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WO1980001485A1 - Procede de production d'un polymere d'olefine - Google Patents

Procede de production d'un polymere d'olefine Download PDF

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Publication number
WO1980001485A1
WO1980001485A1 PCT/JP1980/000006 JP8000006W WO8001485A1 WO 1980001485 A1 WO1980001485 A1 WO 1980001485A1 JP 8000006 W JP8000006 W JP 8000006W WO 8001485 A1 WO8001485 A1 WO 8001485A1
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WO
WIPO (PCT)
Prior art keywords
compound
compounds
hafnium
vanadium
organic
Prior art date
Application number
PCT/JP1980/000006
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English (en)
Japanese (ja)
Inventor
T Tanaka
E Tanaka
Original Assignee
Mitsubishi Chem Ind
T Tanaka
E Tanaka
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from JP430779A external-priority patent/JPS5598205A/ja
Priority claimed from JP1128779A external-priority patent/JPS55104302A/ja
Priority claimed from JP4322879A external-priority patent/JPS55135108A/ja
Application filed by Mitsubishi Chem Ind, T Tanaka, E Tanaka filed Critical Mitsubishi Chem Ind
Publication of WO1980001485A1 publication Critical patent/WO1980001485A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond

Definitions

  • the present invention relates to a method for producing an olefin polymer. More specifically, new catalysts or vanadium and vanadium compounds, including vanadium and vanadium compounds, have been introduced. Including new
  • Catalyst systems have been proposed. This catalyst system has a very high catalytic activity, and the resulting polymer has a narrow particle size distribution and a high bulk density. 4 (7
  • the polymer obtained by this catalyst system had a narrow molecular weight distribution and was suitable for injection molding, but it was suitable for extrusion molding or pro-molding. However, it was not suitable for applications requiring a large space.
  • multi-step polymerization and polymer blends are widely used as a method for producing a polymer with a wide molecular weight distribution using a catalyst having a high polymerization activity but a narrow molecular weight distribution.
  • Methods have been proposed. However, each of these methods requires a large and complicated apparatus, and requires a high degree of technology to adjust the molecular weight ratio and mixing ratio of the polymer to be mixed.
  • the catalyst may be a combination of a catalyst component for producing a polymer having a relatively high molecular weight and a catalyst component for producing a relatively low molecular weight which is usually used.
  • the present inventors have also used a catalyst in which a titanium compound, a vanadimidic compound, and a zirconium compound are combined, as described in Japanese Patent Application No. 197 Therefore, a method for producing a polymer having a wide molecular weight distribution was proposed.
  • the present inventors have further developed a polymer having an extremely wide molecular weight distribution by using a combination of a vanadium-hafnium-based catalyst and a titanium-based catalyst.
  • a method that can be produced based on the polymerization activity was found. According to this method, the amount ratio of the titanium compound, the vanadium compound, and the hafnimium conjugate in the catalyst is changed]), It describes the molecular weight distribution of the polymer obtained by one catalyst system.
  • the gist of the present invention is
  • vanadium compounds selected from vanadium halogen compounds and organic oxygenated compounds (a) vanadium compounds selected from vanadium halogen compounds and organic oxygenated compounds; and ( ⁇ ) halogen halide compounds A solid catalyst component obtained by mixing and reacting a hafnium compound selected from a product and an organic oxygenated compound.
  • a vanadium compound selected from the group consisting of a vanadium nitrogen compound and an organic oxygenated compound
  • the titanium compound, vanadium dimethyl compound and hafnium compound used for the preparation of the solid catalyst component in the present invention contain the organic oxygen of each metal. Selected from halogenated compounds and halogenated compounds.
  • organic oxygenated compound of metal as used herein means that a molecule has at least / at least / metal-oxygen-organic bond in this order.
  • OVP1 Means a compound. And / molecule warm! ) At least / piece
  • a hydrocarbon group such as an alkyl group, a cycloalkyl group, an aryl group, an aryl group, an aryl group, or an aryl group.
  • Alkyl groups and the like are used.
  • a metal halogen compound is a compound that is at least /
  • At least one metal-halogen bond is provided.
  • Nitrogen, chlorine, bromine, and iodine can be used. This
  • X represents the halogen atom described above, and Me is titanium, vanadium, or hafnium.
  • a is d? ⁇ a ⁇ /, 3 ⁇ 4clf ⁇ 0 ⁇ ⁇ b ⁇ ⁇ ⁇ c ⁇ ⁇ DL ⁇ '> ⁇ , and ax ⁇ 2 + ti + c is equal to the valence of each metal. Is an integer of /
  • a server Na di U beam compounds have the general formula [VOa / i (ORi) TD 1 X 1 c 1 d 1 (where, a 1,, c 1 each click ⁇ a 1 ⁇ /, and ⁇
  • / represents a hydrocarbon group, for example, an alkyl group, a cycloalkyl group, an aryl group, an alkylaryl group or an arylalkyl group.
  • X 1 represents a halogen atom.
  • Value or price of Panamax di ⁇ -time I arsenide compound represented by) is a good or arbitrariness, Chi jar of this, the general formula VO (0R 2) a2 ⁇ _ a2 ( in the formula, a? Gu ⁇ a 2 ⁇ And R2 and ⁇ 2 are the same as Rl and ⁇ 1 .)
  • VBr 4 VC 4 or the like is mentioned, et al. Are.
  • Complexes with various Lewis bases such as VBr ⁇ .2 (butyl ether) may be used.
  • Compounds containing several different organic groups or halogen atoms can be used, and some different vanadium compounds can be used.
  • the hafnium compound is represented by the general formula [HfOa 3 (OR 3 ) 3 ⁇ 4 3 X 3 c 3 d 3 (wherein a 3 3 ⁇ 4 3 c 3 lf ⁇ 0 ⁇ 3 ⁇ / 0 ⁇ D 3 ⁇ V-,
  • R 3 X 3 is the same as Ri X 1 . )
  • a multivalent hafnium compound represented by is preferred,
  • R 3 X 3 is Ru same der to R 1 _ X 1.
  • Halogen particularly preferred are the tetravalent hafni umui dani compounds.
  • a Le co hexa Lee de e.g. Hf (0- nC 4 H 9) 4
  • Tetrahalide such as HfC, HfBr ⁇ ;
  • HfOG 2 Oral compounds such as HfOG 2. (This compound is usually
  • a solid catalyst component is prepared by mixing and reacting
  • both compounds should be in the presence or absence of diluent
  • WIPO WIPO
  • the pressure condition is not particularly limited, but may be around normal pressure.
  • the two compounds are mixed, but the two compounds may be reacted simultaneously with or after the mixing.
  • One small rather as also of and during contact the compound is rather was favored and the this that a liquid, one least for the well of both compounds for this has organic oxygen groups i.e. ORi, the OR 2 or OR 3 / FOB
  • it is a compound. Therefore, when both compounds are solid, it is preferable to use a diluent so as to dissolve at least one of them.
  • the resulting mixture or reaction product may be used as it is as a solid catalyst component, or a solid can be separated from the reaction product to be a solid catalyst component.
  • a liquid substance is used as a diluent
  • the diluent is removed to precipitate a solid, and the obtained solid is separated to obtain a solid catalyst component.
  • both compounds may be mixed or reacted to produce a solid catalyst component and, at the same time, combined with an organic aluminum compound component to provide a catalyst for olefin polymerization. it can.
  • any of the usual inert hydrocarbon solvents can be used, but the number of carbon atoms is from ⁇ to.
  • alkanes cycloalkanes and aromatic hydrocarbons
  • examples of these compounds include hexane, hebutane, hexopen hexan, benzene, tonolene, and xylene.
  • polar solvents for example, ethylene chloride
  • Examples include tellurium and pyridin.
  • Halogen-containing anodized aluminum such as luminum monochloride
  • Silicon compounds such as silicon tetrachloride and tin tetrachloride.
  • X 4 represents a halogen atom
  • II represents o ⁇ n ⁇ J
  • the compound represented by) which represents the number of) is particularly preferred.
  • X 4 are the same as those exemplified earlier for R 1 and X 1
  • n is the number of, /, /., ⁇ 2
  • a liquid material is prepared by mixing and reacting the dime compound and the hafdium compound in the presence or absence of a diluent to prepare a liquid substance, and then halogenate the liquid substance.
  • Preferred is a method in which the catalyst is reacted and the solid catalyst component is separated from the reaction mixture.
  • the mixing or reaction of the vanadium compound and the hafnium munich compound is carried out as described above, and the mixture or reaction is necessary so that the reaction mixture becomes liquid.
  • the corresponding diluent is added.
  • a reaction is performed by adding a halogenating agent to the obtained liquid, and the reaction is carried out if the mixture obtained as described above is sufficiently liquid in the absence of a diluent.
  • an inert solvent an inert hydrocarbon solvent is usually used among those exemplified above as the diluent.
  • the polar solvent is distilled off under reduced pressure prior to the reaction with the halogenating agent. It may be removed by the above method, or the reaction with the halogenating agent may be carried out without removing it.
  • the reaction with the halogenating agent is carried out without the mixture of the vanadium munich compound and the hafnium compound to which the inert solvent has been added, or the reaction with the halogenating agent.
  • the reaction Preferably at room temperature to friendship2 C, more preferably at 0 ° C./s 0 C.
  • the reaction may be performed at a temperature of C, and a solid insoluble in an inert solvent is obtained. Is separated and washed with an inert solvent.
  • the second method for reacting the J component is as follows:
  • reaction conditions are the same as those described above.
  • the reaction is performed to prepare a solid catalyst component.
  • W1PO It is preferable to use a general formula Ti (on 6 ) a e zj_ a6 (where a 6 is a number that is q a6 ⁇ , and X 6 is the same as R ⁇ ⁇ above).
  • the tetravalent titanium compounds mentioned are particularly preferred. Bromine is the most preferred halodan atom. These compounds include alcoholic acid
  • Ti (0-nG 4 H 9 ) 3 Br, T (0 - n - CH 9) 3 include C like mosquitoes. These compounds and species s complex of Le y scan bases, for example, IBR 4 ⁇ 2 (Puchinore et one te le), using iBr 3 (0 -nC 4 H 9 ) ⁇ E chill ⁇ Se Te over preparative like You may. Compounds containing several different organic groups or halogen atoms can be used, and some different titanium compounds can be used.
  • the organic aluminum compound has a general formula
  • X 7 is Ru Ah at C B gain down atoms.
  • R 7 is
  • alkyl groups and alkyl groups are preferable to choose from alkyl groups and alkyl groups.
  • These compounds include A (C 2 H 5 ) 3 , AZ (0 2 H 5 ) 2 C ⁇ ,
  • the organic aluminum compound includes bromide.
  • Aluminum-dimethyl compounds are most preferred. Wrinkle, smell
  • the polymerization is carried out using the components in the presence of hydrogen in the polymerization reaction zone.
  • OV.PI "W.PO 2 preferably a hydrocarbon group of / to ⁇ , where m is
  • R 8 is preferably selected from an alkyl group, a cycloalkyl group, an aryl group, an aryl group, and an aryl group. .
  • the organic dibromide aluminum dibromide compounds in which m is / in the general formulas such as AA (C 2 H 5 ) Br 2 and A ⁇ (GH 3 ) Br 2 are shown. Use is preferred. Also, the use of several different organic aluminum compounds can result in the use of several different organic groups or organic aluminum compounds containing a halogen atom. It is also possible to use a My dagger. Aluminum trihalide and organic aluminum compounds can be used in combination. Among these, when a mixture of an organic aluminum dibromide compound and an organic aluminum dichloride compound is used, a catalyst having a special characteristic can be obtained. You.
  • the molecular weight distribution is too wide, it may cause unstable flow of the melt during melt molding.
  • irregular patterns may be formed on the skin of the molded product.
  • the olefin polymer obtained by using the catalyst produced by using the above mixture has a high molecular weight distribution and a high extrudability, but does not have a high meltability. Stable flow and success e 'K'
  • the mixing ratio of the two is in the range of /// 0 to / -0 by the atomic ratio of B i C.
  • the components may be added and mixed in an arbitrary order and reacted.
  • a titanium compound, a vanadium compound, and a hafnium compound are mixed, and an organic aluminum compound is added to the obtained mixture or the reaction product to be reacted.
  • a titanium compound, a vanadium compound, and a hafnium compound are added and mixed.
  • the order of addition of each compound can be arbitrarily selected.
  • a reaction may occur between the compounds.
  • Mixing can be performed in the presence or absence of a diluent, but it is preferred that the mixture be liquid (even a slurry).
  • the mixture be liquid (even a slurry).
  • the arc Ru added diluent is a c diluent Shi preferred, conventional inert
  • all hydride solvents can be used, the use of alkanes having up to 2 carbon atoms, cyclopialkanes, and aromatic hydrocarbons is preferred.
  • OMP1 WiKJ New These compounds include hexan, heptane, cyclohexan benzene, xylene, -xylene and the like.
  • a polar solvent can be used. These solvents include, for example, ethylene dike mouth light, alcohols of carbon ⁇ / to cf, esters of carboxylate, ethers of ethers. , Pyridin and the like. The addition of titanium, vanadium, and hafnium may be carried out as a solution of the polar solvent and the inert hydrocarbon solvent described above.
  • the mixture or the reaction product of the titanium compound, vanadium compound and hafnium mulphide compound obtained as described above is reacted with the organic aluminum compound.
  • a solid catalyst component The reaction with the organic aluminum compound can be carried out with the mixture obtained as described above or the reaction-even if the product is sufficiently liquid in the absence of a diluent, it is inert. Preferably, it is performed in the presence of a solvent.
  • the inert solvent an inert hydrocarbon solvent is usually used among those exemplified above as the diluent.
  • the polar solvent may or may not be removed by distillation under reduced pressure or other methods prior to the reaction with the organic aluminum compound.
  • the reaction with the organic aluminum compound may be performed as it is.
  • the reaction with an organic aluminum compound is carried out by the addition of an inert solvent to a titanium compound, a vanadium munich compound or a hafnium compound.
  • the reaction may be carried out at a temperature of 0 ⁇ to / 0 C.
  • the second method involves vanadium compounds and
  • the lower organic aluminum compound was added to initiate the reaction.
  • the reaction is continued by adding a titanium compound.
  • the amount of each compound used is titanium compound and vanadium
  • the ratio, or u / t, is preferably u / t>
  • Gram equivalent Gram atom of element Z Defined by valence of element
  • the advantage is that it is particularly easy to produce a wide polymer.
  • the Panadium conjugate, the hafnium compound, the titanium compound, and the organic aluminum compound are reacted to prepare a solid catalyst component.
  • Some of the hafdium compounds may be replaced with zirconium compounds.
  • a zirconium compound a halogen compound or an organic oxygenated compound is used.
  • UO is there.
  • the tetravalent zirconium-myi conjugate represented by) is particularly preferred.
  • Halogen is preferably chlorine or bromine.
  • Al co key Size Lee de e.g. Zr (0-n- C 4 H 9) 4 Zr (OC 2 H 5) 4; full d Roh key Size Lee de example if Zr (OC 6 H 5) *;. Tel breath leaves La y de e.g.
  • Complexes with various Lewis bases, such as ZrC ⁇ 4 ⁇ o2 (ethynoleate acetate), may be used.
  • Compounds containing several different organic groups or halogen atoms Alternatively, a number of different zirconium munich compounds can be used.
  • the dose of each compound is determined by the atomic ratio of titanium, vanadium, zirconium, and platinum to each atom.
  • (Zr + Hf) ZTi ratio in the range of 0.2 ⁇ ( ⁇ + ⁇ / ⁇ ⁇ ⁇ ⁇ , (Ti + Zr + Hf) / VJ If 0.0 ⁇ ⁇ (Ti + Zr + Hf) / V ⁇ : /
  • the catalyst system has a wide molecular weight distribution, high extrudability, and causes abnormal flow during molding.
  • Formula ⁇ ⁇ (where r is the number of moles of the alkoxy group in the titanium compound, vanadium compound, zirconia compound, and hamphidic compound.
  • A; is a titanium compound.
  • the quantity ratio of hafnium to ginoleconium is preferably in terms of the atomic ratio of Grams. / ⁇ Zr / Hf ⁇ / h, more preferably h. It is desirable that 2 ⁇ Zr / Hf ⁇ ⁇ .
  • an organic aluminum compound used as a cocatalyst for example, a general formula (Wherein, R 11 represents an alkyl group, aryl or cycloalkyl group, X 11 represents a halogen atom, and represents the number of /).
  • Examples include the compounds described above.
  • the usage ratio of the hydrocarbon-insoluble solid catalyst component and the organic aluminum compound is usually the atomic ratio of ⁇ Z (V + Ti + Hf) .
  • the polymerization of the olefins is carried out using the catalyst system thus prepared, and the olefins used are ethylene, propylene and the like. , One-buten / one-year-old / one-year-old / etc. Also, these orifices can be mixed and copolymerized.
  • the polymerization reaction can be performed by either solution polymerization in an inert solvent or slurry polymerization, or gas-phase polymerization in the absence of a solvent! ) sell.
  • the inert solvent is usually supplied in the presence of an inert solvent by supplying the olefin or mixture of olefins while maintaining the temperature and pressure at a given level.
  • aliphatic hydrocarbons such as pentane, hexane, heptane, octane, and isooctane; cyclopentane; cyclohexene.
  • '' 'Aromatic' hydrocarbons and the like are used such as alicyclic hydrocarbons such as san, benzene, and toluene.
  • the polymerization reaction is usually performed at normal temperature to a temperature of 0 ° C and normal pressure.
  • the pressure is selected from the range of atmospheric pressure.
  • the effect of controlling the molecular weight by hydrogen is large, and a polymer having a desired molecular weight can be easily obtained.
  • the amount of hydrogen that must be present depends on the polymerization conditions and the desired molecular weight of the olefin polymer.
  • the advantage that the catalyst system has a high polymerization activity is obtained, and in addition, the vanadium-hafnium system catalyst has a high molecular weight orifice. It has the advantage that a polymer can be obtained, and a vanadium-hafnium-titanium catalyst has a titanic compound, a panadimidic compound, a hafnium compound and By changing the ratio of the components of the organic aluminum compound, the molecular weight distribution of the obtained polymer can be easily adjusted. -The advantage of easily producing a olefin polymer having excellent moldability in molding can be obtained. BEST MODE FOR CARRYING OUT THE INVENTION
  • the polymerization activity of the catalyst is as follows:
  • melt index is ASTM ⁇ D ⁇ / 23S- ⁇ 7T The value was measured at a load of / 2 and the load was expressed as Ml. Furthermore, the outflow ratio (hereinafter abbreviated as PR) as a measure of the molecular weight distribution shows the shear stress dependence of the melt viscosity. in to value, ASTM ⁇ D ⁇ / 23S- - .
  • Example / except that vanadium tetrachloride was not used at all, a solid catalyst component was obtained in the same manner as in Example /, and c was used as in Example // to obtain a solid catalyst component.
  • the polymerization activity K was / /.
  • Example 2/0. / 3 ⁇ 3. 1 ⁇ 4 0.0 / / Example ⁇ 9.3 / 1 ⁇ 4s-. /? 9 0.002
  • hafnium tetanolmalbutoxide and benzene were mixed respectively in the amounts shown in Table 2 to obtain a homogeneous solution. Then add the amount of ethyl alumi-zum dichloride in the form of a benzene solution of 0.0 mot / in the amount shown in Table 2 at ⁇ C, and add at ⁇ C / hr. followed by drying washed stirred c formed precipitate to Bruno Le Mas Le in hexa down
  • Example 2
  • the mixture was mixed with titanium tetramoxide, 0 mmo ⁇ , and mmo ⁇ . After mixing, 4 benzenes? After adding ⁇ to make a homogeneous solution, add 0 mmo of ethyl aluminum dichloride in 6 in the form of a benzene solution of 1 ⁇ 40.00 / 1, and in C, Stirred for hours. The resulting precipitate was washed with normal hexane and dried to obtain a catalyst powder. This powder //? Use the trisobutyl aluminum. mmoz, hydrogen pressure.
  • Ethylene was additionally introduced to maintain cA, and after 9 hours, the j9 polymerization was stopped by injecting ethanol.
  • Titanium Tetranol Molto Toxide, Natri Trinol Molto Toxide, Hafnium 'Tetranol Molto Toki The sides were mixed in the proportions shown in Table.
  • the resulting precipitate was washed with normal hexane and dried to obtain a catalyst powder.
  • Example 2 instead of the use of the etchant medium> / mmo] ?, the et al. A solid catalyst component was prepared in exactly the same manner as in Example c2 except that 0 mmox was used.
  • the results obtained are shown in Table 3.
  • the polymer obtained was as follows: 1-butene / 0-unit / ethylene-butene-1 / monomer-containing copolymer there were.
  • Titanium trichloride Norema meltone Toxide 0 mmo, Nozil monochloride Renox malt Toxide «2 mmo, tetrasalt The mixture was mixed to prepare a homogeneous solution. Next, at 0 C, reduce the amount of triethylamine / 0 mmo to ⁇ 0.0.
  • the ethyl aluminium dibromide was 77 mmo
  • the et al.real niobium dibromide / ⁇ j * i7 ino and ethyl almiloid A solid catalyst component was prepared and polymerization was carried out in the same manner as in Example ⁇ 2 ⁇ except that a mixture with dimethyl chloride (7 mmo ⁇ ) was used.
  • Titanium lanthanum toxin 2 mm mmo and ⁇ ⁇ ⁇ ⁇ fl fl Mixed with 2 mm mmo, then add zirconium tetrachloride mmo, and then add the final tetrachloride / mmo instantaneously. And added. After the addition, the mixture was stirred for 2 hours with C to obtain a uniform liquid. Benzene J 3 ⁇ is applied to this homogeneous liquid to form a benzene solution, and after heating to C, ethyl alminium dibromide o2 cf 6 mmo ⁇ was added in the form of a volumetric benzene solution and stirred at C / hr.
  • Example J the amount of Hafni-Mich compound was calculated as / s-- , ⁇ ⁇ : ' ⁇ mmo, ⁇ ⁇ / ⁇ o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o
  • the amount of the zirconium tyride is 0 mmoz, the amount of the no and the total zimudium is 0 mmoz, and the amount of ethyl alminium dipromide is 2 ?
  • the autocatalyst was prepared with a nonaluminous hexanox / 0 JL], and the solid catalyst component was charged with / 2 ⁇ .
  • Polymerization was performed in exactly the same manner as in Example " ⁇ " except that the molar ratio of ethylene to butene-1 / in the gas phase was /. ⁇ moz ⁇ on average.
  • the ethylene / butene / copolymer was obtained and the polymerization activity K was / 660.
  • the amount of the dissolving compound is / mo
  • the amount of the nodifying compound is / mmo
  • the amount of the ethyl aluminium dibromide is 2 1 ⁇ 4 0 mmo ⁇
  • the method of the present invention is particularly useful as a method for producing a polyolefin for extrusion molding or a single molding process, particularly for polyethylene. is there.

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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)

Abstract

Un procede de production d'une polyolefine ayant une grande activite de polymerisation et un poids moleculaire eleve ou une polyolefine, en particulier du polyethylene, ayant un poids moleculaire largement distribue et se pretant a l'extrusion ou le moulage par soufflage, consiste a polymeriser une olefine telle que de l'ethylene en utilisant un systeme catalyseur comprenant un compose organique d'aluminium et un catalyseur solide obtenu par melange ou par reaction de composes oxygenes organiques ou d'halogenures de metaux tels que (a) du vanadium (b) de l'hafnium, ou un catalyseur solide obtenu par melange et reaction de composes oxygenes organiques ou d'halogenures de metaux tels que (A) du vanadium, (B) de l'hafnium et (c) du titane avec (D) un compose d'aluminium organique.
PCT/JP1980/000006 1979-01-18 1980-01-17 Procede de production d'un polymere d'olefine WO1980001485A1 (fr)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
JP430779A JPS5598205A (en) 1979-01-18 1979-01-18 Catalyst for olefin polymerization
JP79/4307 1979-01-18
JP1128779A JPS55104302A (en) 1979-02-02 1979-02-02 Production of olefin polymer
JP4322879A JPS55135108A (en) 1979-04-10 1979-04-10 Production of olefin polymer

Publications (1)

Publication Number Publication Date
WO1980001485A1 true WO1980001485A1 (fr) 1980-07-24

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0019637B1 (fr) * 1978-08-09 1983-06-08 Mitsubishi Kasei Corporation Procede de production de polymere d'olefines

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS512790A (en) * 1974-06-27 1976-01-10 Mitsubishi Chem Ind Orefuinno jugohoho
BE840378A (fr) * 1975-04-14 1976-10-05 Procede pour la polymerisation des olefines
JPS5239713B2 (fr) * 1974-10-04 1977-10-06
JPS5239714B2 (fr) * 1974-10-18 1977-10-06

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS512790A (en) * 1974-06-27 1976-01-10 Mitsubishi Chem Ind Orefuinno jugohoho
JPS5239713B2 (fr) * 1974-10-04 1977-10-06
JPS5239714B2 (fr) * 1974-10-18 1977-10-06
BE840378A (fr) * 1975-04-14 1976-10-05 Procede pour la polymerisation des olefines

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0019637B1 (fr) * 1978-08-09 1983-06-08 Mitsubishi Kasei Corporation Procede de production de polymere d'olefines

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