WO2009005074A1 - Composant catalytique solide pour la polymérisation des oléfines, son procédé de fabrication, catalyseur et procédé de fabrication d'un polymère d'oléfine à l'aide du catalyseur - Google Patents

Composant catalytique solide pour la polymérisation des oléfines, son procédé de fabrication, catalyseur et procédé de fabrication d'un polymère d'oléfine à l'aide du catalyseur Download PDF

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WO2009005074A1
WO2009005074A1 PCT/JP2008/061933 JP2008061933W WO2009005074A1 WO 2009005074 A1 WO2009005074 A1 WO 2009005074A1 JP 2008061933 W JP2008061933 W JP 2008061933W WO 2009005074 A1 WO2009005074 A1 WO 2009005074A1
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component
solid catalyst
catalyst component
compound
halogen
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PCT/JP2008/061933
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English (en)
Japanese (ja)
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Hidetoshi Umebayashi
Kenji Saito
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Toho Titanium Co., Ltd
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Priority to JP2009521643A priority Critical patent/JPWO2009005074A1/ja
Publication of WO2009005074A1 publication Critical patent/WO2009005074A1/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 solid catalyst component for polymerizing olefins capable of obtaining an olefin polymer in high yield, a production method and a catalyst thereof, and a method for producing a polymer of olefins.
  • olefins in the polymerization of olefins, it comprises magnesium, titanium, halogen, and a solid catalyst component containing an electron-donating compound as an optional component, an organoaluminum compound, and an electron-donating compound such as an organic cage compound as an optional component.
  • a solid catalyst component containing an electron-donating compound as an optional component, an organoaluminum compound, and an electron-donating compound such as an organic cage compound as an optional component.
  • Patent Document 1 Japanese Examined Patent Publication No. SHO 4 7-4 16 6 6 discloses a solid catalyst component composed of a halogenated titanium compound and an active magnesium halogen compound, and an organoaluminum compound.
  • a method for polymerizing olefins using a catalyst composed of a combination has been proposed.
  • a method for producing a solid catalyst component for polymerizing olefins by co-grinding magnesium halide and titanium halide was shown. Based on this method, various studies have been made on catalyst production methods using pulverization, and many proposals have been made.
  • Patent Document 2 Japanese Patent Laid-Open No. SHO 50-0 6 4 3 8 1
  • a catalyst comprising a combination of a solid catalyst component obtained by supporting titanium halide on a solid support obtained by co-powdering magnesium halide and aluminum alkoxide, and an organic aluminum compound.
  • a method of polymerizing Although it is an effective method, it is not satisfactory for obtaining a polymer in a high yield, and further improvement has been desired.
  • the means of pulverization used in the above prior art is simple, and is very effective from the viewpoint that there are few wastes such as by-products and unreacted materials. There was a limit in terms of further improving the performance. For this reason, in recent years, studies on methods for preparing catalysts by reacting in solution have become the mainstream.
  • Patent Document 3 Japanese Patent Publication No. Sho 4 6-3 4 0 92 2
  • a halogenated titanium compound containing water or alcohol is reacted with a titanium halide compound.
  • a method of polymerizing olefin using a catalyst comprising a combination of the obtained solid catalyst component and an organoaluminum compound It is an excellent method, and many studies based on it have been proposed.
  • it is necessary to use a large amount of reactants, and there are a lot of by-products and unreacted materials, and there are still problems in terms of cost and environment. Was desired.
  • Patent Document 4 Japanese Patent Laid-Open No. Sho 50-0 1 3 1 8 8 7) discloses a combination of a solid catalyst component, which is a complex containing magnesium, titanium, halogen, and tetrahydrofuran, and an organoaluminum compound. A method for polymerizing olefins using a catalyst comprising It is. Further, Patent Document 5 (Japanese Patent Laid-Open No.
  • Sho 54-1440 893 discloses that a porous support is impregnated with a composition containing magnesium, titanium, halogen, and an electron donating compound.
  • a method of superimposing olefins using a catalyst composed of a combination of a solid catalyst component and an organic aluminum compound has been proposed. Although these methods are very effective methods, further improvement has been desired for the problem of obtaining a polymer in a high yield.
  • Patent Document 6 Japanese Patent Laid-Open No. 2_255 8 8 discloses magnesium halide and phthalic acid.
  • a catalyst comprising a combination of a solid catalyst component obtained by co-grinding a diester and a halogenated titanium compound and heat treatment in a hydrocarbon or halogenated hydrocarbon compound and an organoaluminum compound.
  • Patent Document 7 Japanese Patent Publication No. 2 0 4-5 2 7 6 2 1. proposes a catalyst component comprising a titanium compound, a magnesium compound, an electron donating compound, a polymer carrier, and an aluminum compound. ing.
  • the active titanium component effective for the polymerization reaction is dispersed and supported in the magnesium compound as much as possible, so that the yield at the time of polyolefin polymerization can be obtained.
  • the rate is improved.
  • the solid catalyst component in the conventional technology as described above particularly in a method of preparing by co-grinding a magnesium compound and a titanium compound, more effective titanium component is highly dispersed in the magnesium compound in this way, As a result, none improved the yield of olefin synthesis.
  • a solid catalyst component that can adopt a simpler method such as a co-grinding method and can obtain an olefin polymer having a high bulk density in a high yield has been developed and applied industrially.
  • by-products and waste are not generated at all in the production of the solid catalyst component, which not only improves the cost, but also improves safety and further reduces the burden on the environment.
  • the catalytic activity is further improved, not only the productivity can be improved, but also the catalyst component remaining in the polymer can be further reduced, and the problem of the stability of the polymer during the molding process can be eliminated.
  • a solid catalyst component for polymerization was desired.
  • Patent Document 1 Japanese Patent Publication No. Sho 4 7-4 1 6 7 6
  • Patent Document 2 Japanese Patent Application Laid-Open No. Sho 50-0-06 4 3 8 1
  • Patent Document 3 Japanese Patent Publication No. Sho 4 6-3 4 0 9 2
  • Patent Document 4 Japanese Patent Application Laid-Open No. 50 0-1 3 1 8 8 7
  • Patent Document 5 Japanese Patent Application Laid-Open No. 54-1440 893
  • Patent Document 6 Japanese Patent Laid-Open No. 2-5 5 8 08
  • Patent Document 7 Special Table 2 0 0 4 ⁇ 5 2 7 6 2 1
  • an object of the present invention is to produce a solid catalyst component for olefins polymerization and olefins which can be produced by a simple method called co-grinding and can obtain a high bulk density olefin polymer in a high yield. It is an object of the present invention to provide a polymerization catalyst and a method for producing an olefin polymer. Disclosure of the invention
  • the present inventors have made extensive studies, and as a result, the solid catalyst component prepared by co-grinding the halogen-containing magnesium compound and the halogen-containing titanium compound under specific conditions is the conventional solid catalyst component described above.
  • the present inventors have found that a polymer with a high bulk density can be obtained with a higher yield, and the present invention has been completed.
  • the present invention provides a solid catalyst component obtained by co-grinding a halogen-containing magnesium compound (a) and a halogen-containing titanium compound (b).
  • the solid catalyst component has a titanium content of 6 to 15% by weight, an average particle size of 1 to 200 ⁇ m, and an angle of repose of 20 to 60 degrees in the form of powdered olefins.
  • a solid catalyst component is provided.
  • the present invention provides a halogen-containing magnesium compound (a) with a halogen-containing titanium compound (b) continuously or intermittently at an addition rate of 0.2 mol hours or less per mol of the (a)
  • the titanium content in the solid catalyst component is 6 to 15% by weight
  • the average particle size is 1 to 200 ⁇ m
  • the angle of repose is 20 to 60 degrees.
  • the present invention provides a method for producing a solid catalyst component for polymerizing polyolefins to obtain a product.
  • the present invention also provides a titanium content of 6 to 15% by weight, an average particle size of 1 to 500 ⁇ m, by co-grinding of the halogen-containing magnesium compound (a) and the halogen-containing titanium compound (b).
  • a solid catalyst component for polymerizing olefins obtained by obtaining a powdery solid component having an angle of repose of 20 to 60 degrees and contacting the solid component with an oxygen-containing compound (c) is provided. is there.
  • the present invention also provides an olefin-based polymerization catalyst characterized by comprising the above-mentioned (A) solid catalyst component for olefin-based polymerization and (B) an organoaluminum compound.
  • the present invention provides a method for producing an olefin polymer, which comprises polymerizing the olefin in the presence of the above-mentioned catalyst for polymerizing olefins.
  • FIG. 1 is a flow chart showing the steps for preparing the catalyst component and the polymerization catalyst of the present invention.
  • the solid catalyst component (A) (hereinafter sometimes referred to as “component (A)”) in the olefin-based polymerization catalyst of the present invention is a halogen-containing magnesium compound (a) (hereinafter simply referred to as “component (a)”).
  • component (a) a halogen-containing magnesium compound
  • component (b) a halogen-containing titanium compound
  • examples of the halogen-containing magnesium compound (a) include dihalogenated magnesium, halogenated magnesium magnesium, and alkoxymagnesium magnesium.
  • magnesium dihalide and halogenated alkoxymagnesium. These magnesium compounds may be used alone or in combination of two or more.
  • magnesium dihalide is preferable, and specific examples include magnesium dichloride, magnesium dibromide, magnesium diiodide, magnesium difluoride, and magnesium dichloride is particularly preferable.
  • anhydrous magnesium dichloride which is produced as a by-product in the titanium metal plating process, is particularly preferable because it contains extremely little water and impurities. Specifically, it is possible to use a granulated product obtained by roughly crushing anhydrous magnesium dichloride produced as a by-product in the production process of metallic titanium or zirconium.
  • the halogen-containing magnesium compound (a) before the co-grinding only needs to be of a size that can be pulverized by the pulverizer used. However, at the point of contact with the halogen-containing titanium compound (b), the halogen-containing magnesium compound (a) is preferably a powder.
  • the preferred particle properties of the halogen-containing magnesium compound (a) are as follows.
  • the average particle size is 1 to 500 ⁇ , preferably 5 to 200 ⁇ m, more preferably 10 to 100 zm, and has a monomodal particle size distribution. Further, the ratio of particle diameters of 5 to 200 / zm is 80% by volume or more in all particles.
  • the bulk density is usually 0.3 to 1.2. 111 3 , preferably 0.4 to: 1.
  • O gZc m 3 The angle of repose is 20 to 60 degrees, preferably 30 to 60 degrees.
  • the specific surface area is 0. 0 1 ⁇ : 1 5 0m 2 Zg, preferably !; ⁇ 1 50m 2 / g. If the preferred particle property of magnesium dichloride is in the above range, the particle property of the solid component (A) obtained by co-grinding with the component (b) will be suitable.
  • titanium halide or alkoxy titanium halide can be used as the titanium compound.
  • aluminum-reduced titanium trichloride or tetravalent titanium halogen compounds are preferred.
  • Tetravalent titanium Nharogen compounds have the general formula (2); T i (OR 2) in S X 4 _ S (wherein, R 2 represents an alkyl group of from 1 to 4 carbon atoms, X is a halogen atom, s is 0 or an integer of 1 to 3. It is one or more compounds selected from the group consisting of titanium tetrahalide and alkoxytitanium halides represented by the following formula:
  • titanium tetrahalides such as titanium tetrachloride, titanium tetrabromide, and titanium tetraiodide are exemplified as titanium halides, and methoxytitanium tricide rides and ethoxy as alkoxytitanium halides.
  • trimethoxy titanium chloride triethoxy titanium chloride, tripropoxy titanium chloride, tri-n-butoxy titanium chloride and the like.
  • Component (A) has a titanium content in the solid component of 6 to 15% by weight, preferably 6 to 12% by weight, and more preferably 6 to 10% by weight. It is necessary to disperse and contain more titanium atoms in the magnesium halogen compound ( a ) in order to obtain a highly active solid catalyst component. However, it has been difficult for conventional techniques to contain more effective titanium components in a highly dispersed state by co-grinding a magnesium compound and a titanium compound.
  • the present invention is a solid catalyst component that can contain 6% by weight or more of a titanium component to enhance its activity and that maintains good particle properties.
  • the component (A) must be in the form of powder and have good particle properties.
  • Good particle properties refer to the following average particle size, particle size distribution, bulk density, and angle of repose. That is, the average particle size of the solid catalyst component after co-grinding is 1 to 200 m, preferably 5 to 150 / xm, more preferably 10 to 100 ⁇ m, and exhibits a monomodal particle size distribution. ing.
  • the particle diameters are generally uniform, and the ratio of particles present in a particle diameter of preferably 5 to 200 ⁇ is 80 volume among all particles. / 0 or more.
  • the average particle size and particle size distribution are obtained by the laser diffraction scattering method.
  • the bulk density of the ingredient () is usually 0.5 to: I. 5 g / cm 3 , preferably 0.7 to 1.2 g / cm 3 , and the angle of repose is 20 to 60 degrees. It is preferably 30 to 60 degrees.
  • the bulk density was measured according to JISK 6 72 1 (1 9 7 7), and the angle of repose was measured according to JISR 9 30 1-2-2 (1 9 9 9). It is.
  • a powder with a large angle of repose means poor flowability.
  • the specific surface area of the component (A) is 3 to 300 in 2 , g, preferably 50 to 300 m 2 / g. If the particle properties are deteriorated, not only the performance as a catalyst such as activity is deteriorated, but also fluidity is deteriorated when the powder is transferred, and troubles such as clogging in a pipe are caused.
  • the method of co-grinding the halogen-containing magnesium compound (a) and the halogen-containing titanium compound (b) includes, for example, bringing the component (a) and the component (b) into close contact with each other. It is carried out using any pulverizer capable of co-grinding. Examples of the pulverizer include a rotating ball mill, a rod mill, an impact mill, and a vibration mill. The degree of pulverization is carried out so that the component (b) is sufficiently dispersed and contained in the component (a) while maintaining the solid state of the component (a).
  • component (b) per mole of component (a), component (b) is added in an amount of 0.2 mol Z time or less, preferably 0.001 to 0.15 morno time, more preferably 0.001 to 0.1 Co-grind with continuous or intermittent addition at a rate of 3 mole hours.
  • component (b) is added intermittently, the amount added per time is 0.1 mol or less, preferably 0.05 mol or less per 1 mol of component (a).
  • an interval of at least 1 minute, preferably 30 minutes or more is added after one addition so that the total component (b) addition rate is within the above range. That is, when the component (b) is intermittently added, the addition rate is a value obtained by dividing the total amount of the component (b) by the time (h) from the first addition to the last addition.
  • the temperature for co-grinding is from 20 to 70 ° C, preferably from 20 to 40 ° C, and the total grinding time is from 1 to 300 hours, preferably from 5 to 200 hours.
  • component (b) By adding component (b) at a lower rate as described above, As such, good particle properties can be obtained.
  • the addition rate of component (b) is increased, the particle properties are deteriorated and the activity is lowered in the polymerization of olefins.
  • the pulverization can be carried out by either a wet method or a dry method, but dry pulverization is preferred in order to further improve the powder properties.
  • component ( ⁇ ′) of the present invention is a combination of the halogen-containing magnesium compound (a) and the halogen-containing titanium compound ( b ). It is obtained by bringing the solid catalyst component (A) obtained by pulverization into contact with an oxygen-containing compound (c) (hereinafter sometimes referred to as “component (c)”). ) between this contacting, melt Furore high one DOO, as can be obtained a highly active polymer.
  • oxygen-containing compounds methanol, ethanol, 1-pro Panonore, Lee Sopurono ⁇ 0
  • 1-butanol monoure isobutanol, t-butanol, pentanol, hexanol, heptanol, n-octanol, 2-ethylhexanol, decanol, stearyl anolol, a Alcohols such as linoleanolo cornore, cyclopentanol monole, cyclohexanol, benzenole alcohol, phenols such as phenol, cresol and naphthol, polyhydric alcohols such as ethylene glycol and propanediol, catechol, etc.
  • Polysiloxane is a polymer that has a siloxane bond (one S i _ O bond) in the main chain, and is also called force S, silicone oil, and has a viscosity at 25 ° C of 0.0 2 to 100 cm 2. It is a chain, partially hydrogenated, cyclic or modified polysiloxane having a liquid / viscous state at room temperature, having / s (2 ⁇ : I 0 00 0 0 centistokes).
  • esters such as alcohols, ethers, monocarboxylic acid esters, dicarboxylic acid diesters, metal alkoxide compounds, and the like are preferably used. These may be used alone or in combination of two or more.
  • the force to bring the component (c) into contact with the component (A) to obtain the component ( ⁇ ') is performed in an inert gas atmosphere and in a state where moisture and the like are removed.
  • the contact can be selected by any method. Preferable methods include a method of contacting while pulverizing in a pulverizer, and a method of contacting while stirring in a container equipped with a stirrer.
  • the contact temperature is the temperature at the time of contact of each component, and may be the same temperature as the reaction temperature or a different temperature.
  • the contact temperature may be a relatively low temperature range from ⁇ 20 ° C. to room temperature, or may be a relatively high temperature range from near room temperature to 200 ° C.
  • the reaction time is 1 minute or longer, preferably 10 minutes or longer, more preferably 30 minutes or longer.
  • the solid state of the solid component (A) may be maintained, or may be suspended or dissolved.
  • component (A) After contact between component (A) and component (c), excess component (c) may be removed.
  • component (A) When contacting component (A) with component (c), or When the component (C) is removed, the hydrocarbon compound (d) (hereinafter simply referred to as “component
  • Component (d) includes benzene, toluene, xylene, ethylbenzen, ethynoltoluene, propylbenzene, butylbenzene, pentinobenzene, hexylbenzene, heptinolebenzene, octylbenzene, decylbenzene, dodecylbenzene, vinylolbenzene, Aromatic hydrocarbon compounds such as limethylbenzen and jetylbenzene, aliphatic hydrocarbon compounds such as pentane, hexane, heptane, octane, decane, dodecane, undecane, tridecane, tetradecane, kerosene, and alicyclic hydrocarbon compounds Halogenated hydrocarbon compounds are used. These may be used alone or in combination of two or more.
  • component (e) metal oxides such as silica, alumina, magnesia, titania and zirconia, layered compounds such as montmorillonite and mica, activated carbon, polymer Contacting solid matter such as particles (hereinafter sometimes referred to as “component (e)”) is preferable in terms of controlling the shape and particle size distribution of the catalyst.
  • the component (A) obtained by co-grinding the component (a) and the component (b) is brought into contact with the component (c), Smash.
  • the component (A) obtained by co-grinding the component (a) and the component (b) is brought into contact with the component (c), and a stirring and mixing process is performed. After stirring and mixing, the excess component (c) is removed. If component (e) is used, contact it before removing excess component (c). To remove excess component (c), it can be dried or washed with component (d).
  • the co-grinding method in the preparation method of the solid catalyst component ( ⁇ ′) is the same as the co-pulverization method in the component ( ⁇ ) preparation method.
  • a halogen-containing magnesium compound (a) such as anhydrous magnesium dichloride is added to a halogen-containing titanium compound such as titanium tetrachloride.
  • component (c) is added to component (A) with an oxygen-containing compound such as alcohol, ether, ester, metal alkoxide compound, and further co-ground to obtain a solid catalyst component ( ⁇ ′).
  • an oxygen-containing compound such as alcohol, ether, ester, metal alkoxide compound
  • a halogen-containing titanium compound such as titanium tetrachloride
  • a halogen-containing magnesium compound (a) such as anhydrous magnesium dichloride.
  • component (A) is contacted with an oxygen-containing compound such as alcohol, ether, ester or metal alkoxide compound (c), and stirred and mixed in a temperature range of ⁇ 20 to 200 ° C. Or it is set as a solution state. Further, a component (e) such as silica or alumina is brought into contact, dried, and washed with a hydrocarbon compound (d) such as hexane or toluene to obtain a solid catalyst component ( ⁇ ′).
  • an oxygen-containing compound such as alcohol, ether, ester or metal alkoxide compound (c)
  • a component (e) such as silica or alumina is brought into contact, dried, and washed with a hydrocarbon compound (d) such as hexane or toluene to obtain a solid catalyst component ( ⁇ ′).
  • the amount of each component used in preparing the solid catalyst component ( ⁇ ) or the solid catalyst component ( ⁇ ') is as follows: the halogen-containing titanium compound (b) is 0.1 per mole of the halogen-containing magnesium compound (a). ⁇ 0.8 mol, preferably 0.1 to 0.5 mol.
  • the oxygen-containing compound (c) is 0 ⁇ 0 1 to 1: 100 mol, preferably 0.1 to 1 mol per 1 mol of the magnesium halogen compound (a) in the solid catalyst component (A,). 50 moles.
  • the content of titanium in the solid catalyst component (Alpha ') of the present invention is not particularly default, preferably, titanium from 1.0 to 20 0 weight 0/0, and more preferable properly 2.
  • the magnesium and halogen atom contents in the solid catalyst components (A) and ( ⁇ ′) in the present invention are not particularly defined, but magnesium is 10 to 50% by weight, more preferably 10 to 30% by weight, The halogen atom content is 20 to 90% by weight, more preferably 40 to 80% by weight.
  • the organic aluminum compound ( ⁇ ) (hereinafter sometimes simply referred to as “component ( ⁇ )”) used in forming the olefin-based polymerization catalyst of the present invention includes the following general formula (1); R 1 r A 1 Q 3 _ r (1) (wherein R 1 represents a linear or branched alkyl group having 1 to 4 carbon atoms, Q represents a hydrogen atom or a halogen atom, and r represents 0 ⁇ It is a real number of r ⁇ 3. If it is a compound represented by), it is not particularly limited, but R 1 is preferably an ethyl group or an isobutyl group, and Q is preferably a hydrogen atom, a chlorine atom or a bromine atom.
  • R is preferably 2 or 3, particularly preferably 3.
  • organoaluminum compound (B) include triethyl aluminum, jetyl aluminum chloride, triisobutyl aluminum, jetyl aluminum bromide, and jetyl aluminum hydride. 1 type or 2 or more types can be used. Triethylaluminum and trisobutylaluminum are preferable.
  • the method for producing an olefin-based polymer of the present invention includes the above-described solid catalyst component (A) or polymerization or copolymerization of olefins in the presence of a catalyst comprising the solid catalyst component ( ⁇ ′) and the component ( ⁇ ).
  • olefins include ethylene, propylene, 1-butene, 1-pentene, 3-methyl-1-butene, 4-methyl-1- 1-pentene, and vinylolcyclohexane. These olefins are one or two. More than one species can be used in combination. In particular, ethylene, propylene and 1-butene are preferably used. Particularly preferred is ethylene.
  • ethylene polymerization it can be copolymerized with other olefins.
  • Copolymerized examples of the olefins include propylene, 1-butene, 1-pentene, 1-hexene, 1-octene, 3-methinole 1-butene, 4-methinole 1-pentene, vinylcyclohexane, etc.
  • Olefins can be used alone or in combination of two or more.
  • propylene, 1-butene, 1-hexene, and 1-octene are preferably used.
  • the organoaluminum compound (B) is a solid catalyst component (A) or It is used in the range of 1 to 200000 moles, preferably 20 to 1 000 moles per mole of titanium atoms in the solid catalyst component ( ⁇ ′).
  • the order of contacting the components is arbitrary, but it is desirable to first introduce the organoaluminum compound ( ⁇ ) into the polymerization system and then contact the solid catalyst component ( ⁇ ) or the solid catalyst component ( ⁇ ′).
  • the polymerization method in the present invention can be carried out in the presence or absence of an organic solvent, and the olefin monomer such as propylene can be used in any state of gas and liquid.
  • the polymerization temperature is 200 ° C. or lower, preferably 100 ° C. or lower, and the polymerization pressure is 0.0 1 to 10 MPa, preferably 0.1 to 5 MPa. Either continuous polymerization or batch polymerization is possible.
  • the polymerization reaction may be performed in one stage or in two or more stages.
  • the catalytic activity and the production are achieved.
  • preliminary polymerization can be performed prior to the main polymerization.
  • the same olefins as those used in the main polymerization, or monomers such as styrene and a silicon compound having a double bond such as vinylsilane may be used. You can.
  • a 1 liter stainless steel grinding pot is filled with 4 29 ml of stainless steel balls with a diameter of 25.4 mm, with an average particle size of 40/1 m, 5-20 1 1 2 g (1.18 moles) of anhydrous magnesium chloride with 85% by volume of particles present in a particle size of 0 m and an angle of repose of 42 degrees, and titanium tetrachloride 6 3 g was added in a nitrogen atmosphere and co-ground for 3 hours under conditions of an amplitude of 3 mm and a rotation speed of 1400 rpm. Next, 6.3 g of titanium tetrachloride was added and co-ground for 3 hours under the same conditions.
  • the bulk density was measured to be 0.9 g / cm 3 , and the angle of repose was measured to be 48 degrees.
  • no by-products or waste were produced.
  • ethylene was polymerized, and the produced polymer was filtered and dried under reduced pressure to obtain a solid polymer.
  • the filtrate is condensed to obtain a polymer dissolved in the polymerization solvent, the amount of which is (M), and the amount of the solid polymer is (N).
  • the polymerization activity (Y) per titanium in the solid catalyst component is represented by the following formula.
  • melt index (Ml) indicating the melt flow rate of the produced solid polymer (N) was measured according to A STM D 1 2 3 8, J I S K 7 2 10.
  • a stainless steel grinding pot with an inner volume of 1 liter is filled with 4 29 ml of stainless steel balls with a diameter of 25.4 mm, and the average particle size is 40 ⁇ ⁇ , 5 to 2 0 0
  • Anhydrous magnesium chloride 1 1 2 g (1.17 76 mol) and titanium tetrachloride 3 7 . 8 g (0.19 9 moles) was added almost simultaneously under a nitrogen atmosphere, 2 at an amplitude of 3 mm and a rotational speed of 1 400 rpm.
  • the solid catalyst component was obtained by co-grinding for 0 hour. As a result, the pulverized product adhered to the ball for pulverization and did not become powder.
  • a solid catalyst component was prepared in the same manner as in Example 1, except that the minute X was 3 times, 19 hours 45 minutes X 1 time.
  • the titanium content in this solid component was 6.4% by weight.
  • the particle size distribution of this solid catalyst component could not be measured because the particle size was too large.
  • the average particle size was over 200 ⁇ .
  • This solid catalyst component had poor powder flowability, and the bulk density and angle of repose could not be measured.
  • a polymerization catalyst was formed and polymerized in the same manner as in Example 1. The polymerization results are shown in Table 1.
  • a 1 liter stainless steel grinding pot is filled with 4 29 ml of stainless steel balls with a diameter of 25.4 mm, with an average particle size of 40 m, 5 to 200
  • Anhydrous magnesium chloride with a particle ratio of 85% by volume in the particle and an angle of repose of 42 degrees 1 38 g (1.45 mol) and titanium tetrachloride 12 g (0.06 3 mol) was added almost simultaneously in a nitrogen atmosphere, and powdered together for 20 hours under the conditions of an amplitude of 3 mm and a rotational speed of 1400 rpm. Crushed.
  • the solid catalyst component was obtained by removing from the crushing pot.
  • the titanium content in the solid catalyst component was measured and found to be 2.0% by weight.
  • the average particle size of the solid catalyst component was measured to be 52 ⁇ m, and it was a monomodal particle size distribution in which 82% by volume of the particles existed between 5 and 200 ⁇ m.
  • the angle of repose was measured to be 45 degrees.
  • a polymerization catalyst was formed and polymerized in the same manner as in Example 1. The polymerization results are shown in Table 1.
  • a 1 liter stainless steel grinding pot is filled with 4 29 ml of stainless steel balls with a diameter of 25.4 mm, with an average particle size of 40 ⁇ m, 5 to 20
  • the proportion of particles present in the particle size between 0 ⁇ m is 85% by volume in the particles, and the angle of repose is 42 degrees
  • titanium tetrachloride 8. 7 g was added in a nitrogen atmosphere and co-ground for 3 hours under the conditions of an amplitude of 3 mm and a rotation speed of 1400 rpm. Next, 8.7 g of titanium tetrachloride was added and co-ground for 3 hours under the same conditions.
  • the bulk density was measured to be 1.0 g / cm 3 , and the angle of repose was measured to be 54 degrees.
  • Example 3 A polymerization catalyst was formed and polymerized in the same manner as in Example 1 except that the solid catalyst component obtained above was used. The polymerization results are shown in Table 1. Example 3
  • a solid catalyst component was obtained in the same manner as in Example 2, except that 2.5 ml of ethyl propionate was used instead of 2.5 ml of ethanol.
  • the titanium content in the solid catalyst component was measured and found to be 4.0% by weight.
  • a polymerization catalyst was formed and polymerized in the same manner as in Example 2. The polymerization results are shown in Table 1.
  • Example 2 In the same manner as in Example 2, a solid component was obtained. Next, a 10 Om 1 tetrahydrofuran was charged into a 50 Om 1 round bottom flask equipped with a stirrer and sufficiently substituted with nitrogen gas. g (anhydrous magnesium chloride 5.0 g, titanium tetrachloride equivalent to 2.7 g) was charged. The temperature was raised to 60 ° C. and reacted for 3 hours to dissolve the solid components. After cooling to 40 ° C. or lower, n—heptane 25 O m 1 was charged to precipitate a solid. After stirring for 10 minutes, the solid component was washed with n-heptane to obtain a solid catalyst component. The titanium content in the solid catalyst component was measured and found to be 2.4% by weight.
  • a polymerization catalyst was formed and polymerized in the same manner as in Example 2. The polymerization results are shown in Table 1.
  • a solid catalyst component was prepared in the same manner as in Example 2, except that X was 5 times, 15 hours X 1 time.
  • the titanium content in this solid component is 8.8% by weight.
  • the solid is 8 5 mu Ie was measured an average particle size of the catalyst component, a mono-modal, were particle size distribution is 8 5 vol 0/0 of particles exist between. 5 to 2 0 0 mu m .
  • the angle of repose was measured and found to be 58 degrees.
  • Example 4 a solid catalyst component was obtained in the same manner as in Example 4 except that the above solid component was used.
  • the titanium content in the solid catalyst component was measured and found to be 2.8% by weight.
  • Titanium tetrachloride added 8.7 g 6 times, co-grinding time 3 hours X 5 times 5 hours XI times instead of titanium tetrachloride 8.7 g added 6 times, co-grinding time 30
  • a solid catalyst component was prepared in the same manner as in Example 2, except that the minute X was 5 times and 17.5 hours X 1 time.
  • the titanium content in this solid component is 8.8% by weight.
  • the average particle size of the solid catalyst component was measured to be 96 ⁇ m, which was a monomodal particle size distribution in which 82% by volume of the particles existed between 5 and 200 m.
  • Example 4 a solid catalyst component was obtained in the same manner as in Example 4 except that the above solid component was used.
  • the titanium content in the solid catalyst component was measured and found to be 2.5% by weight.
  • a polymerization catalyst was formed and polymerized in the same manner as in Example 2. The polymerization results are shown in Table 1.
  • a solid catalyst component was obtained in the same manner as in Example 4 except that anhydrous magnesium chloride 5. O g and titanium tetrachloride 2.7 g were charged separately instead of 7.7 g of the solid component. . When the titanium content in this solid catalyst component was measured It was 3.1% by weight.
  • a polymerization catalyst was formed and polymerized in the same manner as in Example 2. The polymerization results are shown in Table 1.
  • a solid catalyst component was prepared in the same manner as in Example 2 except that 9.2 g of aluminum reduced titanium trichloride was used instead of 8.7 g of titanium tetrachloride.
  • the titanium content in this solid component is 8.8% by weight.
  • the average particle size of this solid catalyst component was measured to be 3 8 / im, monomodal and 85 volume of particles. /. Existed between 5 and 200 ⁇ m in particle size.
  • the bulk density was 0.8 g cm 3 and the angle of repose was 36 degrees.
  • a solid catalyst component was obtained in the same manner as in Example 4 except that 7.9 g of the solid component was used instead of 7.7 g of the solid component.
  • the titanium content in the solid catalyst component was measured and found to be 2.6% by weight.
  • a polymerization catalyst was formed and polymerized in the same manner as in Example 2. The polymerization results are shown in Table 1.
  • Solid component 7. instead of 7 g, anhydrous magnesium chloride 5.
  • O g and aluminum A solid catalyst component was obtained in the same manner as in Example 4 except that 2.9 g of nitrogen-reduced titanium trichloride was charged separately. The titanium content in the solid catalyst component was measured and found to be 3.8% by weight.
  • a polymerization catalyst was formed and polymerized in the same manner as in Example 2. The polymerization results are shown in Table 1.
  • a 1 liter stainless steel crushing pot is filled with 4 2 9 m 1 of stainless steel balls with a diameter of 25.4 mm, with an average particle diameter of 40 ⁇ , 5 to 2
  • Anhydrous magnesium chloride with a proportion of 85% by volume, an angle of repose of 42 °, a specific surface area of 15 m 2 , g, titanium tetrachloride, titanium tetrachloride 9. 2 g was added in a nitrogen atmosphere and co-ground for 3 hours. Next, 9.2 g of titanium tetrachloride was added, and the mixture was co-ground for 3 hours under the conditions of an amplitude of 3 mrn and a rotational speed of 1400 rpm.
  • the bulk density was 1.0 g / cm 3 , the angle of repose was 55 °, and the specific surface area was 160 m 2 nog.
  • a stainless steel grinding pot with an inner volume of 1 liter was filled with a stainless steel ball having a diameter of 25.4 mm in a volume of 4 29 m 1, and the above solid component 65 g, triethoxy 15 g of aluminum was added under a nitrogen atmosphere and co-ground for 12 hours.
  • the solid component was obtained by removing from the crushing pot.
  • the titanium content in this solid component is 7.6 wt. /. Met.
  • a polymerization catalyst was formed and polymerized in the same manner as in Example 2. The polymerization results are shown in Table 1.
  • a 1-liter stainless steel crushing pot is filled with 4 2 9 ml of stainless steel balls with a diameter of 25.4 mm, with an average particle size of 4 ⁇ ⁇ ⁇ , 5 to 200 ⁇ m.
  • the proportion of particles present in the particle size between 85% by volume in the particle, anhydrous magnesium chloride with an angle of repose of 42 degrees 41 g (0.4 3 mol), titanium tetrachloride 24 g, triethoxyaluminum 15 g was added almost simultaneously in a nitrogen atmosphere and co-ground for 32 hours under conditions of an amplitude of 3 mm and a rotation speed of 1 400 rpm.
  • the solid catalyst component was obtained by removing from the crushing pot.
  • the titanium content in the solid catalyst component was 9.3 wt%. This solid catalyst component was too sticky, and the particle size distribution and angle of repose could not be measured.
  • a polymerization catalyst was formed and polymerized in the same manner as in Example 2.
  • the polymerization results are shown in Table 1. '
  • a polymerization catalyst was formed and polymerized in the same manner as in Example 2. The polymerization results are shown in Table 1.
  • the catalyst of the present invention exhibits high polymerization activity when used for the polymerization of olefins, and can provide a high bulk density olefin polymer, providing polyolefin with high productivity and low cost. obtain.
  • the olefin-based polymerization catalyst using the solid catalyst component of the present invention is used for the polymerization of olefins, a polymer having a very high activity and a high bulk density can be obtained.
  • the solid catalyst component of the present invention can be produced by a simpler method with less waste such as by-products and unreacted materials. Therefore, productivity can be improved, catalyst components remaining in the polymer can be further reduced, and the stability problem of the polymer during molding can be solved. Furthermore, the environmental load can be reduced by industrially using the solid catalyst component of the present invention.

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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

L'invention porte sur un catalyseur pour la polymérisation des oléfines, qui est composé d'un composant catalytique solide pulvérulent (A) pour la polymérisation des oléfines, qui est obtenu par co-pulvérisation d'un composé halogénure de magnésium (a) et d'un composé halogénure de titane (b), et d'un composé organique de l'aluminium (B) représenté par la formule générale suivante : R1rAlQ3-r. Le composant catalytique solide pulvérulent (A) a une teneur en titane dans la teneur en matières solides de 6-15 % en poids, un diamètre moyen de particule de 1-200 µm et un angle d'éboulement de 20-60 degrés. Lorsque la polymérisation d'une oléfine est effectuée en présence de ce catalyseur, un polymère d'oléfine ayant une masse volumique apparente élevée peut être obtenu avec un haut rendement.
PCT/JP2008/061933 2007-06-29 2008-06-25 Composant catalytique solide pour la polymérisation des oléfines, son procédé de fabrication, catalyseur et procédé de fabrication d'un polymère d'oléfine à l'aide du catalyseur WO2009005074A1 (fr)

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Citations (17)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5345688A (en) * 1976-10-07 1978-04-24 Mitsubishi Petrochem Co Ltd Production of olefin polymerization catalyst component
JPS5590510A (en) * 1978-12-28 1980-07-09 Mitsubishi Petrochem Co Ltd Preparation of olefin polymer
JPS5883006A (ja) * 1981-11-13 1983-05-18 Mitsui Petrochem Ind Ltd オレフインの重合方法
JPS5956407A (ja) * 1982-08-20 1984-03-31 フイリツプス・ペトロリユ−ム・コンパニ− オレフイン重合用触媒の製法および用法
JPS61276806A (ja) * 1985-06-03 1986-12-06 Toho Titanium Co Ltd オレフイン類重合用触媒成分の製造方法
JPS61296006A (ja) * 1985-06-24 1986-12-26 Toho Titanium Co Ltd オレフイン類重合用触媒成分の製造方法
JPS6289707A (ja) * 1985-09-06 1987-04-24 フイリツプス　ペトロリユ−ム　コンパニ− オレフインの重合用触媒の製造方法
JPS62127304A (ja) * 1985-11-27 1987-06-09 Toho Titanium Co Ltd オレフイン類重合用触媒成分の製造方法
JPS63120705A (ja) * 1986-11-10 1988-05-25 Toho Titanium Co Ltd オレフイン類重合用触媒
JPS63122711A (ja) * 1986-11-12 1988-05-26 Toho Titanium Co Ltd オレフイン類重合用触媒
JPS63132909A (ja) * 1986-11-26 1988-06-04 Toho Titanium Co Ltd オレフイン類重合用触媒
JPS63308003A (ja) * 1986-10-06 1988-12-15 Toho Titanium Co Ltd オレフイン類重合用触媒
JPH01229006A (ja) * 1988-03-09 1989-09-12 Toho Titanium Co Ltd オレフイン類重合用触媒
JPH02196805A (ja) * 1989-01-26 1990-08-03 Toho Titanium Co Ltd オレフイン類重合用触媒
JPH0496912A (ja) * 1990-08-16 1992-03-30 Tokuyama Soda Co Ltd プロピレンの予備重合方法
JPH06145248A (ja) * 1992-03-16 1994-05-24 Phillips Petroleum Co オレフィンの重合によるコポリマーの製造方法
JPH06279523A (ja) * 1993-03-24 1994-10-04 Mitsui Petrochem Ind Ltd オレフィン重合用固体状チタン触媒成分、オレフィン重合用触媒およびこれを用いるオレフィンの重合方法

Patent Citations (17)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5345688A (en) * 1976-10-07 1978-04-24 Mitsubishi Petrochem Co Ltd Production of olefin polymerization catalyst component
JPS5590510A (en) * 1978-12-28 1980-07-09 Mitsubishi Petrochem Co Ltd Preparation of olefin polymer
JPS5883006A (ja) * 1981-11-13 1983-05-18 Mitsui Petrochem Ind Ltd オレフインの重合方法
JPS5956407A (ja) * 1982-08-20 1984-03-31 フイリツプス・ペトロリユ−ム・コンパニ− オレフイン重合用触媒の製法および用法
JPS61276806A (ja) * 1985-06-03 1986-12-06 Toho Titanium Co Ltd オレフイン類重合用触媒成分の製造方法
JPS61296006A (ja) * 1985-06-24 1986-12-26 Toho Titanium Co Ltd オレフイン類重合用触媒成分の製造方法
JPS6289707A (ja) * 1985-09-06 1987-04-24 フイリツプス　ペトロリユ−ム　コンパニ− オレフインの重合用触媒の製造方法
JPS62127304A (ja) * 1985-11-27 1987-06-09 Toho Titanium Co Ltd オレフイン類重合用触媒成分の製造方法
JPS63308003A (ja) * 1986-10-06 1988-12-15 Toho Titanium Co Ltd オレフイン類重合用触媒
JPS63120705A (ja) * 1986-11-10 1988-05-25 Toho Titanium Co Ltd オレフイン類重合用触媒
JPS63122711A (ja) * 1986-11-12 1988-05-26 Toho Titanium Co Ltd オレフイン類重合用触媒
JPS63132909A (ja) * 1986-11-26 1988-06-04 Toho Titanium Co Ltd オレフイン類重合用触媒
JPH01229006A (ja) * 1988-03-09 1989-09-12 Toho Titanium Co Ltd オレフイン類重合用触媒
JPH02196805A (ja) * 1989-01-26 1990-08-03 Toho Titanium Co Ltd オレフイン類重合用触媒
JPH0496912A (ja) * 1990-08-16 1992-03-30 Tokuyama Soda Co Ltd プロピレンの予備重合方法
JPH06145248A (ja) * 1992-03-16 1994-05-24 Phillips Petroleum Co オレフィンの重合によるコポリマーの製造方法
JPH06279523A (ja) * 1993-03-24 1994-10-04 Mitsui Petrochem Ind Ltd オレフィン重合用固体状チタン触媒成分、オレフィン重合用触媒およびこれを用いるオレフィンの重合方法

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