
natta catalyst
supported ziegler
copolymer
supported
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP96911489A
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German (de)
English (en)
Other versions
EP0825897A4 (fr
Inventor
Anthony-J. Dimaio
Craig C. Meverden
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Equistar Chemicals LP
Original Assignee
Quantum Chemical Corp
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Filing date
Publication date
Application filed by Quantum Chemical Corp filed Critical Quantum Chemical Corp
Publication of EP0825897A1 publication Critical patent/EP0825897A1/fr
Publication of EP0825897A4 publication Critical patent/EP0825897A4/fr
Withdrawn legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F4/00—Polymerisation catalysts
    • C08F4/02—Carriers therefor
    • C08F4/027—Polymers
    • 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
    • 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
    • C08F4/602—Component covered by group C08F4/60 with an organo-aluminium 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
    • C08F4/603—Component covered by group C08F4/60 with a metal or compound covered by group C08F4/44 other than an organo-aluminium compound
    • C08F4/6032—Component of C08F4/60 containing at least two different metals
    • C08F4/6035—Component of C08F4/60 containing at least two different metals containing magnesium

Definitions

  • the present invention relates to a novel supported Ziegler-Natta catalyst and catalyst system 5 useful for polymerizing or copolymerizing ⁇ -olefins. More specifically, the supported Ziegler-Natta catalyst of the present invention comprises an organometallic component; a transition metal component; and a particulate functionalized copolymeric support material. ° The instant invention also relates to a method of preparing a microfine particulate functionalized copolyiTieric support material as well as to a process for (co)polymerizing ⁇ -olefins using the supported Ziegler- Natta catalyst of the present invention.
  • Ziegler-type catalysts which usually include components of a metal of Group IV-VIB and organometallic compounds of Groups I-IIIA of the Periodic Table of Elements, are widely utilized in the polymerization of olefins. These catalysts are known to effectively promote the high yield polymerization of olefins possessing the desired characteristics of these polymers. However, the use of conventional Ziegler-type catalysts are subjected to important failings. Thus, new and improved catalysts are continually being sought
  • One such improvement comprises supporting the above-identified Ziegler-type catalyst components on refractory inorganic oxide supports, such as Si0 2 , l-O j and MgO. These supports are available in variety of
  • inorganic oxide supports have several deficiencies.
  • inorganic oxide supports must be calcined at high temperatures or chemically treated with appropriate reagents to remove physically adsorbed water from the surface of the support.
  • the presence of water on the surface of inorganic oxide supports is well known in the art as being a catalytic poison which can adversely affect the catalytic activity of the catalyst.
  • inorganic oxide supports have a limited maximum pore size which also can restrict the catalytic performance of the catalyst. Although large pore size inorganic oxides are available, these materials may be friable and the use thereof as catalyst supports may, through attrition, lead to the formation of unwanted fine particles.
  • inorganic oxides not only adsorb water but other commonly occurring catalyst poisons, such as oxygen.
  • polymeric supports employed in the prior art are organic polymers such as polyethylene, polypropylene, polystyrene, polyvinyl alcohol, poly(styrene-divinylbenzene) , poly(methylmethacrylate) and the like.
  • polymeric supports usually require no dehydration prior to the use thereof; they can be easily functionalized which afford more opportunities to prepare tailored made catalysts; they are inert; they can be prepared with a wide range of physical properties, via chemical and mechanical means to intentionally give porosity, morphology and size control to the catalyst; and they offer a cost advantage over inorganic oxide supports.
  • the present invention is directed to a novel
  • Ziegler-Natta catalyst that is useful in the homopolymerization or copolymerization of ⁇ -olefins which comprises a particulate functionalized polymeric support, at least one organometallic compound and at least one transition metal compound.
  • the particulate functionalized polymeric support of the present invention includes copolymers of an ⁇ -olefin and a monomer which may be a vinyl ester or an acrylate, the latter being used in a generic sense to include esters of acrylic as well as methacrylic acid.
  • Ziegler-Natta catalysts of the present invention in combination with suitable cocatalysts, provide an a- olefin polymerization catalyst system which produces polymers comprised predominantly of ethylene and/or propylene with densities ranging from about 0.90 to about 0.97 and having a desirable balance of rheological and physical properties making them useful in a wide range of applications.
  • the particulate functionalized copolymeric support is a microfine powder comprised of particles that are spherical or substantially spherical.
  • microfine means that the particles of the support material have a median particle size of from about 1 to about 500 microns.
  • the microfine powders which are employed in the present invention are prepared by heating a copolymer to a temperature above the melting point of the copolymer in the presence of a nonionic surfactant; dispersing the mixture produced in the heating step in a dispersant to produce droplets of a desired size; and cooling the dispersion to a temperature below the melting point of the copolymer.
  • a process for polymerizing one or more ⁇ -olefins is provided.
  • at least one ⁇ -olefin is polymerized under olefin polymerization conditions utilizing the catalyst system of the present invention which includes the particulate functionalized copolymer suppoit, organometallic compound(s) and transition metal compound(s) as the solid catalyst component, along with a suitable cocatalyst component (s) .
  • the particulate functionalized supports of the instant invention are copolymers of an ⁇ -olefin and a vinyl ester or an acrylate.
  • acrylate being used in the generic sense to encompass esters of both acrylic and methacrylic acid.
  • the copolymers from which the particulate functionalized supports of the present invention are obtained are produced by copolymerizing an ⁇ -olefin, especially ethylene and/or propylene, with one or more monomers selected from the group consisting of vinyl esters, lower alkyl acrylates, arylacrylates and methacrylate monomers .
  • Copolymerizations of ⁇ -olefins and the above monomers are well known and are generally carried out at pressures of up to about 30,000 psi and temperatures of from about 150°C to about 250°C in the presence of suitable catalysts.
  • a typical process for copolymerizing ethylene and lower alkyl acrylates is described in U.S. Patent No. 2,200,429 while a typical process for copolymerizing ethylene and vinyl acetate is described in British Patent Specification 1443394.
  • the above-mentioned copolymers have an ⁇ - olefin as the major constituent. More preferably, the copolymers of the invention have from about 50.1 to about 99.9 weight percent C 2 . 3 ⁇ -olefin copolymenzed with from about 0.1 to about 49.9 weight percent of the monomer. Preferably, the copolymers will contain from about 70 to about 99 weight percent ethylene, propylene or mixtures thereof and from about 1 to about 30 weight percent of one of the above-identified monomers. In one highly useful embodiment, the copolymer supports comprise from about 80 to about 95 weight percent ethylene and about 5 to about 20 weight percent acrylate or vinyl ester monomer.
  • the vinyl esters employed in the present invention may be a vinyl ester of a C 2 -C 6 aliphatic carboxylic acid, such as vinyl acetate, vinyl propionate, vinyl butyrate, vinyl pentanoate or vinyl hexanoate. Of these vinyl esters, vinyl acetate is particularly preferred.
  • the acrylate monomer utilized in the present invention has the formula
  • CH 2 CRCOR 1 where R is hydrogen or methyl and R 1 is an alkyl group having from about 1 to about 12 carbon atoms or an aryl group having from about 6 to about 12 carbon atoms .
  • Alkyl groups may be straight chain or branched and can be saturated or unsaturated.
  • Aryl groups can be unsubstituted, e.g., phenyl, or can contain one or more hydrocarbyl substituents, e.g., benzyl, tolyl, xylyl .
  • acrylate comonomers which can be used for the copolymer include: methyl acrylate, ethyl acrylate, isopropyl acrylate, allyl acrylate, n- butyl acrylate, t-butyl acrylate, neopentyl acrylate, n- hexyl acrylate, cyclohexyl acrylate, benzyl acrylate, phenyl acrylate, tolyl acrylate, xylyl acrylate, 2- ethylhexyl acrylate, 2-phenylethyl acrylate, n-decyl acrylate, isobornyl acrylate, n-octadecyl acrylate, methyl methacrylate, ethyl methacrylate, propyl methacrylate, n-butyl methacrylate, sec-butyl methacrylate, n-pentyl methacrylate
  • alkyl acrylate comonomers having the above structural formula where R is hydrogen and R 1 is a C,. 4 alkyl group are particularly useful. Of these, methyl acrylate, ethyl acrylate and n-butyl acrylate are especially preferred.
  • the particulate supports are ethylene-methyl acrylate, ethylene-ethyl acrylate, ethylene-vinyl acetate and ethylene-n-butyl acrylate copolymers.
  • the melt index of the copolymers can range from about 0.1 up to about 400 g/10 min. or above.
  • the melt index is in the range of from about 1 up to about 125, and more preferably, from about 1 up to about 60. All melt indexes referred to herein are determined at 190°C in accordance with ASTM D 1238, condition E, and are expressed in grams per 10 minutes.
  • Ziegler-Natta catalysts of the invention are particulate products comprised of discrete particles whose median particle size can range from about 1 up to about 1500 microns, and more preferably, from about 1 to about 1000 microns .
  • the copolymer powders can be obtained by spray drying or the copolymer can be precipitated from solution by the addition of a suitable precipitating agent, e.g., methanol.
  • the particulate supports obtained by spray drying the copolymer or copolymers may also be ground or milled to produce powders within the acceptable size range. Mechanical grinding may be carried out under ambient conditions if the copolymer has a sufficiently high melting point and does not degrade under the grinding conditions; however, it is more customary to cryogenically grind the copolymers.
  • Suitable particulate supports can also be produced using conventional solution and dispersion processes.
  • the supports are "microfine" powders of functionalized copolymers obtained by dispersion processes. Particles produced by these processes are spheroidal or substantially spheroidal in shape.
  • Microfine powders produced using dispersion processes in addition to having spheroidal particles, also have substantially narrower particle size distributions than reactor powders or powders produced by precipitation, grinding or milling.
  • Preferred microfine functionalized polymer supports are comprised of discrete particles which are spheroidal or substantially spheroidal in shape and have a median particle size (diameter) from about 1 microns to about 500 microns. More preferably, the median particle size is from about 5 microns to about 300 microns and in an especially useful embodiment, the median particle size is from about 20 to about 200 microns. Median diameters as used herein are obtained from the particle volume distribution curve.
  • copolymers of the present invention are converted to microfine powders using the dispersion technique of U.S. Pate'nt Nos. 3,422,049, 3,432,483 and
  • the copolymer is charged to the reactor with a polar liquid medium and nonionic surfactant and a dispersion is formed in accordance with conventional dispersing procedures described in the art.
  • the dispersing apparatus may be any device capable of delivering sufficient shearing action to the mixture at elevated temperature and pressure. Conventional propeller stirrers designed to impart high shear can be used for this purpose.
  • the vessel may also be equipped with baffles to assist in dispersing the copolymer. Particle size and particle size distribution will vary depending on the shearing action which, in turn, is related to the stirrer design and rate of stirring.
  • Agitation rates can vary over wide limits but the speed of the stirrer will usually be controlled so that the tip speed is between about 400 and about 4000 ft/min and, more commonly, about 800 and about 3500 ft/min. Higher tip speeds are generally used for batch operation, usually about 2500-3500 ft/min. Tip speeds for continuous procedures most generally range between about 800 and about 3000 ft/min.
  • the dispersion process is typically carried out in a vessel which enables the powder-forming process to be conducted at elevated temperature and pressure.
  • the temperature will vary depending on the specific polymer being used, it will typically range from about 175°C to about 250°C. Since the fluidity of polymers is temperature related, it may be desirable to carry out the process at temperatures substantially above the melt point of the copolymer to facilitate formation of the dispersion; however, the temperature should not exceed the thermal degradation temperature of the polymer.
  • Stirring is commenced after the desired temperature is reached and continued until a dispersion of the desired droplet size is produced. This will vary depending on the particular copolymer being used, temperature, amount and type of surfactant, and other process variables, but generally will range from about 5 minutes to about 2 hours. Stirring is most commonly maintained for a period of from about 10 to about 30 minutes.
  • a polar liquid medium which is not a solvent for the copolymer is employed as the dispersant in the formation of the microfine powder support.
  • These polar media are hydroxylic compounds and can include water, alcohols, polyols and mixtures thereof.
  • the weight ratio of polar liquid medium to polymer ranges from about 0.8:1 to about 9:1 and, more preferably, from about 1:1 to about 5:1. It is particularly advantageous to use water as the dispersing medium or a liquid medium where water is the major component.
  • the pressure of the process is not critical so long as a liquid phase is maintained. In general, the pressure can range from about 1 up to about 250 atmospheres.
  • the process can be conducted at autogenous pressure or the pressure can be adjusted to exceed the vapor pressure of the liquid medium at the operating temperature. Most generally, with aqueous dispersions, the pressure will range from about 5 to about 120 atmospheres .
  • one or more dispersing agents are necessarily employed.
  • Useful dispersing agents are nonionic surfactants which are block copolymers of ethylene oxide and propylene oxide.
  • these nonionic surfactants are water-soluble block copolymers of ethylene oxide and propylene oxide and have molecular weights greater than about 3500.
  • the amount of nonionic surfactant employed can range from about 4 to about 50 percent, based on the weight of the copolymer.
  • the nonionic surfactant is present in a concentration of from about 7 to about 45 percent, based on the weight of the copolymer.
  • Pluronic These products are obtained by polymerizing ethylene oxide onto the ends of a preformed polyoxypropylic base. Both the molecular weight of the polyoxypropylene base and the polyoxyethylene segments can be varied to yield a wide variety of products.
  • One such compound found to be suitable in the practice of the process of this invention is the product designated as F-98 wherein a polyoxypropylene of average molecular weight of 2,700 is polymerized with ethylene oxide to give a product of molecular weight averaging about
  • This product contains 20 weight percent propylene oxide and 80 weight percent ethylene oxide.
  • Pluronic- surfactants include F-88 (M.W. 11,250, 20% propylene oxide, 80% ethylene oxide) , F-108 (M.W. 16,250, 20% propylene oxide, 80% ethylene oxide) , and P-85 (M.W. 4,500, 50% propylene oxide, 50% ethylene oxide) . These compounds, all containing at least about
  • Tetronic ® 707 and Tetronic ® 908 are most effective for the present purposes. Tetronic ® 707 has a 30 weight percent polyoxypropylene portion of
  • Tetronic ® 908 2,700 molecular weight polymerized with a 70 weight percent oxyethylene portion to give an overall molecular weight of 12,000.
  • Tetronic ® 908 has a 20 weight percent polyoxypropylene portion of 2,900 molecular weight polymerized with an 80 weight percent oxyethylene portion to give an overall molecular weight of 27,000.
  • useful Tetronic* surfactants have molecular weights above 10,000 and contain a major portion by weight of ethylene oxide.
  • the powder-forming process may also be conducted in a continuous manner. If continuous operation is employed, the ingredients are continuously introduced to the system while removing the dispersion from another part of the system. The ingredients may be separately charged or may be combined for introduction to the autoclave.
  • the particulate copolymer supports and especially the microfine spheroidal powders described above can be used to prepare any Ziegler-Natta catalyst composition.
  • the supported catalysts of the present invention preferably comprise (a) an organometallic compound, complex or mixtures thereof; (b) a transition metal, transition metal compound or mixtures thereof; and (c) the functionalized copolymer support.
  • One or more additional components such as electron donors or halogenating agents may also be present.
  • Organometallic compounds suitable for use in the present invention include, for example, compounds of formulae I, II and III which are as follow: (I) R ⁇ tOR 3 ) ⁇ .
  • M 1 is a metal of Group IA of the Periodic Table of Elements
  • R 2 and R 3 are the same or different and are hydrocarbyl groups, preferably containing from about 1 to about 20 carbon atoms and preferably selected from the group consisting of alkyl groups containing from about 1 to about 20, more preferably from about 1 to about 12, carbon atoms; alkenyl groups containing from about 2 to about 20, preferably from about 2 to about 12, carbon atoms; cycloalkyl or aryl groups containing from about 6 to about 20, preferably from about 6 to about 14, carbon atoms; or alkaryl or aralkyl groups containing from about 7 to about 20, preferably from about 7 to about 16, carbon atoms; and a is zero or 1;
  • M 111 is a metal of Group IIIA of the
  • Periodic Table of Elements d and e are each zero, 1, 2 or 3, subject to the provisos that at least one of d and e is other than zero and the sum of d and e is not more than 3;
  • Y is hydrogen or halogen;
  • R 2 and R 3 are as defined in formula I, subject to the provisos that when d is 2 or 3 , each R 2 can be the same or different, or when e is 2 or 3, each R 3 can be the same or different.
  • Organometallic compounds encompassed by formula I above include, for example: alkali metal alkyls, such as lithium alkyls (e.g., methyl lithium , ethyl lithium, butyl lithium, and hexyl lithium) ; alkali metal cycloalkyls, such as lithium cycloalkyls (e.g., cyclohexyl lithium) ; alkali metal alkenyls, such as lithium and sodium alkenyls (e.g., allyl lithium and allyl sodium) ; alkali metal aryls, such as lithium aryls (e.g.
  • alkali metal aralkyls such as lithium and sodium aralkyls (e.g., benzyl lithium, benzyl sodium and diphenylmethyl lithium)
  • alkali metal alkoxides such as lithium and sodium alkoxides (e.g., lithium methoxide, sodium me hoxide and sodium ethoxide)
  • alkali metal aryloxides such as sodium aryloxides (e.g., sodium phenolate) ; and the like.
  • Organometallic compounds within the scope of formula II above include, for example:
  • Grignard reagents e.g., methyl magnesium chloride, methyl magnesium bromide, methyl magnesium iodide, ethyl magnesium chloride, ethyl magnesium bromide, cyclohexyl magnesium chloride, allyl magnesium chloride, phenyl magnesium chloride, phenyl magnesium bromide and benzyl magnesium chloride
  • metal alkyls such as dialkyl magnesium compounds (e.g., dimethyl magnesium, butyl ethyl magnesium and dibutyl magnesium) and dialkyl zinc compounds (e.g., diethyl zinc)
  • metal alkoxides such as magnesium alkoxides
  • Hydrocarbyloxy metal halides such as alkoxymagnesium halides (e.g., pentyloxymagnesium chloride, 2-methyl-1-pentyloxymagnesium chloride and 2- ethyl-1-hexyloxymagnesium chloride) , and the like.
  • alkoxymagnesium halides e.g., pentyloxymagnesium chloride, 2-methyl-1-pentyloxymagnesium chloride and 2- ethyl-1-hexyloxymagnesium chloride
  • Organometallic compounds within the ambit of formula III above, where e is other than zero include aluminum-n-butoxide, aluminum ethoxide, aluminum ethylhexoate, diethylaluminum ethoxide, diisobutylaluminum ethoxide, diisobutylaluminum 2,6-di- tert-butyl-4-methyl phenoxide, and the like; and where e is zero compounds of formula III-a below can be employed in the instant invention:
  • R 2 is as defined in formula I, M 111 and
  • Y are as defined in formula III and f is 1, 2 or 3, subject to the proviso that when f is 1, Y is X, as defined in formula II.
  • Organometallic compounds within formula Ill-a above include for example: trimethylaluminum (TMAL) , triethylaluminum
  • TEAL triisobutylaluminum
  • TIBAL triisobutylaluminum
  • DEH diisobutylaluminum
  • DIBAH dimethylaluminum bromide
  • DEC diethylaluminum chloride
  • DEC diisobutylaluminum bromide
  • DEC diisobutylaluminum bromide
  • organometallic compounds outside the scope of generic formulae I-III are also contemplated for use in the present invention.
  • the organometallic compounds outside the scope of generic formula I-III include, but are not limited to, ethylaluminum sesquichloride (EASC) , (C 2 H 5 ) ,Al 2 Cl 3 ; linear or cyclic aluminoxanes such as those described in U.S. Patent Nos .
  • Organometallic compounds are also contemplated by the instant invention.
  • an organometallic compound of magnesium may be complexed with an organoaluminum halide to form a Mg-Al complex.
  • the magnesium-aluminum complexes which may be used in the present invention are well known in the art and are disclosed in Aishima et al . , U.S. Patent No. 4,004,071 at column 3, lines 34-40 and column 3, lines 30-36, the contents of which are incorporated herein by reference.
  • the complex is prepared according to the teachings of
  • the organometallic compounds are the alkyls, alkoxides or aryls of magnesium or its complexes thereof.
  • an alkyl, alkoxide or aryl of magnesium (or its complexes) is utilized in conjunction with an alkyl, alkoxide or aryl of aluminum (or its complexes) .
  • magnesium dialkyls and aluminum trialkyls, wherein the alkyl moieties contain from about 1 to about 8 carbon atoms are particularly preferred.
  • Known transition metals or transition metal compounds employed in the preparation of Ziegler-Natta catalysts can be used for the catalysts of the invention. Suitable transition metal compounds are compounds of metals of Group IVB, VB, VIB or VIIB of the
  • transition metal compounds are compounds of titanium, vanadium, molybdenum, zirconium or chromium, such as TiCl 3 , TiCl 4 , alkoxy titanium halides, VC1 3 , VC1 4 , VOCl,, alkoxy vanadium halides, MoCl 5 , ZrCl 4 , HfCl 4 and chromium acetylacetonate.
  • Mixtures of transition metal compounds to provide dual site bimetallic catalysts, such as titanium and vanadium-containing catalysts, can also be employed.
  • Compounds of titanium and/or vanadium are especially useful for the catalysts of the invention.
  • the Ziegler-Natta catalysts of this invention are generally employed with a cocatalyst, sometimes also referred to as a catalyst promoter or catalyst activator.
  • the cocatalyst employed in the present invention contains at least one metal selected from
  • cocatalysts are known and widely used in the polymerization art and can include metal alkyls, hydrides, alkylhydrides, and alkylhalides, such as alkyllithium compounds, dialkylzinc compounds, trialkylboron compounds, trialkylaluminum compounds, alkylaluminum halides, alkylaluminum hydrides, and the like. Mixtures of cocatalytic agents can also be employed.
  • Illustrative organometallic compounds which can be used as cocatalyst include n-butyllithium, diethylzinc, di-n-propylzinc, triethylboron, trimethylaluminum, triethylaluminum, triisobutylaluminum, tri-n-hexylaluminum, ethylaluminum dichloride, ethylaluminum dibromide, ethylaluminum dihydride, diethylaluminum chloride, di-n-propylaluminum chloride, and the like.
  • Preferred cocatalysts are Group
  • metal alkyls and alkyl metal halides especially wherein the metal is aluminum and the alkyl group contains from about 1 to about 8 carbon atoms.
  • Triethylaluminum and triisobutylaluminum are highly useful cocatalysts for the supported Ziegler-Natta catalysts of the invention and are particularly preferred.
  • Cocatalysts are employed in amounts effective to promote (increase) the polymerization activity of the supported Ziegler-Natta catalyst.
  • the amount of cocatalyst used can vary widely but most generally the molar ratio of the metal of the cocatalyst to the transition metal ranges from about 1:1 to about 500:1 and, more preferably, from about 5:1 to about 200:1.
  • aluminum alkyls or aluminum alkyl halides are employed as the cocatalyst with a titanium compound and magnesium compound, the
  • Al/Ti molar ratio generally ranges from about 5:1 to about 100:1.
  • the catalyst may be activated in-situ by adding the cocatalyst and supported catalyst separately to the polymerization or the supported catalyst and activator may be pre-contacted before introduction to the polymerization reactor.
  • Cocatalysts for polymerization may be employed singly in the manner described, or in concert with other such modifiers, activators or promoters to enhance activity or influence resin properties.
  • cocatalyst modifiers is described, e.g. in U.S. Patent
  • Preferred compounds which may be employed as cocatalyst modifiers include halocarbons such as carbon tetrachloride, carbon tetrabromide, dichloromethane, dibromomethane, 1, 1, 1-trichloroethane and a number of commonly available chlorofluorocarbons (CFC's) and hydro-chlorofluoracarbons (HCFC's) ; halosilanes such as silicon tetrachloride, trichlorosilane, dichlorosilane; and alkoxysilanes such as dimethoxysilane, diethoxysilane, diisopropoxysilane, trimethoxysilane and tetramethoxysilane, and more preferably the alkoxysilane is diisopropyldimethoxysilane, diisobutyldi- methoxysilane, phenyltriethoxysilane and cyclohexyltri ⁇ meth
  • the Ziegler-Natta catalysts of the invention are prepared utilizing conventional organometallic compounds and transition metal components, in accordance with standard catalyst-forming procedures.
  • the support is contacted with the organometallic compound in an aliphatic C 5 . e hydrocarbon.
  • the product is contacted with the transition metal compound.
  • the organometallic compound and the transition metal compound are generally dissolved in an aliphatic hydrocarbon for introduction. A slight exotherm may be observed upon contacting the organometallic compound with the support material.
  • the support may be allowed to remain in contact with the organometallic compound for periods of up to 20 hours or more but reaction is sufficiently complete within about 30 minutes.
  • All or a portion of the aliphatic hydrocarbon may be removed after contacting with the organometallic compound and the intermediate catalyst product may be washed, if desired. While it is not necessary, it is possible to wash and/or dry the catalyst precursor before contacting with the transition metal compound. In general, it has been observed that resins with higher bulk densities are produced using catalysts which have been prepared without washing between the contacting steps. If all or part of the aliphatic hydrocarbon is removed from the catalyst precursor, it will be redispersed in fresh, aliphatic hydrocarbon prior to contacting with the transition metal compound.
  • a change in color of the catalyst e.g., from pale yellow to brown when TiCl 4 is used, is usually observed upon contacting with the transition metal compound; however, the hydrocarbon medium will typically remain colorless. Reaction with the transition metal compound will generally be complete in 30 minutes or less; however, extended contact times do not appear to adversely affect the catalysts. While it is not necessary, the supported catalyst may be washed and dried after recovery. After the transition metal is reacted, the supported catalyst is recovered for use in polymerizations.
  • Supported catalysts obtained in this manner are fine, free-flowing powders having particles not differing substantially in size, shape and particle size distribution from that of the copolymer support material used for their preparation.
  • the supported catalysts can contain from about 0.25 up to about 25 weight percent transition metal. More typically, transition metal contents will range from about 0.5 to about 10 percent.
  • magnesium contents will range from about 0.1 to about 25 and, more preferably, about 0.25 to about 10 weight percent and magnesium/transition metal molar ratios will range from about 4:1 to about 0.25:1 and, more preferably, from about 2.25:1 to about 0.5:1.
  • the magnesium compound has the structural formula R 2 Mg wherein R is an alkyl group containing from about 1 to about 8 carbon atoms and the transition metal compound has one of the following structural formulas:
  • V(0R 4 )_(0) m X n wherein R 4 is an aliphatic or aromatic hydrocarbyl group containing from about 1 to about 12 carbon atoms; X is
  • x is 0, 1 or 2
  • y is 1 to 4 inclusive
  • x+y 3 or 4
  • 1 is 0 or 1-5
  • m is 0 or 1
  • Suitable titanium compounds encompassed by the above formula are TiCl 3 , TiCl 4 , Ti(0CH 3 )Cl 3 Ti (0C 6 H 5 ) Cl 3 , Ti(OC 2 H s ) 2 Cl 2 , Ti(OC 2 H s ) 3 Cl, Ti (0C 4 H 2 C1 2 and Ti (OC 4 H 9 ) 4 .
  • TiCl 4 is especially useful in the preparation of the catalyst of this invention.
  • Suitable vanadium compounds encompassed by the above formula include vanadium oxyhalides, vanadium carboxylates and vanadium halides.
  • VC1 ho and V0C1 3 are particularly preferred in the present invention.
  • the formation of the catalyst may also involve reaction with known electron donors including alcohols, phenols, ketones, aldehydes, carboxylic acids, carboxylic acid esters, ethers, and the like.
  • Particularly useful electron donors include the alkyl esters of aliphatic carboxylic acids, aliphatic alcohols, aliphatic ketones and aliphatic ethers.
  • Ziegler-Natta catalysts typically contain halogen, primarily chlorine.
  • the source of the halogen most commonly is provided by the magnesium or transition metal compound.
  • Halogenated titanium and vanadium compounds are particularly useful halogen sources.
  • Halogen can, however, be supplied by a halogenating agent such as hydrogen halides, organohalides, aluminum halides, silicon halides or phosphorus halides.
  • the catalyst of the invention can be used in virtually any polymerization procedure where supported
  • the supported catalysts of the invention are useful for the preparation of homopolymers and copolymers of alpha-olefins containing from about 2 to about 8 carbon atoms. Most preferably, they are used to produce polymers comprised predominantly of ethylene and/or propylene with densities ranging from about 0.90 to about 0.97 and having a desirable balance of rheological and physical properties making such polymers useful in applications such as blow molding, injection molding, rotomolding, rotolining, extrusion, coextrusion, film forming and the like.
  • the polymers produced herein have the same morphology as the supported catalyst used in the polymerization process. That is, the polymers produced by the instant process have substantially spherical particles and a median particle size which depends on both the median particle size of the catalyst particles and the amount of polymer produced per unit amount of catalyst employed in the polymerization. The median particle size can thus range from about 10 to about 5000 microns.
  • Such polymer particles produced in the present invention possess a better bulk density and fluidization compared to prior art polymer particles prepared from conventional polymeric supported catalysts.
  • the polymer particles produced in the present invention are compatible with the functionalized polymeric supports. Thus, no residual gels are formed during the polymerization process which are attributable to the catalyst support.
  • the powder produced in this operation was analyzed using laser light scattering to measure the size distribution thereof by volume. This technique used the principle of diffraction of the particles as the measurement means.
  • Size Analyzer with proper lens configuration for the expected particle size interfaced with a computer was used. It read the diffraction pattern and digitally performed the necessary integrations.
  • water was charged to the water bath and circulated through the sample measuring chamber. After obtaining the baseline measurement, the agitator and sonic vibrator were activated and the copolymer powder was added to the water bath until the obscuration reading was 0.3. Mixing and circulation were controlled to obtain acceptable dispersion without excessive foaming. A drop of liquid detergent was added to facilitate dispersion. After eight minutes agitation, measurements were commenced and the size distribution data was automatically tabulated. The cumulative volume undersize and volume frequency was tabulated for 32 size classes together with useful derived parameters. A logarithmic plot was also produced. Duplicate runs were made for each copolymer powder sample. The particle size reported in the examples was the median diameter
  • D(v,0.5) for the volume distribution curve.
  • the range reported in the examples was for 80 percent of the volume distribution curve, i.e., from D(v,0.1) to
  • Patent No. 3,422,049 particulate microfine supports were produced from the following ethylene-acrylate and ethylene-vinyl acetate copolymers.
  • All of the above-prepared copolymer supports were free-flowing powders comprised of discrete particles having spherical morphology, i.e., the individual particles are spherical or substantially spherical in shape.
  • Copolymer Support A was also more fully characterized and found to have a surface area of 2.1 m 2 /g, a pore volume of 0.021 cc/g and average pore radius of 203 A by the BET method. These measurements were carried out using an Autosorb-6 [trademark] instrument and the physical measurements were determined using the techniques described in S. Lowel et al . , "Powder Surface
  • the copolymer support had a weight average molecular weight (M w ) of 110,400, number average molecular weight ⁇ M n ) of 24,700 and MWD (M Hook/M n )of 4.50.
  • Copolymer Supports A, B and D-G were utilized as obtained from the powder-forming process.
  • a commercial microfine EVA powder (Copolymer Support H) was also included.
  • a particulate support was obtained by cryogenically grinding EMA1. Cryogenic grinding of this sample was conducted by mechanical means, using a Wiley mill which was equipped with a recirculating refrigerant.
  • the polymer sample i.e.
  • EMA1 was ground along with dry ice so as to not incur polymer melting.
  • the polymer was also ground so as to pass through a 20 mesh size screen.
  • the resulting ground powder identified as Copolymer Support I (not shown in Table 1) and having an average particle size of
  • the catalyst precursor was recovered by filtration, washed once with 100 ml heptane, and then re-slurried in 100 ml fresh heptane.
  • Two (2) ml 1.0M TiClcliff in heptane was then added with vigorous stirring and the pale yellow support immediately turned brown.
  • the supported polymer was recovered by filtration, washed two times with 75 ml heptane and then dried under vacuum. Analysis showed the catalyst to contain 1.44% Mg and 1.37% Ti .
  • the molar ratio of Mg/Ti was 2.06.
  • This preparative example illustrates that a substantial portion of the organometallic compound interacts with the support particles. Washing the catalyst after both the addition of the organometallic compound as well as after the addition of the transition metal compound in a solvent suitable for the dissolution of both free reagents serves to remove virtually all materials which might otherwise be considered to interact independently of the support. Analysis of the final catalyst composition revealed that the catalyst retained 33% and 77% of the magnesium and titanium employed, respectively.
  • the supported catalyst was used to prepare ethylene homopolymer and copolymers of ethylene and butene-l.
  • an amount of isobutane was used to bring the total volume of comonomer and isobutane to 500 ml .
  • Hydrogen was added to control molecular weight and triethylaluminum (TEAL) was used as the cocatalyst.
  • Polymerizations were carried out at 80°C and 500 psig. Ethylene gas was used to maintain this pressure.
  • the reactor was vented and cooled to ambient temperature to recover the copolymer. Details of each polymerization and characteristics of the resins produced are provided in Table 2.
  • MIR HLMI/MI
  • HLMI was determined by ASTM D-1238, Condition F, reported as g/10 minutes.
  • Measurements were performed on an unmodified reactor powder sample by pouring the sample through a 33 mm ID funnel into a 100 cc stainless steel cup without tapping or shaking, then leveling off the top with a straight edge and weighing by difference. Values reported as the mean of two measurements in g/cm'.
  • Weight and number average molecular weight determinations i.e., M w and M Kunststoffe, were made using a Waters GPC on a mixed sized, crosslinked divinylbenzene column with 1, 2, 4-trichlorobenzene as a solvent at 135°C with a refractive index detector.
  • EXAMPLE V A supported catalyst was prepared utilizing Copolymer Support A.
  • the reagents used were the same as used in Example I except that the catalyst precursor obtained after reaction of the support with BEM was not washed with additional heptane and the resulting supported catalyst, obtained after reaction with the TiCl 4 , was not washed. After both reactions, the heptane was removed by stripping under vacuum. After removing the solvent from the catalyst precursor by evaporating under vacuum (with BEM) , the catalyst precursor was re-slurried with 50 ml fresh heptane before addition of TiCl 4 . After the second reaction (with TiCl 4 ) , stripping was continued to dryness.
  • 5 grams Copolymer Support A, 5 ml BEM and 2 ml TiCl 4 were used.
  • the resulting catalyst contained 1.34% Mg, 1.48% Ti and the Mg/Ti molar ratio was 1.77.
  • the catalyst was used to polymerize ethylene and polymerization details are provided in Table 4.
  • EXAMPLE VI Using the modified catalyst preparation procedure of Example V, a supported catalyst was prepared using 5 grams Copolymer Support A, 5 ml BEM and 4 ml TiCl 4 .
  • the catalyst product contained 1.31% Mg, 2.80% Ti and the Mg/Ti molar ratio was 0.93.
  • the catalyst was used to homopolymerize ethylene and polymerization details are provided in Table 4.
  • the copolymer support was slurried in 75 ml pentane. After contacting the support with the MAGALA for 45 minutes at room temperature, the TiCl 4 was added directly to the slurry and agitation continued for 30 minutes. The supported catalyst was recovered by removing pentane using the a nitrogen purge. The supported catalyst contained 1.30% Ti , 1.07% Mg and 0.20% Al.
  • EXAMPLE XIV A supported vanadium catalyst was prepared utilizing the copolymer supports of the invention. To a slurry of 5.0 grams of Copolymer Support A in 80 ml heptane were added the following in the order indicated:
  • the dried supported catalyst contained 5.62% V, 1.07% Mg and 1.59% Al . Polymerization details obtained using the supported vanadium catalyst are reported in Table 4.
  • EXAMPLE XV To demonstrate the ability to use other olefin-acrylate copolymers in the preparation of the supported catalysts of the invention, 5 grams Copolymer Support E was slurried with 75 ml pentane and contacted with 5 ml (0.633M) BEM for 30 minutes at room temperature while stirring. Two (2.0) ml (1.0M) TiCl 4 was then added and stirred for an additional 30 minute period.
  • the dried supported catalyst which contained 1.36% Ti and 1.19% Mg was evaluated for the polymerization of ethylene. Detarils of the polymerization and results are provided in Table 4.
  • EXAMPLE XVI Using a procedure identical to that described in Example XV, except that the copolymer support used was Copolymer Support F, a supported catalyst was prepared containing 1.34% Ti and 1.23% Mg.
  • the supported catalyst was used to polymerize ethylene and polymerization details and results are provided in Table 4.
  • Ethylene was polymerized using the supported catalyst and polymerization details and results are provided in Table .
  • EXAMPLE XVIII Using a procedure identical to that described in Example XV, except that the copolymer support used was Copolymer Support G, a supported catalyst was prepared containing 1.23% Ti and 1.30% Mg.
  • the supported catalyst was used for the polymerization of ethylene and polymerization details and results are provided in Table 4.
  • EXAMPLE XIX This example demonstrates the use of the copolymeric ethylene-vinyl acetate Support Material H of Table I.
  • the catalyst of this example was prepared by slurrying five (5.0) grams of the EVA material H with 100 ml dry heptane under a nitrogen atmosphere in a 250 ml roundbottom flask equipped with stirring bar. Five (5.0) ml of 0.633 M BEM was added and the resultant mixture was stirred for 30 minutes at room temperature under nitrogen. Thereafter, 0.2 ml of 1.0M TiCl 4 in heptane was added, changing the color of the copolymeric support to a dark brown. After a 30 minute interval, heptane was removed by purging with nitrogen gas and drying the resultant catalyst .
  • the supported catalyst prepared using the above deposition process contained 1.29% Ti and 1.33% Mg.
  • EXAMPLE XX Another supported catalyst was prepared using the EVA support material used in Example XIX except that the catalyst was prepared using a filtration procedure. In accordance with this procedure, the slurry containing EVA, BEM and heptane was allowed to react overnight at room temperature under nitrogen. After this reaction, the slurry was filtered and washed once with 100 ml of dried heptane. The washed material was thereafter re-slurried in 100 ml of heptane and 2 ml of a solution of 1.0M TiCl. in heptane was added, changing the color of the resin to a light brown. This mixture was stirred for 30 minutes, filtered and then washed with 100 ml of heptane. The catalyst thus formed was vacuum dried to leave a flaxen- yellow powder containing 1.57% Ti and 0.47% Mg.
  • EXAMPLE XXI In this example, a supported vanadium catalyst was prepared utilizing the EVA material of Table I. To a slurry of 5.0 grams of the Copolymer Support H in 80 ml of heptane were added the following in the order indicated:
  • a supported catalyst was prepared in accordance with Example I, except that 10.0 grams of a microfine, spheroidal high density polyethylene powder (HDPE) made by the same dispersion process as used for Copolymer Support A and having a median particle diameter of 40 microns was used as the support material. Twenty (20.0) ml of 0.633 M BEM was added to the slurried support under nitrogen at room temperature. No color change or exotherm was observed during this contacting step, which was allowed to proceed for 20 hours. After this time period, the heptane was filtered off.
  • HDPE microfine, spheroidal high density polyethylene powder
  • the Mg-treated polymer was then washed with 100 ml of heptane, filtered, and re-slurried once again in heptane.
  • Four (4.0) ml of 1.0 M TiCl 4 in heptane was then added to the treated support with vigorous stirring and the support immediately upon contact changed to an off-white shade. After 30 minutes of rapid stirring, the heptane was filtered off.
  • the recovered supported material was washed twice with heptane (75 ml in each wash) , then dried in vacuo. Analysis showed that the catalyst contained 0.038% Ti and 0.042 Mg.
  • the reaction was allowed to proceed for 20 hours, after which the heptane was filtered off.
  • the treated polymer was washed once with 100 ml of heptane, filtered, then re-slurried again in heptane.
  • Three (3.0) ml of 1.0 M TiCl 4 in heptane was added to the re-slurried heptane with vigorous stirring. No color change of either the support or heptane was observed.
  • the heptane was filtered off.
  • the recovered supported material was washed twice with heptane (two 75 ml portions) and then dried in vacuo.
  • the supported catalyst contained 0.013% Ti and 0.017% Mg.
  • the supported catalyst of this comparative example was inactive in polymerizing ethylene compared to the catalysts of the present invention.
  • EXAMPLE XXII In this example, the catalyst of Example II was utilized as the catalytic agent in the gas phase polymerization of ethylene. The polymerization was conducted in a 2.5 liter stirred gas phase reactor. The cocatalyst TEAL (3.0 ml) was added to the reactor containing a 200 gram bed of polyethylene; the reactor was pressurized with nitrogen to a pressure of 142 psig

Abstract

La présente invention concerne un catalyseur de Ziegler-Natta de type nouveau à support pouvant être utilisé dans la polymérisation d'α-oléfines. Plus précisément, le catalyseur de Ziegler-Natta à support de la présente invention comprend un support copolymère particulaire fonctionnalisé, un composé organo-métallique et un composé à base de métal de transition. L'invention décrit également un procédé de type nouveau pour préparer les supports copolymères particulaires fonctionnalisés de l'invention.
EP96911489A 1995-03-29 1996-03-29 Catalyseur a support polymere pour la polymerisation d'olefines Withdrawn EP0825897A4 (fr)

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US41267995A 1995-03-29 1995-03-29
PCT/US1996/004356 WO1996030122A1 (fr) 1995-03-29 1996-03-29 Catalyseur a support polymere pour la polymerisation d'olefines
US412679 1999-10-05

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CN114591455A (zh) * 2020-12-03 2022-06-07 中国石油天然气股份有限公司 催化剂及其制备方法、烯烃聚合催化剂体系

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US6218331B1 (en) * 1995-03-29 2001-04-17 Equistar Chemicals, L.P. Polymer-supported catalyst for olefin polymerization
US6063725A (en) * 1995-11-07 2000-05-16 Mitsui Chemicals, Inc. Olefin polymerization catalyst system
JPH1171421A (ja) * 1997-07-03 1999-03-16 Sumitomo Chem Co Ltd オレフィン重合用固体触媒成分、オレフィン重合用触媒、及びオレフィン系重合体の製造方法
US6544921B1 (en) * 1999-09-28 2003-04-08 Sumitomo Chemical Comapny, Limited Solid catalyst component and catalyst for olefin polymerization, process for producing olefin polymer and process for producing solid catalyst component for olefin polymerization
GB0023662D0 (en) 2000-09-27 2000-11-08 Borealis Tech Oy Supported catalyst
EP1231223B1 (fr) * 2001-02-07 2004-04-28 Saudi Basic Industries Corporation Procédé de polymérisation d'oléfines
DE60104809T2 (de) 2001-02-07 2005-01-05 Saudi Basic Industries Corp. Katalysatorzusammensetzung für die Olefinpolymerisation und Verfahren zu ihrer Herstellung

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US3746681A (en) * 1961-12-20 1973-07-17 Nat Distillers Chem Corp Process of preparing finely divided thermoplastic resins
GB2036761A (en) * 1978-11-28 1980-07-02 Inst Khim Fiz Akad Nauk Ssr & Catalyst for di-, oligo-, co- and poly- merization of vinyl monomers
US4900706A (en) * 1987-03-17 1990-02-13 Sumitomo Chemical Company, Limited Process for producing olefin polymers and catalyst used therein
WO1994020545A1 (fr) * 1993-03-08 1994-09-15 Queen's University At Kingston Catalyseur sur un support en polymere pour la polymerisation et la copolymerisation d'olefines

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CN114591455B (zh) * 2020-12-03 2023-10-31 中国石油天然气股份有限公司 催化剂及其制备方法、烯烃聚合催化剂体系

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KR19980703413A (ko) 1998-11-05

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