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WO2022094508A1 - Polypropylène produit à l'aide de donneurs d'électrons internes styréniques modifiés - Google Patents

Polypropylène produit à l'aide de donneurs d'électrons internes styréniques modifiés Download PDF

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Publication number
WO2022094508A1
WO2022094508A1 PCT/US2021/071535 US2021071535W WO2022094508A1 WO 2022094508 A1 WO2022094508 A1 WO 2022094508A1 US 2021071535 W US2021071535 W US 2021071535W WO 2022094508 A1 WO2022094508 A1 WO 2022094508A1
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Prior art keywords
polymerization
compound
solid catalyst
contact
catalyst component
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PCT/US2021/071535
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English (en)
Inventor
Christopher G. Bauch
Todd S. EDWARDS
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Exxonmobil Chemical Patents Inc.
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Publication of WO2022094508A1 publication Critical patent/WO2022094508A1/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
    • C08F110/04—Monomers containing three or four carbon atoms
    • C08F110/06—Propene

Definitions

  • the present invention relates to a method for producing a solid catalyst component for olefin polymerization, a method for producing a catalyst for olefin polymerization, and a method for producing an olefin polymer.
  • olefins such as propylene have been polymerized using a solid catalyst for olefin polymerization (also referred to as a “solid catalyst”), and the obtained olefin polymer has been molded by various molding machines, stretching machines, and the like after being melted, and has been utilized in various applications such as containers and films in addition to molded articles such as automotive parts and home electric parts.
  • a solid catalyst for olefin polymerization also referred to as a “solid catalyst”
  • a solid catalyst component for olefin polymerization prepared by a magnesium compound, a titanium halogen compound and an electron-donating compound also referred to as a “solid catalyst component”
  • a solid catalyst component obtained by bringing an organoaluminum compound and an organosilicon compound into contact with each other are known, and a large number of methods for producing the same have also been proposed.
  • JP-A-2001-503079 describes a solid catalyst component containing two kinds of internal electron-donating compounds of weak solubility and strong solubility.
  • JP-A-2010-43267 proposes a solid catalyst component in which a bifunctional electronic-donating compound ED selected from a diester, a diketone, a diamine, and a di ether and a monofunctional electron-donor MD selected from a ether, an ester, an amine, and a ketone are contained in an amount ratio in which the molar ratio of ED/MD is larger than 30 in order to donate high activity and stereospecificity to a solid catalyst when used for (co)- polymerization of propylene or a higher alpha olefin to a solid catalyst.
  • ED bifunctional electronic-donating compound ED selected from a diester, a diketone, a diamine, and a di ether
  • a monofunctional electron-donor MD selected from a ether, an ester, an amine, and a ketone
  • the inventors have found that a novel type of electron donor system for a Ziegler- Natta type solid catalyst is useful in producing polypropylenes having improved stereoregularity.
  • a polypropylene having a p-xylene solubles (XS) content of 1.5 wt% or less based on the weight of the polypropylene, wherein the polypropylene is made by combining propylene with a solid catalyst comprising a magnesium compound having been contacted with a styrenic compound.
  • XS p-xylene solubles
  • the magnesium compound and the styrenic compound are brought into contact with each other to obtain a preliminary contact material, and then the preliminary contact material, a titanium halogen compound, and one or more internal electrondonating compounds are brought into contact with each other to obtain a solid catalyst component that is contacted with the propylene.
  • a “polypropylene” is a polyolefin comprising at least 80, or 90, or 95, or 98 wt%, by weight of the polypropylene, of propylene derived units, and most preferably is a homopolymer of propylene derived units.
  • the melt flow rate (MFR) of the polypropylene can be within a range from 1, or 5, or 10, or 15, or 20, or 25 g/10 min to 45, or 55, or 100, or 300, or 350, or 400, or 450, or 500, or 1000, or 2000, or 2500 g/10 min, as measured per ASTM 1238, 2.16 kg at 230 °C.
  • the polypropylene can form thermoplastic blends including from 1 wt% to 95 wt% by weight of the blend of the polypropylene, and is most preferably blended with a propylene-based elastomer.
  • the polypropylene is preferably crystalline, as evidenced by having a melting point temperature (Tm) greater than 110 °C, greater than 115 °C, and greater than 130 °C, or within a range from 110, or 115, or 130 °C to 150, or 160, or 170 °C.
  • Tm melting point temperature
  • the term “crystalline,” as used herein characterizes those polymers which possess high degrees of inter- and intra-molecular order.
  • the polypropylene can have a heat of fusion at least 60 J/g, at least 70 J/g, or at least 80 J/g, as determined by Differential Scanning Calorimetry (DSC) analysis. The heat of fusion is dependent on the composition of the polypropylene.
  • a polypropylene homopolymer preferably has a higher heat of fusion than copolymer or blend of homopolymer and copolymer.
  • the thermal properties of the polypropylene and propylene- based elastomers were determined using DSC.
  • DSC data was obtained using a Perkin- Elmer DSC, where 7.5 mg to 10 mg of a sheet of the polymer to be tested was pressed at approximately 200 °C to 230 °C, then removed with a punch die and annealed at room temperature for 48 hours. The samples were then sealed in aluminum sample pans. The DSC data was recorded by first cooling the sample to -50 °C and then gradually heating it to 200 °C at a rate of 10 °C/minute. The sample was kept at 200 °C for 5 minutes before a second coolingheating cycle was applied. Both the first and second cycle thermal events were recorded.
  • the polypropylenes described herein can also include so called “impact copolymers.”
  • an “impact copolymer” is a two-phase polypropylene comprising a matrix phase of a polypropylene (“PP”) comprising within a range from 0, 0.1 to 2, or 3 wt%, by weight of the polypropylene, or ethylene or another a-olefin, and a dispersed phase of an EPR comprising within a range from 5, or 10 wt% to 20, or 30, or 40, or 50, or 50 wt%, by weight of the EPR, of ethylene and/or another a-olefin.
  • PP polypropylene
  • EPR dispersed phase of an EPR comprising within a range from 5, or 10 wt% to 20, or 30, or 40, or 50, or 50 wt%, by weight of the EPR, of ethylene and/or another a-olefin.
  • impact copolymers are made in an in situ polymerization process wherein each component is made in series-type reactors to form one component (either the PP or EPR), then the other thus forming the combination of the PPZEPR, wherein the EPR is finely dispersed in the PP matrix phase.
  • the term “catalyst” refers to the solid magnesium and halogencontaining titanium compound described herein as well as the internal electron donors (1) and (2), and preferably the external electron donor(s) and organoaluminum desirable to effect polymerization of olefins to polyolefins.
  • Compounds that include a solid magnesium and halogen-containing titanium compound with at least one internal electron donor are also referred to as “Ziegler-Natta” catalysts.
  • the present invention has been completed based on such findings.
  • the present invention provides the following (1) to (4):
  • (1) The method for producing a solid catalyst component for olefin polymerization is characterized in that a magnesium compound and a styrenic compound represented by the following general formula (I) are brought into contact with each other to obtain a preliminary contact material, and then the preliminary contact material, the titanium halogen compound, and the internal electron-donating compound are brought into contact with each other to obtain a solid catalyst component for olefin polymerization.
  • R1 is any group selected from a linear alkyl group having 1 to 8 carbon atoms, a branched chain alkyl group having 3 to 8 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms, and an aromatic group having 6 to 12 carbon atoms
  • n and m are each an integer of 0 or more
  • n + m is 1 to 30,000
  • X is a polymerization unit having 9 to 50,000 total carbon atoms having the following constitutional unit (A) (a saturated, linear C4 hydrocarbon) and/or the following constitutional unit (B) (a saturated, iso-C5 hydrocarbon).
  • R1 is an aromatic group having 6 to 12 carbon atoms.
  • step (2) the method for producing a catalyst for olefin polymerization is characterized in that a solid catalyst component for olefin polymerization obtained by the production method described in (1) above and an organoaluminum compound represented by the following general formula (II) are brought into contact with each other:
  • R2nAlQ3-p (II) [0020]
  • R2 is an alkyl group having 1 to 6 carbon atoms
  • Q is a hydrogen atom or a halogen atom
  • p is a real number of 0 ⁇ p ⁇ 3
  • each R2 may be the same or different from each other, and when a plurality of Q is present, each Q may be the same or different from each other.
  • step (3) the method for producing a catalyst for olefin polymerization according to (2) above, wherein a solid catalyst component for olefin polymerization obtained by the production method described in (1) above, an organoaluminum compound represented by the general formula (II), and an external electron-donating compound are brought into contact with each other.
  • step (4) the method for producing an olefin polymer is characterized in that polymerization of olefins is carried out using a catalyst for olefin polymerization obtained by the production method described in (2) or (3) above.
  • the present invention it is possible to provide a method for producing a solid catalyst component for olefin polymerization capable of producing a polymer having excellent polymerization activity and excellent stereospecificity, a method for producing a catalyst for olefin polymerization, and a method for producing an olefin polymer.
  • solid catalyst component for polymerizing olefins according to the present invention
  • a method for producing a solid catalyst component for olefin polymerization according to the present invention is characterized in that a magnesium compound and a styrenic compound represented by the general formula (I) are brought into contact with each other to obtain a preliminary contact material, and then the preliminary contact material, the titanium halogen compound, and the internal electron-donating compound are brought into contact with each other to obtain a solid catalyst component for olefin polymerization.
  • R1 is any group selected from a linear alkyl group having 1 to 8 carbon atoms, a branched chain alkyl group having 3 to 8 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms, and an aromatic group having 6 to 12 carbon atoms, and n and m are each an integer of 0 or more, n + m is 1 to 30,000, and X is a polymerization unit having 9 to 50,000 total carbon atoms having the constitutional unit (A) and/or the constitutional unit (B).
  • the magnesium compound is not particularly limited as long as it is a conventionally known product.
  • magnesium compound examples include one or more selected from magnesium dihalide, dialkylmagnesium, alkylmagnesium halide, dialkoxymagnesium, diaryloxymagnesium, alkoxymagnesium halide, magnesium fatty acid, and the like.
  • magnesium dihalide a mixture of magnesium dihalide and dialkoxymagnesium, and dialkoxymagnesium are preferred, and particularly, dialkoxymagnesium is preferred.
  • dialkoxymagnesium include one or more selected from dimethoxymagnesium, diethoxymagnesium, dipropoxymagnesium, dibutoxymagnesium, ethoxymethoxymagnesium, ethoxypropoxymagnesium, and butoxyethoxymagnesium, of which diethoxymagnesium is particularly preferable.
  • Examples of the method for producing dialkoxymagnesium include the methods exemplified in JP-A-58-4132, JP-A-62-51633, JP-A-3-74341, JP-A-4-368391, JP-A-8-73388, and the like.
  • a magnesium compound and a styrenic compound represented by the general formula (I) are brought into contact with each other to obtain a preliminary contact.
  • R1 is any group selected from a linear alkyl group having 1 to 8 carbon atoms, a branched alkyl group having 3 to 8 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms, and an aromatic group having 6 to 12 carbon atoms.
  • R1 is a linear alkyl group having 1 to 8 carbon atoms
  • examples of R1 include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, and an octyl group.
  • R1 is a branched chain alkyl group having 3 to 8 carbon atoms
  • examples of R1 include a iso-propyl group, a iso-butyl group, a sec-butyl group, a tert-butyl group, a isopentyl group, a neopentyl group, a sec-pentyl group, a tert-pentyl group, a 3 -methylhexyl group, and a 2-ethylhexyl group.
  • R1 is a cycloalkyl group having 3 to 8 carbon atoms, for example, cyclopropyl group, methylcyclopropyl group, ethyl cyclopropyl group, cyclobutyl group, methylcyclobutyl group, methylcyclobutyl group, ethyl cyclobutyl group, cyclopentyl group, methylcyclopentyl group, ethylcyclopentyl group, cyclohexyl group, methylcyclohexyl group, ethyl cyclohexyl group, cycloheptyl group, methylcycloheptyl group, cyclooctyl group, and the like can be mentioned as R1.
  • R1 is an aromatic group having 6 to 12 carbon atoms
  • examples of R1 include a phenyl group, a methylphenyl group, an ethylphenyl group, a benzyl group, a naphthyl group, and a biphenyl group.
  • Rl an aromatic group having 6 to 12 carbon atoms is preferred, and a benzoyloxy group is more preferred.
  • n and m are each an integer of 0 or more.
  • n+m is 1 to 30,000, preferably 2 to 20,000, more preferably 2 to 10,000, still more preferably 10 to 5000, still more preferably 50 to 1000, and still more preferably 100 to 500.
  • X is a polymerization unit having a total number of carbon atoms of 9 to 50,000 having the constitutional unit (A) and/or the constitutional unit (B).
  • the total number of carbon atoms of X is 9 to 50,000, preferably 9 to 25,000, more preferably 9 to 10,000, and still more preferably 9 to 5000.
  • the structure of the compound represented by the general formula (I) can be specified by analysis using gel permeation chromatography (GPC), nuclear magnetic resonance apparatus ('H-NMR, "C-NMR) and Fourier transform infrared spectrophotometer (FT-IR).
  • GPC gel permeation chromatography
  • 'H-NMR nuclear magnetic resonance apparatus
  • FT-IR Fourier transform infrared spectrophotometer
  • the number average molecular weight (Mn) of the compound represented by the general formula (I) is specified by gel permeation chromatography (GPC).
  • Mn number-average molecular weight
  • the number average molecular weight (Mn) was calculated from the retention time obtained by GPC measurement based on a calibration curve showing a correlation between the retention time using standard polystyrene and the number average molecular weight (Mn)
  • Measuring instrument 400 MHz ECA400 'H resonance frequency, manufactured by Nippon Electronics Co., Ltd. (JEOL)
  • the compound represented by the general formula (I) acts as a protective agent for the adsorption site of the internal electron-donating compound in the carrier, and inhibits the excessive adsorption of the internal electron-donating compound having weak solubility (strong adsorption property) on the carrier, so that the amount of the internal electron-donating compound adsorbed on the carrier can be adjusted, particularly when two or more kinds of the internal electron-donating compounds are used.
  • the compound represented by the general formula (I) has a faster adsorption rate on a carrier than each electron-donating compound, and can prevent the adsorption of an internal electron-donating compound having weak solubility (strong adsorption property) for a certain period of time, and is considered to have a property of not preventing the adsorption of an internal electron-donating compound having strong solubility (weak adsorption property) by desorbing from a carrier after a lapse of a certain time, and is considered to suitably act as the above-mentioned protective agent.
  • the amount of contact of the compound represented by the general formula (I) with respect to the magnesium compound is preferably 0.001 to 0.500, more preferably 0.005 to 0.350, and still more preferably 0.050 to 0.200 on a mass basis.
  • the contact amount of the compound represented by the above general formula (I) is within the above range, the content ratio of the strongly soluble (weakly adsorptive) internal electron-donating compound in the solid catalyst component can be easily controlled within a desired range.
  • the contact temperature is preferably from -20 to 50 °C, more preferably from -10 to 40 °C, and still more preferably from 0 to 30 °C
  • the contact time is preferably from 3 to 360 minutes, more preferably from 5 to 240 minutes, and still more preferably from 5 to 120 minutes.
  • a preliminary contact compound of a magnesium compound and a compound represented by the general formula (I), a titanium halogen compound, and an internal electron-donating compound are brought into contact with each other.
  • the titanium halogen compound is not particularly limited as long as it is a tetravalent titanium halogen compound and is a conventionally known product.
  • the titanium halogen compound include one or more kinds selected from titanium tetrahalide, alkoxytitanium halide, and the like.
  • Examples of such a titanium halogen compound include titanium tetrahalide or alkoxytitanium halide represented by the following general formula (III):
  • R3 represents a hydrocarbon group having 1 to 10 carbon atoms
  • Y represents a halogen atom
  • i is an integer of 0 to 3.
  • titanium tetrahalide such as titanium tetrachloride, titanium tetrabromide, or titanium tetraiodide is preferred, and titanium tetrachloride is more preferred.
  • the internal electronic-donating compound is not particularly limited as long as it can donate an electron pair at the time of preparation of a solid catalyst component and a functional group for donating an electron pair is an organic compound containing an oxygen atom or a nitrogen atom.
  • the internal electron-donating compound may be used alone or in combination of two or more, and when the internal electron-donating compound is used in combination of two or more kinds, two or more kinds of internal electron-donating compounds having different adsorption properties to the magnesium compound may be mentioned.
  • the strength or weakness of the adsorption property of the internal electronic-donating compound to the magnesium compound can be determined by the magnitude of the amount of the internal electron-donating compound (the amount of the internal electron-donating compound in the solid catalyst component) remaining in each solid catalyst component when the solid catalyst component is prepared under the same conditions while using a stirred product obtained by stirring 20 g of the magnesium compound used at the time of preparation of the solid catalyst component with 60 mL of toluene and each internal electron-donating compound of the same weight stirred under a temperature of -6 °C, while changing only the internal electron-donating compound to be used.
  • each solid catalyst component it can be defined that the internal electronic-donating compound having a larger residual amount is stronger in adsorption property, and that the internal electron-donating compound having a smaller residual amount is weaker in adsorption property.
  • the amount of the internal electronic-donating compound in the above solid catalyst component can be determined by hydrolyzing a solid catalyst, and then extracting an internal electron-donating compound using an aromatic solvent, and measuring this solution by a gas chromatography FID (Flame Ionization Detector, flame ionization type detector) method, as described later.
  • FID Gas chromatography FID
  • the internal electron-donating compound may be a phthalate ester compound or a compound other than a phthalate ester compound (also referred to as a “non-phthalate compound”).
  • the above phthalate ester compound is a compound having the following phthalate ester structure (IV):
  • R4, R5, R6, R7, R8 and R9 are hydrogen or organic groups, and when more than one R is present, each R may be the same or different from each other, and R4, R5, R6, R7, R8 and R9 may be the same or different from each other.
  • Specific examples of the phthalate ester compound include di-n-propyl phthalate, diethyl phthalate, di-normal butyl phthalate, and di-isobutyl phthalate.
  • R4, R5, R6, and R7 are each hydrogen
  • R8 and R9 are selected from Cl to CIO linear or branched alkyls.
  • the non-phthalate compound is a compound having no phthalate ester structure described above in the molecule, and does not correspond to a phthalate ester compound such as a compound represented by the general formula (IV).
  • a phthalate ester compound such as a compound represented by the general formula (IV).
  • the non-phthalate compound include one or more kinds selected from a diether compound, a ether carbonate compound, an aliphatic carboxylic ester compound, a ether-carboxylic ester compound, a dicarbonate compound, and the like.
  • non-phthalate compounds specifically, ethyl maleate, benzylidene malonate, 2,3-diisopropylhexane-l,2-dicarbonate diethyl, cyclohexane-l,2-dicarbonate di-n- propyl, cyclohexane-l,2-dicarbonate di-n-butyl, cyclohexene-l,2-dicarbonate di-n- propyl, cyclohexene- 1,2-dicarboxylate n-butyl, 3-ethoxy-2-t-butylpropionate, 3-ethoxy-2-t- pentylpropionate ethyl, 2,4-pentanedioldibenzoate, 3-methyl5-t-butyl-l,2-phenylenebenzoate, and 3,5-diisopropyl-l,2-phenylenebenzoate, 2-ethoxyethyl carbonate, 2-prop
  • non-phthalate internal donors include branched (iso, tert, etc.) C5 to C20 alcohols, branched C5 to C20 ethers, branched C5 to C20 di-alcohols, branched C5 to C20 di-ethers, and combinations thereof, an example of which includes compounds such as 2- isopropyl -2-isopentyl- 1,3 -dimethoxypropane.
  • the internal donors used in the process to produce polypropylenes described herein include one phthalate ester compound and one non-phthalate compound, preferably a branched C5 to C20 diether compound.
  • the combination of the internal electron-donating compounds may be a combination of phthalate ester compounds different from each other, or a combination of a phthalate ester compound and a non-phthalate compound different from each other.
  • a polymer represented by the above general formula (I) is brought into contact with a magnesium compound in advance, and then a titanium halogen compound and an internal electron-donating compound are brought into contact with the obtained preliminary contact material.
  • titanium halogen compound and the internal electron-donating compound there is no particular limitation on the order of contact of the titanium halogen compound and the internal electron-donating compound with respect to the above pre-contact.
  • the titanium halogen compound and the internal electron-donating compound may be separately contacted with respect to the preliminary contact described above, or may be brought into contact with each other at the same time.
  • the titanium halogen compound and the internal electron-donating compound may be brought into contact with each other by collectively adding or partially adding a total amount to each of the above preliminary contacts, and such split addition may be performed continuously or intermittently.
  • the addition interval may be constant or not constant.
  • the addition interval is preferably from 1 minutes to 60 minutes, more preferably from 3 minutes to 30 minutes, and still more preferably from 5 minutes to 15 minutes.
  • a solid catalyst component is prepared by bringing a preliminary contact product, a titanium halogen compound, and an internal electron-donating compound into contact with each other, it is preferable to carry out the preparation under an inert gas atmosphere.
  • the temperature at which the preliminary contact, the titanium halogen compound and the internal electron-donating compound are brought into contact with each other may be a relatively low temperature range around room temperature when they are simply brought into contact with each other and stirred and mixed, or when they are dispersed or suspended and subjected to a modification treatment.
  • a temperature range of 40 to 130 °C is preferred, and in this case, it is preferable that the reaction is carried out by holding at the same temperature after contact of each component.
  • the temperature at the time of obtaining the above product is less than 40 °C, the reaction does not proceed sufficiently, and the resulting solid catalyst component hardly exhibits sufficient performance.
  • the reaction time in obtaining the above product is preferably 1 minutes or more, more preferably 10 minutes or more, and still more preferably 30 minutes or more.
  • the amount ratio of each component to be used in preparing the solid catalyst component varies depending on the preparation method, it may be appropriately determined.
  • the content of the titanium atom, the magnesium atom, the halogen atom, and the internal electron-donating compound constituting the obtained solid catalyst component is not particularly limited within a range capable of exhibiting the effect of the present invention.
  • the obtained solid catalyst component preferably contains 1.0 to 10.0% by mass of titanium atoms, more preferably 1.5 to 8.0% by mass, and still more preferably 1.5 to 5.0% by mass.
  • the obtained solid catalyst component preferably contains 10.0 to 70.0% by mass of magnesium atoms, more preferably contains 10.0 to 50.0% by mass, still more preferably contains 15.0 to 40.0% by mass, and still more preferably contains 15.0 to 25.0% by mass.
  • the obtained solid catalyst component preferably contains 20.0 to 90.0% by mass of a halogen atom, more preferably contains 30.0 to 85.0% by mass, still more preferably contains 40.0 to 80.0% by mass, and still more preferably contains 45.0 to 80.0% by mass.
  • the obtained solid catalyst component preferably contains an internal electrondonating compound in an amount of 0.5 to 30.0% by mass, more preferably 1.0 to 25.0% by mass, and still more preferably 2.0 to 20.0% by mass in total.
  • the content of titanium atoms contained in the solid-state catalytic components means a value measured according to the method described in JIS 8311- 1997 “titanium determination method in titanium ore” (oxidation-reduction titration).
  • the content ratio of magnesium atoms contained in the solid catalyst component means a value measured by a EDTA titration method in which a solid catalyst component is dissolved in a hydrochloric acid solution and titrated with a EDTA solution.
  • the content of halogen atoms contained in the solid catalyst component means a value measured by a silver nitrate titration method in which a solid catalyst component is treated with a mixed solution of sulfuric acid and pure water to obtain an aqueous solution, and then a predetermined amount is collected and a halogen atom is titrated with a silver nitrate standard solution.
  • the content of the internal electronic-donating compound means a value obtained by hydrolyzing a solid catalyst and then extracting an internal electron-donating compound using an aromatic solvent, and measuring the solution by a gas chromatography FID (Flame Ionization Detector, flame ionization type detector) method.
  • the magnesium compound and the compound represented by the above general formula (I) are brought into contact with each other in advance, and then the obtained preliminary contact compound, the titanium halogen compound, and the internal electronic-donating compound are brought into contact with each other, whereby the content of the internal electron-donating compound in the solid catalyst component can be easily controlled in an appropriate range.
  • a method for producing a catalyst for olefin polymerization according to the present invention is characterized in that a solid catalyst component for olefin polymerization obtained by a production method according to the present invention and an organoaluminum compound represented by the general formula (II) are brought into contact with each other.
  • the organoaluminum compound represented by the general formula (II) includes one or more kinds selected from trialkylaluminum such as triethylaluminum, triisopropylaluminum, tri-n-butylaluminum, triisobutylaluminum, and the like, and alkylaluminum halides such as diethylaluminum chloride, and diethylaluminum bromide, and the like.
  • organoaluminum compounds one or more selected from alkylaluminum halide such as diethylaluminum chloride; trialkylaluminum such as triethylaluminum, tri-n-butylaluminum, triisobutylaluminum, and the like are preferable, and one or more selected from triethylaluminum and triisobutyl aluminum are more preferable.
  • alkylaluminum halide such as diethylaluminum chloride
  • trialkylaluminum such as triethylaluminum, tri-n-butylaluminum, triisobutylaluminum, and the like are preferable
  • triethylaluminum and triisobutyl aluminum are more preferable.
  • an external electron-donating compound is further brought into contact with each other together with a solid catalyst component for olefin polymerization obtained by the production method according to the present invention and an organoaluminum compound represented by the general formula (II).
  • an external electron-donating compound for example, one or more organosilicon compounds selected from phenylalkoxysilane, alkylalkoxysilane, phenylalkylalkoxysilane, cycloalkylalkoxysilane, cycloalkylalkylalkoxysilane, (alkylamino) alkoxysilane, alkyl (alkylamino) alkoxysilane, alkylaminosilane, and the like can be mentioned.
  • organosilicon compounds selected from phenylalkoxysilane, alkylalkoxysilane, phenylalkylalkoxysilane, cycloalkylalkoxysilane, cycloalkylalkylalkoxysilane, (alkylamino) alkoxysilane, alkyl (alkylamino) alkoxysilane, alkylaminosilane, and the like can be mentioned.
  • one or more kinds selected from dicyclopentyl-bis-(ethylamino) silane, cyclopentylcyclohexyl-bis-(ethylamino) silane, bis-(perhydroisoquinolino) dimethoxysilane, diethylaminotrimethoxysilane, or diethylaminotriethoxysilane are more preferred.
  • a solid catalyst component for olefin polymerization obtained by the production method according to the present invention an organoaluminum compound represented by the general formula (II) and, if necessary, an external electron-donating compound may be contacted in the absence of olefins to prepare a catalyst for olefin polymerization, or as described below, a catalyst for olefin polymerization may be prepared by contacting (in a polymerization system) in the presence of olefins.
  • each component constituting the catalyst for olefin polymerization described above is arbitrary, for example, it is desirable to charge an organoaluminum compound represented by the above general formula (II) first into a polymerization system, and then charge and contact the above-mentioned external electrondonating compound, and then charge and contact the above-mentioned solid catalyst component for olefin polymerization.
  • an organoaluminum compound represented by the above general formula (II) first into a polymerization system, and then charge and contact the above-mentioned external electrondonating compound, and then charge and contact the above-mentioned solid catalyst component for olefin polymerization.
  • the contact ratio of each component is arbitrary so long as it does not affect the effect of the present invention, and is not particularly limited.
  • the contact amount of an organoaluminium compound expressed by the above general formula (II) per mol of titanium atom in the solid catalytic component for polymerization of olefins is preferably 1-2000 mol, and it is preferable to be 50-1000 mol.
  • the contact amount of the above-mentioned external electron-donating compound is preferably 0.002 to 10 mol, more preferably 0.01 to 2 mol, and still more preferably 0.01 to 0.5 mol per 1 mol of the above-mentioned organoaluminum compound.
  • the content of each of the solid catalyst component for olefin polymerization, the organoaluminum compound represented by the general formula (II), and the external electron-donating compound is preferably an amount corresponding to the contact amount of each of the above components.
  • a method for producing an olefin polymer according to the present invention is characterized in that polymerization of olefins is performed using a catalyst for olefin polymerization obtained by the production method according to the present invention.
  • polymerization of olefins may be homopolymerization or copolymerization with other a- olefins.
  • examples of the olefin to be polymerized include one or more kinds selected from ethylene, propylene, 1 -butene, 1 -pentene, 4-m ethyl- 1 -pentene, vinyl cyclohexane, and the like.
  • olefins one or more kinds selected from ethylene, propylene and 1 -butene are preferred, and propylene is more preferred.
  • olefins are propylene, they may be homopolymerization of propylene, but may be copolymerization with other a-olefins.
  • Examples of the olefin copolymerized with propylene include one or more kinds selected from ethylene, 1 -butene, 1 -pentene, 4-methyl-l -pentene, vinyl cyclohexane, and the like.
  • the method for producing an olefin polymer according to the present invention may be carried out in the presence or absence of an organic solvent.
  • an olefin monomer such as propylene can be used in any state of gas and liquid.
  • the polymerization temperature is preferably 200 °C or less, more preferably 100 °C or less
  • the polymerization pressure is preferably 10 MPa or less, and more preferably 5 MPa or less.
  • polymerization of olefins can be performed by any of a continuous polymerization method and a batch polymerization method.
  • the polymerization reaction may be carried out in one stage or may be carried out in two or more stages.
  • the olefins are polymerized using the catalyst for olefin polymerization obtained by the production method according to the present invention (also referred to as the present polymerization)
  • the contact order of each component constituting the catalyst for olefin polymerization and the monomer (olefins) described above is arbitrary, but preferably, an organoaluminum compound is first charged into a prepolymerization system set in an inert gas atmosphere or an olefin gas atmosphere, and then a solid catalyst component for olefin polymerization obtained by the production method according to the present invention is charged and contacted, and then an olefin such as propylene is brought into contact alone or a mixture of one or more of olefins such as propylene and other olefins is preferably brought into contact.
  • an organoaluminum compound is first charged into a prepolymerization system set in an inert gas atmosphere or an olefin gas atmosphere, and then a solid catalyst component for olefin polymerization obtained by the production method according to the present invention is charged and contacted, and then an olefin such as propylene is brought into contact alone or
  • an organoaluminum compound is first charged into a pre-polymerization system set in an inert gas atmosphere or an olefin gas atmosphere, and then an external electron-donating compound is charged and contacted, and further, a solid catalyst component for olefin polymerization obtained by the manufacturing method according to the present invention is brought into contact, and then an olefin such as propylene is brought into contact alone or a mixture of one or more of olefins such as propylene and other olefins is brought into contact.
  • examples of the polymerization method include a slurry polymerization method using a solvent of an inert hydrocarbon compound such as cyclohexane or heptane, a bulk polymerization method using a solvent such as liquefied propylene, and a gas phase polymerization method substantially without using a solvent, and a bulk polymerization method or a gas phase polymerization method is preferred.
  • propylene-ethylene block copolymerization is typical in which a random copolymerization in which propylene and a small amount of ethylene are polymerized in one stage and a homopolymerization of propylene is carried out in a first stage (first polymerization tank), and a copolymerization of propylene and other a-olefins such as ethylene is carried out in a second stage (second polymerization tank) or a multistage (multistage polymerization tank) further, and a block copolymerization of propylene and other a-olefins is preferred.
  • the block copolymer obtained by the block copolymerization is a polymer containing segments in which two or more kinds of monomer compositions are continuously changed, and refers to a polymer in which two or more kinds of polymer chains (segments) having different primary structures such as monomer species, comonomer species, comonomer composition, comonomer content, comonomer sequence, and stereoregularity are connected in one molecular chain.
  • a block copolymerization reaction of propylene with another a-olefin is usually carried out by bringing propylene alone or propylene into contact with a small amount of a a-olefin (ethylene or the like) in the presence of a catalyst for olefin polymerization obtained by the production method according to the present invention, and then bringing the propylene into contact with a a-olefin (ethylene or the like) at a later stage.
  • the polymerization reaction of the preceding stage may be repeatedly performed a plurality of times, or the polymerization reaction of the subsequent stage described above may be repeatedly performed by a multiple stage reaction multiple times.
  • the series copolymerization reaction of propylene with other a-olefins is carried out by adjusting the polymerization temperature and time so that the proportion of the polypropylene portion (occupying the finally obtained copolymer) is 20 to 90% by mass in the previous stage, and then, in the subsequent stage, propylene and ethylene or other a-olefin are introduced, and the rubber portion ratio such as ethylene-propylene rubber (EPR) is preferably 10 to 80% by mass.
  • EPR ethylene-propylene rubber
  • the polymerization temperature at the front stage and the rear stage is both preferably 200 °C or less, more preferably 100 °C or less, still more preferably 75 to 80 °C, the polymerization pressure is preferably 10 MPa or less, more preferably 6 MPa or less, and still more preferably 5 MPa or less.
  • any of a continuous polymerization method and a batch polymerization method can be employed, and the polymerization reaction may be performed in one stage or in two or more stages.
  • the polymerization time (residence time in the reactor) is 1 minutes to 5 hours at each polymerization stage of each of the polymerization stages at the preceding stage or the subsequent stage, or even at the time of continuous polymerization.
  • Examples of the polymerization method include a slurry polymerization method using a solvent of an inert hydrocarbon compound such as cyclohexane or heptane, a bulk polymerization method using a solvent such as liquefied propylene, and a gas phase polymerization method substantially without using a solvent, and a bulk polymerization method or a gas phase polymerization method is suitable, and a reaction at a later stage is preferably a gas phase polymerization reaction for the purpose of suppressing elution of EPR from polypropylene particles in general.
  • a method for conveniently producing a catalyst for polymerization of olefins that has a polymerization activity equivalent to or higher than that of the case using a solid catalyst component in which a styrenic internal donor compound is used, and that can produce a polypropylene with excellent stereoregularity.
  • the polypropylene can be made by a process for polymerization of olefins that is carried out by using the catalyst as described herein for polymerization of olefins.
  • an objective polymer of olefins can be produced by carrying out homopolymerization or copolymerization of olefins by using the catalyst for polymerization of olefins.
  • copolymerization with another olefin may also be carried out.
  • olefins to be copolymerized examples include ethylene, 1- butene, 1 -pentene, 4-methyl-l -pentene and vinyl cyclohexane, and one of them or two or more of them may be used.
  • the olefin one or two or more selected from ethylene and 1 -butene are preferable.
  • the amount of the organoaluminum compounds constituting the catalyst for polymerization of olefins described above is preferably 1 to 2000 mol, and more preferably 50 to 1000 mol per mol of titanium atoms in the contact product for polymerization of olefins.
  • the amount of the external electron donor constituting the catalyst for polymerization of olefins described above is preferably 0.002 to 10 mol, more preferably 0.01 to 2 mol of, and still more preferably 0.01 to 0.5 mol per mol of the organoaluminum compounds.
  • the method for producing a polypropylene it is preferable that, while the contact product for polymerization of olefins the organoaluminum compounds represented by the general formula (3) and the external electron donor optionally used are brought into contact in the presence of olefins (in the polymerization system), thereby preparing a contact product (a catalyst for polymerization of olefins), the olefin be polymerized.
  • the organoaluminum compounds be charged into the polymerization system at first, and then, the contact product for polymerization of olefins be charged.
  • organoaluminum compounds be charged into the polymerization system at first, the external electron donor be charged next, and then, the contact product for polymerization of olefins be charged.
  • the method for producing polypropylene can be performed in the presence of or in the absence of an organic solvent.
  • olefin monomers such as propylene can be used either in a gaseous state or in a liquid state.
  • the polymerization temperature is preferably 200°C or lower, and more preferably 100°C or lower.
  • the polymerization pressure is preferably 10 MPa or less, and more preferably 5 MPa or less.
  • the method for producing polypropylene can be either continuous polymerization method or batch polymerization method.
  • the polymerization reaction may be carried out in one stage or may be carried out in two or more stages.
  • the order of contact of each component constituting the catalyst for polymerization of olefins described above and a monomer (olefin) is arbitrary, but preferably, it is preferable that the organoaluminum compounds be charged at first into the preliminary polymerization system that has been set to an inert gas atmosphere or olefins gas atmosphere, the contact product for polymerization of olefins be charged next and brought into contact, and then olefins such as propylene be brought into contact alone, or a mixture of olefins such as propylene and one or two or more of other olefins be brought into contact.
  • olefins such as propylene be brought into contact alone, or a mixture of olefins such as propylene and one or two or more of other olefins be brought into contact.
  • the organoaluminum compounds be charged at first into the preliminary polymerization system that has been set to an inert gas atmosphere or olefins gas atmosphere, the external electron donor be charged next and brought into contact, the contact product for polymerization of olefins be further brought into contact, and then olefins such as propylene be brought into contact alone, or a mixture of olefins such as propylene and one or two or more of other olefins be brought into contact.
  • the production is carried out through multistage polymerization in two or more stages, and normally, the copolymer can be obtained by polymerizing propylene using the catalyst for polymerization at the first stage and copolymerizing ethylene and propylene at the second stage.
  • an a-olefin other than propylene can be polymerized together or alone at the second stage or at the time of subsequent polymerization. Examples of the a-olefin include ethylene, 1 -butene, 4-methyl-l -pentene, vinyl cyclohexane, 1 -hexene and 1 -octene.
  • polymerization process to make the inventive impact copolymers is carried out by adjusting the polymerization temperature and residence time such that the proportion of the polypropylene matrix phase is within a range from 5, or 10, or 20 wt% to 80, or 90, or 95 wt%, and then, at the second stage, ethylene and propylene or another a-olefin are introduced and polymerization is carried out such that the proportion of the EPR dispersed phase is within a range from 5, or 10, or 20 wt% to 80, or 90 wt%.
  • the impact copolymers comprise (or consist essentially of) within a range from 5 wt% to 40 wt% EPR, and within a range from 60 wt% to 95 wt% polypropylene.
  • the stage to produce the polypropylene can take place in two or more series reactors, each run under identical conditions (e.g., level of hydrogen, comonomer, temperature, identity or level of external electron donor(s), etc.) to make the same type of polypropylene, or under different conditions to make a polypropylene that is bimodal in some feature such as molecular weight or comonomer content.
  • the first stage to produce the polypropylene matrix phase takes place in a slurry polymerization process
  • the second stage to produce the EPR finely dispersed within the matrix phase takes place in one or more gas phase reactors.
  • the polymerization temperatures at the first stage and the second stage are both preferably 200°C or lower, and more preferably 100°C or lower.
  • the polymerization pressure is preferably 10 MPa or less, and more preferably 5 MPa or less.
  • the polymerization time at each polymerization stage, or the residence time in the case of continuous polymerization is normally 1 minute to 5 hours.
  • Examples of the polymerization method include a slurry polymerization method in which a solvent of an inert hydrocarbon compound such as cyclohexane and heptane is used, a bulk polymerization method in which a solvent such as liquefied propylene is used, and a gas phase polymerization method in which a solvent is substantially not used.
  • Examples of the preferable polymerization method may include the bulk polymerization method (especially slurry polymerization) and the gas phase polymerization method.
  • Hydrogen can be added to one or more of the slurry loop reactors that produce the polypropylene to control its properties.
  • hydrogen can also (or alternatively) be added to the gas phase reactor that produce the EPR portion of the impact copolymer, or both.
  • hydrogen added to the slurry loop reactors can be carried over to the gas phase reactors in whole or in part, and can be regulated by removing excess hydrogen within or prior to entering the gas phase reactor using a mechanical separator such as by a cycling transfer system or using a chemical agent such as titanocene catalyst (see e.g., US 10,544,237).
  • hydrogen can be added to the gas phase reactors to control the molecular weight of the EPR.
  • the molecular weight e.g., as evidenced by the melt flow rate or intrinsic viscosity
  • the molecular weight of the polypropylene and EPR components of the impact copolymer can be varied.
  • the melt flow rate of the polypropylene portion of the impact copolymer can vary from 5, or 10, or 20, or 50, or 100 g/10 min or more, preferably within a range from 5, or 10, or 20, or 50, or 100 g/ 10 min to 200, or 250, or 300, or 350, or 400, or 450, or 500, or 800, or 1000 g/10 min or more.
  • the EPR portion of the impact copolymer can have an intrinsic viscosity within a range from 2, or 2.5, or 3 dL/g to 6, or 7, or 8, or 9, or 10, or 12 dL/g or more. Any molecular weight combination of polypropylene and EPR can be combined to make an impact copolymer.
  • unfinished polypropylene granules which could include homopolymer, random copolymer, and/or impact copolymers, leaves the final stage of reaction in a granular form still containing light hydrocarbons, primarily the propylene and sometimes ethylene or other co- or termonomers used to produce the polymer, either trapped within the granules or in the gas phase surrounding the granules.
  • the granules are routed through one or more low-pressure (generally 2 barg or less) separation vessels to remove as much of this hydrocarbon as possible.
  • small amount of light hydrocarbons such as monomers, as well as smaller quantities of heavier oligomers remain trapped in the polymer and surrounding vapor space.
  • the contact amount of Compound A with respect to the above diethoxymagnesium was 1/10 by mass (weight) ratio.
  • stirring was provided, and a total amount of the above pre-contact (diethoxymagnesium containing liquid) was added into a mixed solution of 50 mL of toluene and 40 mL of titanium tetrachloride, which was preloaded into a round bottom flask having a volume of 500 mL replaced with nitrogen gas, and served as a suspension.
  • reaction product 20 mL of titanium tetrachloride and 100 mL of toluene were added, and the temperature was raised to 100 °C, and a treatment for reacting for 15 minutes was performed 2 times, followed by washing with 150 mL of n-heptane at 40 °C 6 times to obtain a solid catalyst component.
  • the content of titanium atoms in the obtained solid catalyst component was 2.1% by mass, the content of di-n-propyl phthalate was 13.5% by mass, and the terminal substituent of the above styrene-based copolymer was not determined.
  • a propylene homopolymer (PP) was obtained by charging 1.4 L of liquefied propylene and 67 mmol of hydrogen gas into an autoclave with a stirrer containing the above catalyst for olefin polymerization, preliminary polymerization was carried out at 20 °C for 5 minutes, and then the temperature was raised, and a polymerization reaction was carried out at 70 °C for 60 minutes.
  • a polymer (PP) of 40 g and a p-xylene of 200 mL were charged, and the external temperature was set at a temperature higher than or equal to the boiling point of xylene (150 °C), whereby the polymer was dissolved over a period of 2 hours while maintaining the temperature of p-xylene inside the flask under the boiling point (137 to 138 °C).
  • a solid catalyst component was obtained in the same manner as in Example 1, except that the above-mentioned terminal-substituted styrene-based copolymer was not added. [00188] Note that the content of titanium atoms in the obtained solid catalyst component was 2.0% by mass, and the di-n-propyl phthalate content was 13.8% by mass.
  • a catalyst for olefin polymerization was prepared in the same manner as in Example 1, except that the obtained solid catalyst component was used, and then homopolymerization of propylene was performed.
  • a solid catalyst component was obtained in the same manner as in Example 1, except that a mixture of 4 mL of di-n-propyl phthalate and 4 mL of 2-isopropyl-2-isopentyl- 1,3-dimethoxypropane was added instead of 8 mL of di-n-propyl phthalate.
  • the content of titanium atoms in the obtained solid catalyst component was 1.5% by mass
  • the 2-isopropyl-2-isopentyl-l,3-dimethoxypropane content was 6.7% by mass
  • the di-n-propyl phthalate content was 7.6% by mass
  • the terminal substituent of the above styrene-based copolymer was not contained.
  • a catalyst for olefin polymerization was prepared in the same manner as in Example 1, except that the obtained solid catalyst component was used, and then homopolymerization of propylene was performed.
  • a solid catalyst component was obtained in the same manner as in Example 2, except that the above-mentioned terminal-substituted styrene-based copolymer was not added. [00196] Note that the content of titanium atoms in the obtained solid catalyst component was 1.4% by mass, the 2-isopropyl-2-isopentyl-l,3-dimethoxypropane content was 7.6% by mass, and the di-n-propyl phthalate content was 8.7% by mass.
  • a catalyst for olefin polymerization was prepared in the same manner as in Example 1, except that the obtained solid catalyst component was used, and then homopolymerization of propylene was performed.
  • a solid catalyst component was obtained in the same manner as in Example 1, except that Compound B (HG-252TM manufactured by Kuraray Co., Ltd.) 20 g consisting of a styrene-based copolymer having a styrene-based copolymer having a styrene content of 28% by mass, one end of which was not substituted with a functional group, was added instead of the above-mentioned terminal-substituted styrene-based copolymer.
  • Compound B HG-252TM manufactured by Kuraray Co., Ltd.
  • a catalyst for olefin polymerization was prepared in the same manner as in Example 1, except that the obtained solid catalyst component was used, and then homopolymerization of propylene was performed.
  • a solid catalyst component was obtained in the same manner as in Example 2, except that 0.2 mL of ethyl benzoate was added instead of the above-mentioned terminal- substituted styrene-based copolymer.
  • the content of titanium atoms in the obtained solid catalyst component was 1.5% by mass
  • the 2-isopropyl-2-isopentyl-l,3-dimethoxypropane content was 6.9% by mass
  • the di-n-propyl phthalate content was 8.0% by mass
  • the ethyl benzoate was 0.1% by mass.
  • a catalyst for olefin polymerization was prepared in the same manner as in Example 1, except that the obtained solid catalyst component was used, and then homopolymerization of propylene was performed.
  • Compound A is Septon HG-252TM, wherein one end is substituted with a benzoic acid group (CeEECOO-);
  • Compound B is Septon HG-252TM;
  • Compound C is Ethyl benzoate;
  • Donor A is di-n-propyl phthalate; and
  • Donor B is 2-isopropyl-2-isopentyl-l,3- dimethoxypropane.
  • Example 1 and Example 2 a solid catalyst component produced by contacting one or more internal electron-donating compounds and a titanium halogen compound with each other after previously contacting a magnesium compound with a specific compound is used, so that the obtained solid catalyst component exhibits excellent polymerization activity when subjected to polymerization of olefins, and the stereoregularity of the obtained polymer is also highly maintained.
  • the present invention it is possible to provide a method for producing a solid catalyst component for olefin polymerization capable of producing a polymer having excellent polymerization activity and excellent stereospecificity, a method for producing a solid catalyst for olefin polymerization, and a method for producing an olefin polymer.
  • the phrase “consisting essentially of’ for a composition of matter means that there may be up to 1, or 2, or 3, or 4 wt%, by weight of the polypropylene, of additives such as antioxidants, cross-linking agents, peroxide agents, alkyl radical scavengers, acid neutralizers, nucleating agents, fillers, colorants, polymeric compatibilizers (elastomers, plastomers, LDPE, etc.), hydrocarbon resins, and/or other such additives as are known in the art.
  • additives such as antioxidants, cross-linking agents, peroxide agents, alkyl radical scavengers, acid neutralizers, nucleating agents, fillers, colorants, polymeric compatibilizers (elastomers, plastomers, LDPE, etc.), hydrocarbon resins, and/or other such additives as are known in the art.

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Abstract

L'invention concerne un polypropylène présentant une teneur en substances solubles de p-xylène (XS) égale ou inférieure à 1,5 % en poids par rapport au poids du polypropylène, le polypropylène étant obtenu par combinaison de propylène avec un catalyseur solide comprenant un composé de magnésium ayant été mis en contact avec un composé styrénique. Dans n'importe quel mode de réalisation, le composé de magnésium et le composé styrénique sont mis en contact l'un avec l'autre pour obtenir un matériau de contact préliminaire, puis le matériau de contact préliminaire, un composé halogéné de titane, et un ou plusieurs composés donneurs d'électrons internes sont mis en contact les uns avec les autres pour obtenir un composant de catalyseur solide qui est mis en contact avec le propylène.
PCT/US2021/071535 2020-10-30 2021-09-21 Polypropylène produit à l'aide de donneurs d'électrons internes styréniques modifiés WO2022094508A1 (fr)

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JPH0374341A (ja) 1989-08-16 1991-03-28 Korukooto Eng Kk 球形で粒度分布の狭いマグネシウムアルコラートの合成方法
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JP2001503079A (ja) 1996-09-19 2001-03-06 ボレアリス ポリマーズ オイ α―オレフィンの製造方法、該製造に使用される触媒、およびその調製
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WO2002016480A2 (fr) * 2000-08-22 2002-02-28 Exxonmobil Chemical Patents Inc. Films de polypropylene
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