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WO1999061490A1 - Procede pour la polymerisation en suspension d'ethylene - Google Patents

Procede pour la polymerisation en suspension d'ethylene Download PDF

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Publication number
WO1999061490A1
WO1999061490A1 PCT/EP1999/003417 EP9903417W WO9961490A1 WO 1999061490 A1 WO1999061490 A1 WO 1999061490A1 EP 9903417 W EP9903417 W EP 9903417W WO 9961490 A1 WO9961490 A1 WO 9961490A1
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Prior art keywords
transition metal
polymerization
catalyst
group
metal component
Prior art date
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PCT/EP1999/003417
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German (de)
English (en)
Inventor
Stefan Mecking
Original Assignee
Axiva Gmbh
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Publication of WO1999061490A1 publication Critical patent/WO1999061490A1/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
    • C08F110/00—Homopolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F110/02—Ethene
    • 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
    • C08F4/62—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
    • C08F4/65922—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 containing at least two cyclopentadienyl rings, fused or not
    • C08F4/65925—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 containing at least two cyclopentadienyl rings, fused or not two cyclopentadienyl rings being mutually non-bridged
    • 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
    • C08F4/65922—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 containing at least two cyclopentadienyl rings, fused or not
    • C08F4/65927—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 containing at least two cyclopentadienyl rings, fused or not two cyclopentadienyl rings being mutually bridged

Definitions

  • the present invention relates to a suspension process for the polymerization of ethylene using catalyst compositions comprising a polymerization catalyst based on a late transition metal component and at least one further polymerization catalyst based on a transition metal component.
  • Ziegler-type or metallocene-type catalysts for the polymerization of non-polar olefins such as ethylene and propylene is known.
  • Such catalysts usually consist of an early transition metal compound, for example a titanium or zirconium compound containing halide, in combination with an excess of a cocatalyst
  • catalyst compositions which contain two or more different olefin polymerization catalysts of the Ziegler type or of the metallocene type is known.
  • WO-95 / 11,264 describes the combination of two catalysts, one of which produces a polyethylene of different average molecular weight than the other
  • Polyethylene is often desirable to introduce branching.
  • the use of bimetallic catalysts for the polymerization of ethylene to branched polymers, with oligomerization of part of the ethylene by a catalyst component, and copolymerization of the oligomers thus formed with ethylene by the other catalyst component is known (cf. Beach, David L; Kissin, Yury V .; J. Polym. Be., Polym. Chem. Ed. 1984, 22, 3027-42. Ostoja-Starzewski, KA; Witte, J .; Reichert, KH, Vasiliou, G. in Transition Metals and Organometallics as Catalysts for Olefin Polymerization. Kaminsky, W .; Sinn, H.
  • WO-97 / 48,735 and WO-97 / 38,024 as well as the as yet unpublished German patent application P19707236.4 describe polymerization catalysts which contain an early transition metal component, i.e. a metallocene or a Ziegler catalyst, and a late transition metal component, preferably that in
  • WO-96 / 23,010 listed. It can be used, for example, to produce reactor blends of linear and branched ethylene homopolymers from ethylene. These show advantageous usage properties.
  • the ethylene homopolymers obtained with polymerization catalysts based on late transition metals such as the catalysts described in WO-96 / 23,010
  • conventional ethylene homopolymers obtained with metallocene or Ziegler catalysts when the polymerization is carried out in the liquid phase conventional reaction media, such as hexane or toluene, form a solution in the reaction medium even at temperatures below 100 ° C., as are customary for customary technical suspension processes.
  • reactor blend processes using such catalysts in a liquid phase process this can lead to their separation due to the different solubility of the components of the polymer mixture obtained.
  • reaction mixtures obtained from the polymerization in reaction media such as toluene or hexane are not directly subjected to filtration or centrifugation to separate the polymer from the reaction medium, but first in a larger quantity
  • Precipitant for example acetone or methanol poured in, or the reaction medium is removed under vacuum.
  • the dissolution of part of the polymer product in the reaction medium is usually disadvantageous, since the work-up following the polymerization and the polymerization process itself become more complex and therefore more uneconomical. It will also be a good one
  • the object of the present invention was to provide a method which avoids the disadvantages mentioned above.
  • the present invention thus relates to a suspension polymerization process for the production of polyethylene by polymerizing ethylene in the presence of a catalyst composition
  • At least one polymerization catalyst based on a late transition metal component which produces a polyethylene with a degree of branching of 0-40 branches, preferably 2-35, particularly preferably 5-15, per 1000 methylene groups and
  • precipitant is understood to mean those which reduce the solubility of the polymer in the liquid reaction medium.
  • Complete precipitation means that after the end of the polymerization reaction the reaction medium contains less than 15% (based on the total amount of ethylene converted), preferably less than 5%, of compounds formed by oligomerization or polymerization in solution.
  • the polymerization of ethylene is understood to mean the conversion to polymers which in total contain a maximum of 3% by weight of one or more olefinic comonomers; under polyethylene a polymer obtained by the polymerization of ethylene according to the invention. Under the homopolymerization of
  • Ethylene means the polymerization of ethylene without the addition of comonomers, ethylene homopolymer is a polymer obtained by the homopolymerization according to the invention.
  • An early transition metal is understood to mean the metals from the groups purple to VIIa of the periodic table of the elements and the metals from the group of the lanthanoids.
  • a late transition metal is understood to mean the metals of the Villa and IB groups of the Periodic Table of the Elements.
  • the catalyst composition used according to the invention contains at least two polymerization catalysts, at least one of which is a polymerization catalyst based on a late transition metal component, which produces a polyethylene with a degree of branching of 0-40, preferably 2-35, particularly preferably 5-15.
  • Each transition metal component contains exactly one transition metal.
  • the catalyst composition used according to the invention preferably contains a nickel, palladium, platinum, iron, ruthenium, cobalt or rhodium compound, particularly preferably a nickel, iron or palladium compound.
  • the late transition metal compound preferably contains exclusively or in combination with other ligands, those ligands which coordinate to the metal in a chelating manner via two or more atoms.
  • the two coordinating atoms are preferably nitrogen atoms.
  • Ligands of the following formulas II and / or III are particularly preferred
  • R 7 , R 8 are independently the same or different hydrogen radicals, in which the carbon atom bonded to the nitrogen atom is preferably connected to at least two further carbon atoms.
  • R 7 and R 8 are preferably C 6 -C 20 aryl radicals which are preferably substituted in both ortho positions, e.g. B. with CC 10 alkyl radicals such as methyl or isopropyl.
  • R 9 , R 10 independently of one another, the same or different, form a hydrogen atom or a C-rC.jo hydrocarbon radical, such as C 1 -C 20 alkyl or C 6 -C 20 aryl, or R 9 and R 0 together form a ring system, which is preferably derived from acenaphtenquinone.
  • Nickel or palladium compounds are particularly preferred, especially in the
  • the catalyst composition according to the invention preferably contains the nickel or palladium compounds mentioned in WO-96 / 23,010, which have a bidentate ligand coordinating via nitrogen atoms and are likewise part of the present description.
  • the late transition metal component may already contain the ligand coordinating with the metal, or it may be obtained by combining one suitable transition metal component with the free ligand or a ligand derivative "in situ" (ie in the polymerization reactor).
  • Me methyl
  • Et ethyl
  • Pr isopropyl
  • the catalyst composition contains at least one further catalyst component. This is a catalyst component based on an early transition metal, or a further catalyst component based on a late transition metal according to the above
  • the catalyst composition used according to the invention preferably contains so-called Ziegler catalyst components (as described, for example, in Falbe, J .; Regitz, M.
  • the Ziegler catalyst component is preferably a
  • Compound of a Group IVa metal e.g. titanium, zirconium or hafnium
  • Va e.g. vanadium or niobium
  • via e.g. chromium or molybdenum
  • a Group IVa metal e.g. titanium, zirconium or hafnium
  • Va e.g. vanadium or niobium
  • via e.g. chromium or molybdenum
  • chromium or molybdenum chromium or molybdenum
  • exemplary but non-limiting examples of Ziegler catalyst components are: titanium tetrachloride, zircon tetrachloride,
  • Hafnium tetrachloride titanium trichloride, vanadium trichloride, vanadium oxychloride, chromium trichloride or chromium oxide.
  • Cyclopentadienyl complexes of metals from the purple group and the group of lanthanoids (e.g. lanthanum or yttrium) are preferred, as are metals from group IVa (e.g. titanium, zirconium or hafnium), Va (e.g. vanadium or niobium) or Via the periodic table of the elements (e.g. chromium or molybdenum), cyclopentadienyl complexes of titanium, zirconium or hafnium are particularly preferred.
  • the cyclopentadienyl complexes can e.g. B. bridged or unbridged
  • Biscyclopentadienylkomplexe as z. B. in EP-A-0, 129.368, EP-A-0.561, 479, EP-A-0.545.304 and EP-A-0.576.970, monocyclopentadienyl complexes such as bridged amidocyclopentadienyl complexes z. B.
  • EP-A-0,416,815 polynuclear cyclopentadienyl complexes as described in EP-A- 0,632,063, ⁇ -ligand-substituted tetrahydropentalenes as in EP-A- 0,659,758 or ⁇ -ligand-substituted tetrahydroindenes as described in EP-A-0,661,300.
  • Preferred metallocene catalyst components are unbridged or bridged metallocene compounds of the formula I,
  • M 1 is a metal from the group purple, IVa, Va or Via of the Periodic Table of the Elements, in particular Ti, Zr or Hf,
  • R 1 are identical or different and are a hydrogen atom or SiR 3 3, where R 3 are identical or different, represent a hydrogen atom or a C C. 4 0 carbon-containing group such as CC 2 -alkyl, C r C 10 fluoroalkyl, C 1 -C 10 -alkoxy, C 6 -C 20 aryl, C 6 -C 10 fluoroaryl, C 6 -C 10 aryloxy, C 2 -C 10 alkenyl, C 7 -C 40 arylalkyl, C 7 -C 40 - Are alkylaryl or C 8 -C 40 arylalkenyl, or R 1 are a C r C 30 - carbon-containing group such as CC 25 alkyl, e.g.
  • Oxygen or sulfur main group of the periodic table of the
  • R 2 are the same or different and is a hydrogen atom or
  • R 3 3 represents a hydrogen atom or a C 1 -C 4 -carbon-containing group such as C r C 20 alkyl, C r C 10 fluoroalkyl, C r C 10 alkoxy, C 6 -C 14 - Aryl, C 6 -C 10 fluoroaryl, C 6 -C 10 aryloxy, C 2 -C 10 alkenyl, C 7 -C 40 arylalkyl, C 7 -C 40 alkylaryl or C 8 -C 40 arylalkenyl , or R 2 are a C, -C 30 - carbon-containing group such as C r C 25 alkyl, e.g. B.
  • Z denotes a bridging structural element between the two cyclopentadienyl rings and v is 0 or 1.
  • Z are groups (M 2 RR 5 ) X , in which M 2 is carbon, silicon, germanium or tin, x is 1, 2 or 3, and R 4 and R 5 are identical or different and are a hydrogen atom or a C 1 -C 6 hydrocarbon-containing group such as C 1 -C 10 alkyl, C 6 -C 14 aryl or trimethylsilyl.
  • Z is preferably CH 2 , CH 2 CH 2 , CH (CH 3 ) CH 2 , CH (C 4 H 9 ) C (CH 3 ) 2 , C (CH 3 ) 2 , (CH 3 ) 2 Si, (CH 3 ) 2 Ge, (CH 3 ) 2 Sn, (C 6 H 5 ) 2 Si,
  • Z can also form a mono- or polycyclic ring system with one or more radicals R 1 and / or R 2 .
  • Catalyst components are:
  • Dimethylsilanediylbis (indenyl) zirconium dichloride Dimethylsilanediylbis (tetrahydroindenyl) zirconium dichloride Isopropylidenebis (cyclopentadienyl) zirconium dichloride isopropylidenebis (3-trimethylsilylcyclopentadienyl) zirconium dichloride isopropylidenebis (3-methylcyclopentadienyl) zirconium dichloride isopropylidenebis (3-n-butylcyclopentadienylloridiridyldirconium dichloride)
  • the catalyst composition according to the invention preferably contains one or more activators such as Lewis acids.
  • Boron compounds such as boranes or aluminum compounds such as aluminum alkyls or aluminoxanes are preferably used as Lewis acid activators.
  • suitable activators are boranes such as trifluoroborane, triphenylborane,
  • the activator can be used in any amount, based on the transition metal components of the catalyst composition according to the invention; it is preferably used in an excess or in stoichiometric amounts.
  • the same activator or different activators can be used to activate the early and late transition metal components of the catalyst composition.
  • the same activator is preferably used for all transition metal components.
  • the activation of the different transition metal components can take place at the same location, e.g. B. in the reactor, or at different locations. In a preferred embodiment, an excess of the activator with the early
  • An aluminoxane is preferably used as the activator for the catalyst component based on a late transition metal.
  • An aluminum alkyl is preferably used as the activator for the catalyst component based on an early transition metal in the case of a Ziegler catalyst component and preferably an aluminoxane and / or a borane in the case of a metallocene catalyst component.
  • the catalyst composition according to the invention optionally contains one or more support components.
  • both the early and late transition metal components can be supported, or only one of the two components can be supported.
  • both components are supported in order to ensure a relative spatial proximity of the different ones
  • the carrier component is preferably a porous inorganic or organic solid.
  • the carrier material preferably contains at least one inorganic Halide such as MgCl 2 or an inorganic oxide such as SiO 2 , Al 2 O 3 , MgO, ZrO 2 , TiO 2 , B 2 O 3 , CaO, ZnO, ThO 2 , carbonates such as B. Na 2 CO 3 , K 2 CO 3 , CaCO 3 , MgCO 3 , sulfates such as Na 2 SO 4 , Al 2 (SO 4 ) 3 , BaSO 4 , nitrates such as e.g. B.
  • the carrier material can be pretreated, e.g. B. by heating at temperatures from 50 ° C to 1000 ° C, for. B. in an inert gas stream or in vacuo at 0.01 bar to 0.001 bar, or by mixing or reacting with a chemical compound.
  • the chemical compound can react with catalyst poisons such as aluminum, magnesium, boron or lithium alkylene or lead to a functionalization of the surface of the carrier. It is irrelevant whether the carrier material already carries functional groups or whether these are only introduced after the pretreatment by appropriate reactions on the surface.
  • the support can be made by the individual
  • Catalyst components are mixed in any order. So z. B. the early and late transition metal compound on the optimally pretreated support (z. B. of SiO 2 ) are applied and then mixed with the activator, preferably in the presence of monomer.
  • the present invention relates to a process for the polymerization of ethylene in the presence of the catalyst composition according to the invention.
  • polymerization encompasses a conversion to polymers which contain a maximum of 3% by weight of one or more olefinic comonomers, and a homopolymerization of ethylene.
  • the early and late transition metal components can be active for all monomers used, but a transition metal component can also specifically implement only one or more of the monomers used.
  • ethylene and an ⁇ -olefin which preferably has 3 to 20 carbon atoms, can be used.
  • a mixture of two copolymers is obtained, or a mixture of a copolymer with an ethylene homopolymer.
  • the copolymer with the lower ⁇ -olefin content is preferably formed by the late transition metal component.
  • ethylene is particularly preferably polymerized without the addition of further olefins, a blend of at least two different polyethylenes being obtained.
  • Aliphatic C 3 -C 5 hydrocarbons such as isobutane, are also particularly suitable.
  • the polymerization process takes place in the liquid phase.
  • This can consist of the monomers used or contain an additional suspension medium.
  • the polymerization is preferably carried out using additional suspension media.
  • Inert organic compounds are preferably used as solvents or suspending agents.
  • Aromatic or aliphatic hydrocarbons or mixtures thereof are particularly preferably used.
  • Toluene, xylenes and saturated aliphatic C 6 -C 30 hydrocarbons are particularly suitable.
  • the process can also be carried out in supercritical media.
  • the polymerization process is characterized in that the polymeric products form an additional phase during the polymerization. This allows them to be easily separated from the suspension medium after the reaction, for example by filtration or centrifugation.
  • the polymerization process is carried out in the temperature range from 25 to 150 ° C., particularly preferably 50 to 90 ° C.
  • the process is carried out in the pressure range from 2 to 300 atm, preferably 2 to 100 atm, particularly preferably 3 to 30 atm.
  • reaction conditions e.g. B. temperature
  • chain transfer agents such. B. hydrogen, monomer concentrations, and the
  • Catalyst concentration can be controlled molecular weight distributions, degree of branching and other properties of the polymers formed.
  • the degree of branching of the polymers can be controlled via the concentration of the monomers.
  • the reaction can also take place in two or more reactors connected in cascade. By feeding the catalyst components into the individual Reactors can change the ratio of the two catalysts.
  • the process can be carried out in one or more stages. According to the invention, the conditions are chosen so that the polymeric products form an additional solid phase during the reaction.
  • the productivity of each individual transition metal component is preferably above 1,000 kg polymer / (mol transition metal x h), particularly preferably above 2,000 kg polymer / (mol transition metal x h).
  • the polymerization process according to the invention is suitable for the production of
  • the weight average molecular weights of the individual polymer fractions are preferably in the range from 11 to 10,000 kg / mol, particularly preferably 20 to 1,000 kg / mol.
  • the molar ratio of the proportions of the late transition metal component (s) to the further component (s) can be in the range from 0.1: 99.9 to 99.9: 0.1, preferably 1:30 to 30: 1.
  • the ratio of the proportions of the polymers formed by the late transition metal catalyst and the polymers by the further component (s) can be in the range from 0.1: 99.9 to 99.9: 0.1, preferably 10:90 to 90 : 10, particularly preferably 1: 1 to 1:50.
  • the polymerization process according to the invention is particularly suitable for the homopolymerization of ethylene into a blend of two or more polymers in a liquid process, these occurring during the polymerization as a suspension in the reaction medium and thus being easy to separate, e.g. by filtration or centrifugation.
  • the polymerization process according to the invention is particularly preferably suitable for homopolymerizing ethylene to a blend of two or more polymers, at least one of which has the following branching structure:
  • essentially linear polymer blends can also be produced, the respective polymers having a different molecular mass.
  • the polymerization process according to the invention is particularly preferably suitable for homopolymerizing ethylene to a blend of two or more polymers which has a density in the range from 0.910 to 0.970 g / ml.
  • the process is used to produce blends which contain at least 50% by weight, preferably greater than 80% by weight, of a linear ethylene homopolymer with a weight-average molecular weight of at least M w 200 kg / mol, preferably M w > 1000 kg / mol included.
  • Linear polyethylenes with molecular weights of M w > 1000 kg / mol are difficult to process in thermoplastics or cannot be processed at all, so blends of these polymers are also difficult to produce, for example by extrusion processes.
  • the process according to the invention is therefore particularly suitable for producing blends of very high molecular weight polyethylenes which are very difficult to access from the individual components by subsequent blending processes.
  • the presence of branched portions in high molecular weight polyethylenes can improve their application and processing properties.
  • the production of the polymer blend in the reactor reduces energy consumption, does not require subsequent blend processes and enables simple control of the molecular weight distributions and the like
  • the polymerizations were carried out in a 5L steel autoclave with a heating / cooling jacket and mechanical stirrer.
  • MAO was used as a 10% toluene solution (from Witco).
  • silica-fixed MAO-S TA-2794 from Witco was used, Al content 23% by mass.
  • the Exxsol® used as the reaction medium is a mixture of aliphatic hydrocarbons with a boiling range of 100 to 120 ° C.
  • GPC measurements were carried out on a GPC 210 from PL from polystyrene gel columns from PSS (type SDV, pore size 10 3 , 10 5 , 10 7 Angstrom). The measurements were carried out at 135 ° C in 1,2,4-trichlorobenzene with universal calibration against linear polyethylene. 13 C NMR spectra (75 MHz) were measured at 90 ° C in tetrachloroethane-d 2 / hexachlorobutadiene with CPD - 1 H decoupling. MVIs were determined at 190 ° C according to ISO 1133.
  • the density was determined on pressed plates using the gradient method.
  • Examples 1-4 see Table 1: The autoclave was charged with 3.5 L of solvent, briefly saturated with ethylene under 10 atm, and relaxed to normal pressure. Then, a solution of the early transition metal catalyst component in 10 mL MAO, followed by a solution of the late transition metal catalyst component in 10 mL MAO was added to the autoclave. The autoclave was closed, a constant pressure of 10 atm
  • the polymer suspension obtained was filtered on a suction filter.
  • the polymer product obtained was treated by stirring with HCl acidic acetone, filtration, stirring twice with acetone and subsequent filtration, and then drying in a vacuum drying cabinet.
  • Examples 1 and 2 are within the meaning of the invention. Examples 3 and 4 serve for illustration.
  • Table 2 shows the results of the 13 C NMR spectroscopic investigations of the polymers with regard to their branching structure.
  • Example 6 This example demonstrates the separation of the polymer from the suspension medium by filtration.
  • the polymer product was treated by stirring with HCl acid acetone, filtration, stirring twice with acetone and subsequent filtration, and then drying in a vacuum drying cabinet. 74 g of white powder were obtained. Density 0.949 g / mL
  • the polymerization was carried out analogously to Example 6, but with [bis (t7-butylcyclopentadienyl) ⁇ zirconium dichloride] / MAO as the sole catalyst component and with the addition of 15 mmol H 2 .
  • Example 6 in conjunction with Examples 3, 7, 8 and 9, demonstrates the regulation of the catalyst by hydrogen.
  • the early transition metal component is much more sensitive to hydrogen than the late transition metal component and can therefore be controlled selectively
  • a Ziegler catalyst corresponding to 1 mmol titanium
  • the polymer suspension obtained was filtered on a suction filter.
  • the polymer product obtained was extracted by stirring with HCl acid acetone, filtration, Stirred twice with acetone and each subsequent filtration and then dried in a vacuum drying cabinet. 114 g of white powder were obtained. Density 0.920 g / mL. MVI (21.6 kg) 0.1 mL / 10 min.
  • the polymerization of ethylene was carried out analogously to Example 11, but using the Ziegler catalyst as the sole catalyst component. A polymer was obtained whose MVI cannot be measured due to the low flowability.
  • Examples 11 and 12 demonstrate the production of reactor blends with a high molecular weight linear polyethylene component.
  • the autoclave was charged with 3.5 L of Exxsol, saturated with ethylene by briefly stirring under 10 atm, and depressurized to normal pressure.
  • the autoclave was closed, a constant pressure of 10 atm ethylene was applied and the temperature was raised to 70 ° C. After 55 minutes, the reaction was stopped by rapidly cooling and venting the ethylene.
  • the polymer suspension obtained was filtered on a suction filter.
  • the polymer product obtained was extracted by stirring and subsequent filtration
  • the polymer obtained from the suspending agent shows that it is a linear polyethylene
  • Example 15 The autoclave was charged with 3.5 L of Exxsol, saturated with ethylene by briefly stirring under 10 atm, and depressurized to normal pressure.
  • Vacuum drying cabinet dried. 32 g of white powder were obtained. This example demonstrates the heterogenization of the catalyst.
  • the autoclave was charged with 3.5 L of Exxsol, saturated with ethylene by briefly stirring under 10 atm, and depressurized to normal pressure.
  • the polymer suspension obtained was filtered on a suction filter.
  • the polymer product obtained was stirred with methanol, filtered off and then in one
  • Vacuum drying cabinet dried. 295 g of white powder were obtained. This example demonstrates the heterogenization of the catalyst.
  • B [ ⁇ isopropylidene (fluorenyl) (cyclopentadienyl) ⁇ zirconium dichloride] r

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Abstract

L'invention concerne un procédé pour la polymérisation en suspension d'éthylène à l'aide de compositions catalytiques contenant un catalyseur de polymérisation à base d'un constituant de métal de transition tardif et au moins un autre catalyseur de polymérisation à base d'un constituant de métal de transition précoce ou tardif.
PCT/EP1999/003417 1998-05-28 1999-05-18 Procede pour la polymerisation en suspension d'ethylene WO1999061490A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE19823871.1 1998-05-28
DE19823871A DE19823871A1 (de) 1998-05-28 1998-05-28 Suspensionsphasenverfahren für die Polymerisation von Ethylen

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WO1999061490A1 true WO1999061490A1 (fr) 1999-12-02

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DE (1) DE19823871A1 (fr)
WO (1) WO1999061490A1 (fr)

Cited By (2)

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KR101086603B1 (ko) * 2002-09-27 2011-11-23 토탈 페트로케미칼스 리서치 펠루이 단일 반응기에서 이정점 폴리올레핀의 제조를 위한하프노센 성분을 포함하는 두자리 촉매계
US10926250B2 (en) 2017-12-01 2021-02-23 Exxonmobil Chemical Patents Inc. Catalyst systems and polymerization processes for using the same

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB9918189D0 (en) * 1999-08-02 1999-10-06 Bp Chem Int Ltd Polymerisation process
GB0003363D0 (en) * 2000-02-14 2000-04-05 Bp Chem Int Ltd Polymer blends
EP1650231A1 (fr) * 2004-10-21 2006-04-26 Total Petrochemicals Research Feluy Polyoléfines préparés par une combination de nouveaux catalyseurs à site unique et de metallocènes dans un seul réacteur
EP3717522A1 (fr) * 2017-12-01 2020-10-07 ExxonMobil Chemical Patents Inc. Systèmes de catalyseur et procédés de polymérisation pour leur utilisation
US10961331B2 (en) 2018-12-19 2021-03-30 Chevron Phillips Chemical Company Lp Ethylene homopolymers with a reverse short chain branch distribution

Citations (4)

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EP0009160A1 (fr) * 1978-09-05 1980-04-02 The Dow Chemical Company Catalyseur à efficacité élevée pour la polymérisation d'oléfines et son utilisation
EP0114434A1 (fr) * 1982-12-17 1984-08-01 Stamicarbon B.V. Catalyseur et polymérisation des oléfines avec ce catalyseur
WO1997038024A1 (fr) * 1996-04-09 1997-10-16 Mitsui Chemicals, Inc. Catalyseur de polymerisation d'olefines, procede de polymerisation d'olefines, compositions de polymeres d'olefines et articles thermoformes
WO1997048735A1 (fr) * 1996-06-17 1997-12-24 Exxon Chemical Patents Inc. Systemes de catalyseurs a metal de transition mixte, pour la polymerisation d'olefines

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0009160A1 (fr) * 1978-09-05 1980-04-02 The Dow Chemical Company Catalyseur à efficacité élevée pour la polymérisation d'oléfines et son utilisation
EP0114434A1 (fr) * 1982-12-17 1984-08-01 Stamicarbon B.V. Catalyseur et polymérisation des oléfines avec ce catalyseur
WO1997038024A1 (fr) * 1996-04-09 1997-10-16 Mitsui Chemicals, Inc. Catalyseur de polymerisation d'olefines, procede de polymerisation d'olefines, compositions de polymeres d'olefines et articles thermoformes
EP0893455A1 (fr) * 1996-04-09 1999-01-27 Mitsui Chemicals, Inc. Catalyseur de polymerisation d'olefines, procede de polymerisation d'olefines, compositions de polymeres d'olefines et articles thermoformes
WO1997048735A1 (fr) * 1996-06-17 1997-12-24 Exxon Chemical Patents Inc. Systemes de catalyseurs a metal de transition mixte, pour la polymerisation d'olefines

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR101086603B1 (ko) * 2002-09-27 2011-11-23 토탈 페트로케미칼스 리서치 펠루이 단일 반응기에서 이정점 폴리올레핀의 제조를 위한하프노센 성분을 포함하는 두자리 촉매계
US10926250B2 (en) 2017-12-01 2021-02-23 Exxonmobil Chemical Patents Inc. Catalyst systems and polymerization processes for using the same

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