JP2010222563A - Process for producing prepolymerized catalyst for olefin polymerization and process for producing olefin polymer - Google Patents

Abstract

A prepolymerization catalyst for olefin polymerization having a small content of fine particles is produced.
The method for producing a prepolymerized catalyst for olefin polymerization according to the present invention comprises a fine powder for removing fine prepolymerized catalyst particles for olefin polymerization from an aggregate of prepolymerized catalyst particles for olefin polymerization in which olefin is prepolymerized. A removal step is included. Therefore, it is possible to produce a prepolymerization catalyst for olefin polymerization with a small content of prepolymerization catalyst particles for olefin polymerization, and the olefin polymer can be stably and continuously produced using the obtained prepolymerization catalyst. Can be manufactured.
[Selection] Figure 1

Description

  The present invention relates to a method for producing a prepolymerization catalyst for olefin polymerization and a method for producing an olefin polymer.

  In Patent Document 1, as a method for producing a homogeneous solid catalyst component or a homogeneous solid catalyst applied to gas phase polymerization or slurry polymerization, a fine powder component and / or an indefinite formation component is obtained by utilizing a difference in sedimentation rate with respect to a solvent. A method of removing and producing is described, and a method of producing a prepolymerized catalyst by prepolymerizing an olefin with the catalyst produced by the above-described method is described.

JP 2003-105013 A (published April 9, 2003)

  However, also in the gas phase polymerization or slurry polymerization of olefins using the prepolymerization catalyst obtained by the production method described in Patent Document 1, the olefin polymer particles inside the polymerization reactor, for example, in the enlarged portion of the polymerization reactor Therefore, there is a demand for a method for producing a prepolymerized catalyst for olefin polymerization that can prevent fouling of olefin polymer particles into a polymerization reactor.

  An object of the present invention is to provide a method for producing a prepolymerization catalyst for olefin polymerization capable of preventing fouling of olefin polymer particles to a polymerization reactor, and an olefin polymer using the prepolymerization catalyst for olefin polymerization obtained by the production method. It is in providing the manufacturing method of.

  In order to solve the above-mentioned problems, a method for producing a prepolymerization catalyst for olefin polymerization according to the present invention comprises a prepolymerization catalyst for fine olefin polymerization from an aggregate of prepolymerization catalyst particles for olefin polymerization in which olefin is prepolymerized. A fine powder removing step for removing particles is included.

  In the method for producing an olefin polymer according to the present invention, olefin polymerization is carried out using the prepolymerization catalyst for olefin polymerization produced by the above production method.

  By the production method of the present invention, a prepolymerization catalyst for olefin polymerization capable of preventing fouling of the olefin polymer particles to the polymerization reactor is obtained, and if the olefin is polymerized using the catalyst, the polymerization reactor is supplied to the polymerization reactor. Fouling of the olefin polymer particles can be prevented.

FIG. 1 is an explanatory diagram for explaining an embodiment of a method for producing a prepolymerization catalyst for olefin polymerization according to the present invention.

  Hereinafter, embodiments of the present invention will be described in detail.

[Method for producing pre-polymerization catalyst for olefin polymerization]
The method for producing a prepolymerized catalyst for olefin polymerization according to the present invention includes a fine powder removing step of removing fine prepolymerized catalyst particles for olefin polymerization from an aggregate of prepolymerized catalyst particles for olefin polymerization in which olefin is prepolymerized. To do.

  In the present invention, the prepolymerization is intended to polymerize a small amount of olefin on the olefin polymerization catalyst component prepared for olefin polymerization to form an olefin polymer on the olefin polymerization catalyst component. In the present invention, the prepolymerized catalyst for olefin polymerization is intended to be a catalyst in which olefin is prepolymerized on the catalyst component for olefin polymerization, and may be simply referred to as a prepolymerized catalyst.

  In the present invention, the prepolymerized catalyst particle for olefin polymerization is intended to be a granular material or a powdery material constituting the prepolymerized catalyst, and the prepolymerized catalyst is configured to include an aggregate of the prepolymerized catalyst particles. The The prepolymerized catalyst particles for olefin polymerization are fine prepolymerized catalyst particles having a small particle size that may cause problems such as agglomeration of the prepolymerized catalyst and clogging of the cyclone during the olefin polymerization described above. (Fine powder).

In addition, the particle size of the minute prepolymerized catalyst particles for olefin polymerization is expressed by the following formula (1).
R = (average particle diameter of prepolymerized catalyst particles for olefin polymerization in an aggregate of prepolymerized catalyst particles for olefin polymerization) × 0.65 (1)
Or less than R represented by

  When the content of particles having a particle size of R or less in the prepolymerization catalyst for olefin polymerization is large, the present inventors have problems such as agglomeration of the prepolymerization catalyst and clogging of the cyclone during the olefin polymerization described above. We found that is easy to occur. The method for producing a prepolymerization catalyst for olefin polymerization according to the present invention includes a removal step for removing such prepolymerized catalyst particles for olefin polymerization, and the resulting prepolymerization catalyst for olefin polymerization Since the content of the fine particles is very small, it is possible to prevent the above-described problems during olefin polymerization.

  Here, the average particle diameter of the prepolymerized catalyst particles for olefin polymerization in the aggregate of prepolymerized catalyst particles for olefin polymerization is determined by the size of the olefin polymerization catalyst component and the amount of prepolymerization, but is 80 μm or more and 300 μm or less. It is preferable that The average particle size of the prepolymerized catalyst particles for olefin polymerization in the aggregate of prepolymerized catalyst particles for olefin polymerization can be measured by a known particle size distribution measuring method.

  As the catalyst component for olefin polymerization used in the present invention, a known polymerization catalyst component used for olefin polymerization can be used, and examples thereof include metallocene catalysts, Ziegler type catalysts, Philip type catalysts, and the like. A metallocene catalyst is preferred. Examples of the metallocene catalyst include those formed by contacting a promoter component, a metallocene compound, and an organoaluminum compound.

  The catalyst component for olefin polymerization used in the present invention is more preferably formed by bringing a promoter component, a metallocene compound and an organoaluminum compound into contact with each other. It is known that the aggregate of prepolymerized catalyst particles for olefin polymerization obtained by prepolymerizing olefin with such an olefin polymerization catalyst component is likely to contain fine particles, and the olefin polymerization according to the present invention It is particularly suitable for producing a prepolymerization catalyst for olefin polymerization with a small content of fine powders by the method for producing a prepolymerization catalyst for use.

  Examples of the promoter component used in the present invention include a solid catalyst component formed by bringing an organozinc compound and a halogenated phenol or halogenated alcohol, water and a particulate carrier into contact with each other, an organoaluminum oxy compound and a particulate carrier. And a solid catalyst component formed by bringing a boron compound and a particulate carrier into contact with each other.

  Examples of the particulate carrier include a solvent used for the production of a catalyst component for olefin polymerization or a solid material insoluble in the polymerization solvent, and preferably a porous material having a uniform particle size generally used as a carrier. More preferably, they are inorganic substances or organic polymers, and more preferably inorganic substances. As an inorganic substance, an inorganic oxide, clay, or a clay mineral is mentioned, for example. You may mix and use these some inorganic substance.

Examples of the inorganic oxide include SiO ₂ , Al ₂ O ₃ , MgO, ZrO ₂ , TiO ₂ , B ₂ O ₃ , CaO, ZnO, BaO, and ThO ₂ , and mixtures thereof, SiO ₂ —MgO, SiO. _{2 -Al 2 O 3, SiO 2} -TiO 2, SiO 2 -V 2 O 5, SiO 2 -Cr 2 O 3, and SiO ₂ -TiO ₂ -MgO and the like. These inorganic oxides are preferably SiO ₂ and / or Al ₂ O ₃ , and particularly preferably SiO ₂ (ie, silica).
Examples of the clay or clay mineral include kaolin, bentonite, kibushi clay, gyrome clay, allophane, hysinger gel, vylophilite, talc, ummo group, smectite, montmorillonite group, hectorite, laponite, saponite, vermiculite, ryokdeite stone. Group, palygorskite, kaolinite, nacrite, dickite, halloysite.

  Among these, preferred are smectite, montmorillonite, hectorite, laponite and saponite, and more preferred are montmorillonite and hectorite. Any organic polymer may be used as the organic polymer, and a mixture of plural kinds of organic polymers may be used. The organic polymer is preferably a polymer having a functional group having active hydrogen or a non-proton-donating Lewis basic functional group.

  The cocatalyst component is preferably a solid catalyst component formed by contacting an organozinc compound, a halogenated phenol or halogenated alcohol, water and silica.

  The metallocene compound is preferably a Group 4 transition metal compound having two cyclopentadiene type anion skeletons.

  Further, as the organoaluminum compound, trialkylaluminum, triethylaluminum, tri-n-propylaluminum, tri-n-butylaluminum, triisobutylaluminum, tri-n-hexylaluminum, and trialkyl such as tri-n-octylaluminum Dialkylaluminum chlorides such as aluminum, dimethylaluminum chloride, diethylaluminum chloride, di-n-propylaluminum chloride, di-n-butylaluminum chloride, diisobutylaluminum chloride, and di-n-hexylaluminum chloride, methylaluminum dichloride, ethylaluminum Dichloride, n-propyl aluminum dichloride, n-butyl aluminum dichloride Id, isobutyl aluminum dichloride, and alkyl aluminum dichloride such as n-hexyl aluminum dichloride, dimethyl aluminum hydride, diethyl aluminum hydride, di-n-propyl aluminum hydride, di-n-butyl aluminum hydride, diisobutyl aluminum hydride, and di-n Dialkyl aluminum hydrides such as hexyl aluminum hydride, alkyl (dialkoxy) aluminum such as methyl (dimethoxy) aluminum, methyl (diethoxy) aluminum, and methyl (di-tert-butoxy) aluminum, dimethyl (methoxy) aluminum, dimethyl (ethoxy ) Aluminum and dimethyl (tert-butoxy) al Alkyl (diaryloxy) aluminum such as dialkyl (alkoxy) aluminum such as nium, methyl (diphenoxy) aluminum, methyl bis (2,6-diisopropylphenoxy) aluminum, and methyl bis (2,6-diphenylphenoxy) aluminum, and dimethyl ( Mention may be made of dialkyl (aryloxy) aluminums such as phenoxy) aluminum, dimethyl (2,6-diisopropylphenoxy) aluminum and dimethyl (2,6-diphenylphenoxy) aluminum. Among them, preferred is trialkylaluminum, more preferred is trimethylaluminum, triethylaluminum, tri-n-butylaluminum, triisobutylaluminum, tri-n-hexylaluminum or tri-n-octylaluminum, particularly preferred. Triisobutylaluminum or tri-n-octylaluminum.

  These organoaluminum compounds may be used alone or in combination of two or more.

(Fine powder removal process)
In the fine powder removing step, the prepolymerized catalyst particles for olefin polymerization are removed from the aggregate of prepolymerized catalyst particles for olefin polymerization formed by prepolymerizing olefin to the catalyst component for olefin polymerization, and the fine olefin is removed. A prepolymerization catalyst for olefin polymerization having a low content of prepolymerization catalyst particles for polymerization is obtained.

  The removal of the prepolymerized catalyst particles for olefin polymerization is not intended to completely remove the prepolymerized catalyst particles for olefin polymerization from the aggregate of prepolymerized catalyst particles for olefin polymerization. It is intended to reduce the content of fine olefin polymerization prepolymerization catalyst particles in the prepolymerization catalyst particle aggregate, and preferably the fine olefin polymerization prepolymerization catalyst produced according to the present invention has a small content. The content of the prepolymerized catalyst particles for olefin polymerization is intended to be 5% by weight or less.

  A known classification method can be used as a method for removing minute pre-polymerization catalyst particles for olefin polymerization from the aggregate of pre-polymerization catalyst particles for olefin polymerization, but the olefin is dried after pre-polymerizing the olefin. From the aggregate of prepolymerization catalyst particles for polymerization, the fine prepolymerization catalyst particles for olefin polymerization may be removed in a state of being dried by a dry removal treatment. The aggregate of the prepolymerized catalyst particles for olefin polymerization can be dried using a conventionally known dryer.

  Further, by passing the aggregate of prepolymerized catalyst particles for olefin polymerization through a separation porous material that passes through the prepolymerized catalyst particles for fine olefin polymerization, the prepolymerized catalyst for fine olefin polymerization that passes through the porous material for separation is passed. The polymerization catalyst particles may be removed. Such a fine powder removing step will be described in more detail below with reference to FIG.

  FIG. 1 is an explanatory view for explaining one embodiment of a method for producing a prepolymerization catalyst for olefin polymerization according to the present invention. As shown in FIG. 1, the classifier 1 used in this embodiment includes a suction port 2 for an aggregate of prepolymerized catalyst particles for olefin polymerization, a fan 3 for circulating gas in the classifier 1, and a small olefin polymerizer. Screen for separating preliminarily polymerized catalyst particles (porous body for separation) 4, discharge port 5 for discharging the fractionated prepolymerized catalyst particles for olefin polymerization, and minute prepolymerized catalyst particles for olefin polymerization An outlet 6 is provided for taking out the olefin polymerization prepolymerization catalyst from which has been removed. The sorting screen 4 is fixed in the classification device 1 between the suction port 2 and the discharge port 5, and the outlet 6 is provided closer to the suction port 2 than the sorting screen 4. In the present embodiment, the classification device 1 is filled with nitrogen. The sorting screen 4 can be a mesh or the like in which pores are formed by having a mesh structure with a constant mesh, and the mesh is provided toward the suction port 2 side.

  The aggregate of the prepolymerized catalyst particles for olefin polymerization sucked from the suction port 2 is circulated in the classifier 1 by nitrogen circulating in the classifier 1 by rotating the fan 3. Then, among the prepolymerized catalyst particles for olefin polymerization that have reached the separation screen 4, the prepolymerized catalyst particles for olefin polymerization that pass through the openings of the screen for separation 4 are discharged from the discharge port 5 to the outside of the classification device 1. The prepolymerized catalyst particles for olefin polymerization that do not pass through the openings of the separation screen 4 are taken out from the outlet 6.

  Thus, by separating the particles passing through the separation screen 4 and the particles not passing through and separating them, the prepolymerized catalyst particles for olefin polymerization are removed from the aggregate of the prepolymerized catalyst particles for olefin polymerization. To do. That is, the olefin polymerization prepolymerization catalyst having a desired particle size distribution can be taken out by appropriately selecting the opening of the separation screen 4 in accordance with the particle size of the olefin polymerization prepolymerization catalyst particles to be removed.

  As described above, according to the method for producing a prepolymerization catalyst for olefin polymerization according to the present invention, from the aggregate of prepolymerization catalyst particles for olefin polymerization in which olefin is prepolymerized, fine prepolymerization catalyst particles for olefin polymerization are obtained. Since the fine powder removal process to remove is included, the prepolymerization catalyst for olefin polymerization with little fine powder content can be manufactured. In addition, according to the method for producing a prepolymerized catalyst for olefin polymerization according to the present invention, the prepolymerized catalyst particles for olefin polymerization obtained by prepolymerization of olefin are classified, so that fine powder generated in the prepolymerization stage of the catalyst for olefin polymerization is also removed. It is possible to produce a prepolymerization catalyst for olefin polymerization with a small content of fine powder.

  Further, when the olefin polymerization catalyst component before the olefin is prepolymerized is classified by sieving or spraying, there is a problem that brittle fracture is likely to occur due to collision between the catalyst components and a new fine powder component is generated. However, according to the method for producing a prepolymerized catalyst for olefin polymerization according to the present invention, since the catalyst particles after the prepolymerization of the olefin are classified, such a problem does not occur. Furthermore, it is possible to remove the catalyst component that is not supported on the carrier during the preparation of the catalyst component for olefin polymerization, and it is possible to produce a prepolymerized catalyst for olefin polymerization with good properties.

(Catalyst component preparation process)
The method for producing a prepolymerized catalyst for olefin polymerization according to the present invention may further include a step of preparing a catalyst component for olefin polymerization. That is, in the present invention, from the aggregate of prepolymerized catalyst particles for olefin polymerization obtained by prepolymerizing olefin to the olefin polymerization catalyst component obtained in the preparation step of the olefin polymerization catalyst component, a minute olefin is obtained. The prepolymerized catalyst particles for polymerization may be removed.

(Preliminary polymerization process)
The method for producing a pre-polymerization catalyst for olefin polymerization according to the present invention may further include a pre-polymerization step of pre-polymerizing the olefin with the catalyst component for olefin polymerization. That is, in the present invention, the olefin polymerization catalyst component prepared in the above preparation step is preliminarily polymerized with olefin in the prepolymerization step, and the resulting prepolymerized catalyst particle aggregate for olefin polymerization is used for minute olefin polymerization. The prepolymerized catalyst particles may be removed.

  Examples of the olefin used for the prepolymerization include ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-octene, 4-methyl-1-pentene, cyclopentene, cyclohexene and the like. These can be used alone or in combination of two or more. Preferably, ethylene alone, or a combination of ethylene and α-olefin, more preferably ethylene alone, or at least one α-olefin selected from 1-butene, 1-hexene and 1-octene, and ethylene Is used in combination.

  The content of the prepolymerized polymer in the aggregate of prepolymerized catalyst particles for olefin polymerization is usually 0.01 to 1000 g, and more preferably 0.05 to 500 g, per 1 g of the promoter component. More preferably, it is 0.1 to 200 g.

  The method for prepolymerizing the catalyst component for olefin polymerization may be a continuous polymerization method or a batch polymerization method, and examples thereof include a batch type slurry polymerization method, a continuous type slurry polymerization method, and a continuous gas phase polymerization method. Examples of the method for introducing the catalyst component for olefin polymerization into the polymerization reaction tank for performing prepolymerization include, for example, a method in which an inert gas such as nitrogen and argon, hydrogen, ethylene, and the like are used in a moisture-free state, A method is used in which the components are dissolved or diluted in a solvent and charged in a solution or slurry state.

  When the prepolymerization is performed by the slurry polymerization method, for example, a saturated aliphatic hydrocarbon compound is used as the solvent, and examples of the saturated aliphatic hydrocarbon compound include propane, normal butane, isobutane, normal pentane, isopentane, normal Hexane, cyclohexane, heptane and the like can be mentioned. These may be used alone or in combination of two or more. The saturated aliphatic hydrocarbon compound preferably has a boiling point of 100 ° C. or less at normal pressure, more preferably 90 ° C. or less at normal pressure, and propane, normal butane, isobutane, normal pentane, isopentane, normal hexane. More preferred is cyclohexane.

  Moreover, when prepolymerization is performed by the slurry polymerization method, the amount of the catalyst component for olefin polymerization per liter of the solvent is, for example, 0.1 to 600 g, preferably 0.5 to 300 g. The prepolymerization temperature is, for example, -20 to 100 ° C, preferably 0 to 80 ° C. During the prepolymerization, the polymerization temperature may be appropriately changed. Moreover, the partial pressure of olefins in the gas phase part during prepolymerization is, for example, 0.001 to 2 MPa, and preferably 0.01 to 1 MPa. The prepolymerization time is, for example, 2 minutes to 15 hours.

[Olefin polymer production method]
The method for producing an olefin polymer according to the present invention performs olefin polymerization using the olefin polymerization prepolymerized catalyst produced by the above-described method for producing an olefin polymerization prepolymerized catalyst according to the present invention.

  In the present invention, the polymerization is intended not only for homopolymerization but also for copolymerization, and the polymer is intended not only for homopolymers but also for copolymers. The olefin used for the polymerization of the olefin may be the same as or different from the olefin used for the prepolymerization described above, and a plurality of olefins may be used in combination.

  In the present invention, examples of the method for polymerizing olefins include a gas phase polymerization method, a slurry polymerization method, and a bulk polymerization method. A gas phase polymerization method is preferable, and a continuous gas phase polymerization method is more preferable. The gas phase polymerization reaction apparatus used in the polymerization method is, for example, an apparatus having a fluidized bed type reaction tank, and preferably an apparatus having a fluidized bed type reaction tank having an enlarged portion. A stirring blade may be installed in the reaction vessel.

  As a method for supplying the prepolymerization catalyst for olefin polymerization and other catalyst components to the polymerization reaction tank, for example, a method of supplying in an moisture-free state using an inert gas such as nitrogen or argon, hydrogen, ethylene or the like A method is used in which each component is dissolved or diluted in a solvent and supplied in a solution or slurry state.

  When the olefin is vapor-phase polymerized, the polymerization temperature is, for example, less than the temperature at which the olefin polymer melts, preferably 0 to 150 ° C, more preferably 30 to 100 ° C. An inert gas may be introduced into the polymerization reaction tank, and hydrogen may be introduced as a molecular weight regulator. Further, an organoaluminum compound or an electron donating compound may be introduced.

  The polymerization pressure should just be in the range in which an olefin can exist as a gaseous phase within a fluidized bed reactor, for example, 0.1-5.0 MPa, Preferably it is 1.5-3.0 MPa. Moreover, the gas flow rate in a reactor is 10-100 cm / sec, for example, Preferably it is 20-70 cm / sec. The usage-amount of the co-catalyst component of the prepolymerization catalyst for olefin polymerization used for the gas phase polymerization of olefin is, for example, 0.00001 to 0.001 g with respect to 1 g of olefin.

  Examples of the olefin used for the polymerization include ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1-dodecene, 4-methyl-1-pentene. And olefins having 2 to 20 carbon atoms such as 4-methyl-1-hexene. These may be used independently and may use 2 or more types together. Preferred are ethylene, 1-butene, 1-hexene, 4-methyl-1-pentene and 1-octene.

  The method for producing an olefin polymer according to the present invention is suitable for copolymerization of ethylene and an α-olefin having 3 to 20 carbon atoms, and as a combination of ethylene and α-olefin, ethylene / 1-butene, Ethylene / 1-hexene, ethylene / 4-methyl-1-pentene, ethylene / 1-octene, ethylene / 1-butene / 1-hexene, ethylene / 1-butene / 4-methyl-1-pentene, ethylene / 1- Butene / 1-octene, ethylene / 1-hexene / 1-octene and the like, preferably ethylene / 1-hexene, ethylene / 4-methyl-1-pentene, ethylene / 1-butene / 1-hexene, ethylene / 1-butene / 1-octene, ethylene / 1-hexene / 1-octene.

  Further, in the polymerization of olefin, if necessary, another monomer may be introduced into the polymerization reaction tank, and the other monomer may be copolymerized as long as the effects of the present invention are not impaired. Examples of the other monomers include diolefins, cyclic olefins, alkenyl aromatic hydrocarbons, α, β-unsaturated carboxylic acids, and the like.

  Specific examples thereof include 1,5-hexadiene, 1,4-hexadiene, 1,4-pentadiene, 1,7-octadiene, 1,8-nonadiene, 1,9-decadiene, 4-methyl-1 , 4-hexadiene, 5-methyl-1,4-hexadiene, 7-methyl-1,6-octadiene, 5-ethylidene-2-norbornene, dicyclopentadiene, 5-vinyl-2-norbornene, 5-methyl-2 -Norbornene, norbornadiene, 5-methylene-2-norbornene, 1,5-cyclooctadiene, 5,8-endomethylenehexahydronaphthalene, 1,3-butadiene, isoprene, 1,3-hexadiene, 1,3-octadiene , 1,3-cyclooctadiene, 1,3-cyclohexadiene and other diolefins; cyclopentene, Chlohexene, norbornene, 5-methylnorbornene, 5-ethylnorbornene, 5-butylnorbornene, 5-phenylnorbornene, 5-benzylnorbornene, tetracyclododecene, tricyclodecene, tricycloundecene, pentacyclopentadecene, pentacyclo Hexadecene, 8-methyltetracyclododecene, 8-ethyltetracyclododecene, 5-acetylnorbornene, 5-acetyloxynorbornene, 5-methoxycarbonylnorbornene, 5-ethoxycarbonylnorbornene, 5-methyl-5-methoxycarbonylnorbornene Cyclic olefins such as 5-cyanonorbornene, 8-methoxycarbonyltetracyclododecene, 8-methyl-8-tetracyclododecene, 8-cyanotetracyclododecene; Alkenylbenzene such as tylene, 2-phenylpropylene, 2-phenylbutene, 3-phenylpropylene, p-methylstyrene, m-methylstyrene, o-methylstyrene, p-ethylstyrene, m-ethylstyrene, o-ethylstyrene 2,4-dimethylstyrene, 2,5-dimethylstyrene, 3,4-dimethylstyrene, 3,5-dimethylstyrene, 3-methyl-5-ethylstyrene, p-tertiary butylstyrene, p-second Alkyl styrene such as grade butyl styrene, bisalkenyl benzene such as divinylbenzene, alkenyl aromatic hydrocarbon such as alkenyl naphthalene such as 1-vinylnaphthalene; acrylic acid, methacrylic acid, fumaric acid, maleic anhydride, itaconic acid, itaconic anhydride Acid, bicyclo (2,2,1) -5-heptene-2, Α, β-unsaturated carboxylic acids such as 3-dicarboxylic acids; metal salts of α, β-unsaturated carboxylic acids such as sodium, potassium, lithium, zinc, magnesium, calcium; methyl acrylate, ethyl acrylate, acrylic acid α such as n-propyl, isopropyl acrylate, t-butyl acrylate, 2-ethylhexyl acrylate, methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate , Β-unsaturated carboxylic acid alkyl esters; unsaturated dicarboxylic acids such as maleic acid and itaconic acid; vinyl acetate, vinyl propionate, vinyl caproate, vinyl caprate, vinyl laurate, vinyl stearate, vinyl trifluoroacetate, etc. Vinyl ester; acrylic acid Rishijiru, glycidyl methacrylate, and unsaturated carboxylic acid glycidyl ester of itaconic acid monoglycidyl ester.

  According to the method for producing an olefin polymer according to the present invention, an olefin is polymerized using the prepolymerized catalyst for olefin polymerization produced by the method for producing a prepolymerized catalyst for olefin polymerization according to the present invention. It is possible to stably and continuously polymerize olefins without causing problems such as agglomeration of the prepolymerization catalyst for olefin polymerization and clogging of cyclones.

  The measured value of each item in an Example was measured with the following method.

(1) Density (Unit: Kg / m ³ )
It measured according to the method prescribed | regulated to A method among JISK7112-1980. The sample was annealed according to JIS K6760-1995.

(2) Melt flow rate (MFR, unit: g / 10 minutes)
According to the method defined in JIS K7210-1995, the measurement was performed under the conditions of a load of 21.18 N and a temperature of 190 ° C.

(3) Coarse Grain Ratio The polymer particles were sieved with a sieve having a mesh size of 5 mm, and the weight ratio of the polymer particles that did not pass through the sieve was determined.

(4) Scattering rate The ratio of the amount of powder (mainly fine particles) scattered per unit time in the cyclone installed in the line circulating unreacted raw material gas divided by the amount of product powder generated at the same time was obtained. .

(5) Particle size distribution of prepolymerization catalyst Jet pressure using 0.5 to 350 μm lens with a laser diffraction particle size distribution measuring device (HELOS & ROOD (model number HELOS / KF-M RODOS / M) manufactured by Sympatec Gmbh) (Dispersion pressure) The particle size distribution was measured at 1.5 bar.

[Example 1]
(1) Preparation of promoter component In a reactor equipped with a nitrogen-replaced stirrer, 24 kg of toluene as a solvent, heat-treated silica at 300 ° C. under nitrogen flow (Sypolol 948 manufactured by Devison; average particle size = 55 μm; pore (Volume = 1.67 ml / g; specific surface area = 325 m ² / g) 2.81 kg was added and stirred. Then, after cooling to 5 ° C., a mixed solution of 0.91, 1 kg of 1,1,1,3,3,3-hexamethyldisilazane and 1.43 kg of toluene was maintained in 32 minutes while maintaining the reactor temperature at 5 ° C. It was dripped. After completion of dropping, the mixture was stirred at 5 ° C. for 1 hour and at 95 ° C. for 3.3 hours. Thereafter, the obtained solid product was washed 6 times with 21 kg of toluene. Thereafter, 7.1 kg of toluene was added and allowed to stand overnight to obtain a toluene slurry.

  To the above toluene slurry, 1.75 kg of a 50 wt% diethylzinc hexane solution and 1.0 kg of hexane as a solvent were added and stirred. Then, after cooling to 5 ° C., a mixed solution of 0.78 kg of trifluorophenol and 1.41 kg of toluene as a solvent was added dropwise over 61 minutes while keeping the temperature of the reactor at 5 ° C. After completion of dropping, the mixture was stirred at 5 ° C. for 1 hour and at 40 ° C. for 1 hour. Thereafter, the temperature was lowered to 22 ° C., and 0.11 kg of water was added dropwise over 1.5 hours while keeping the temperature of the reactor at 5 ° C. After completion of dropping, the mixture was stirred at 22 ° C for 1.5 hours, at 40 ° C for 2 hours, and further at 80 ° C for 2 hours. Stirring was stopped and the supernatant liquid was withdrawn until the remaining amount reached 16 liters, and 11.6 kg of toluene was added and stirred. The temperature was raised to 95 ° C. and stirred for 4 hours. The obtained solid product was washed 4 times with 20.8 kg of toluene and 3 times with 24 liters of hexane. Thereafter, the promoter component was obtained by drying. As a result of elemental analysis, Zn = 11 wt%, Si = 30 wt%, F = 5.9 wt%, and N = 2.3 wt%.

(2) Prepolymerization Into a reactor equipped with a stirrer that was previously purged with nitrogen (internal volume 210 liters), 80 liters of butane was charged at room temperature, and then racemic-ethylenebis (1-indenyl) zirconium diphenoxide 89. 5 mmol was charged. Thereafter, the temperature in the reactor was increased to 50 ° C. and stirred for 2 hours. The temperature in the reactor was lowered to 30 ° C., and 0.1 kg of ethylene was added. Next, 701 g of the promoter component obtained in Example 1 (1) was added. Thereafter, 0.1 liter of hydrogen was introduced at normal temperature and pressure. After the system was stabilized, 263 mmol of triisobutylaluminum was added to start prepolymerization.

  After the start of the prepolymerization, the polymerization temperature in the reactor was operated at 30 ° C. for 0.5 hours, and then the temperature was raised to 50 ° C. over 30 minutes. For the first 0.5 hours, ethylene is supplied at 0.7 kg / hour, hydrogen is supplied at a normal pressure and normal pressure at a rate of 0.7 liter / hour. 2.8 kg / hour, hydrogen was supplied at a normal temperature and a normal pressure at a rate of 8.5 liter / hour, and preliminary polymerization was carried out for a total of 7 hours. After completion of the prepolymerization, the reactor internal pressure was purged to 0.5 MPaG, the slurry prepolymerization catalyst was transferred to a dryer, and nitrogen circulation drying was performed to obtain a prepolymerization catalyst. The amount of the prepolymerized ethylene polymer in the prepolymerized catalyst was 28.4 g per 1 g of the promoter component.

  As a result of the particle size distribution measurement, the ratio of particles having an average particle size of 150 μm and 98 μm or less of the prepolymerized catalyst was 9.7 wt%.

(3) Fine powder removal step In a non-liner type high boulder manufactured by Toyo Hitech Co., Ltd. equipped with a mesh with a mesh size of 150 μm, the prepolymerized catalyst obtained in Example 1 (2) above was charged under a nitrogen atmosphere. By removing fine powder, a prepolymerization catalyst for olefin polymerization was obtained.

  As a result of the particle size distribution measurement, the proportion of particles having an average particle size of 185 μm and 120 μm or less was 4.2 wt%, and the proportion of particles having an average particle size of 98 μm or less was 0.6 wt%.

(4) Fluidized bed gas phase polymerization (inner diameter is 50 cm) using a fluidized bed type continuous gas phase polymerization reactor, polymerization temperature: 87 ° C., pressure: 2.0 MPaG, hold-up amount: 80 kg, gas composition: ethylene 86.8 mol%, hydrogen 1.1 mol%, 1-hexene 1.1 mol%, nitrogen 10.7 mol%, hexane 0.3 mol%, circulating gas flow rate: co-reduction of ethylene and 1-hexene under the polymerization conditions of 50 cm / sec. Polymerization was performed.

During the polymerization, the prepolymerization catalyst for olefin polymerization obtained in Example 1 (3) was supplied at a supply amount of 44 g / hr. During the polymerization, triethylamine was supplied at a supply rate of 0.3 mmol / hr and triisobutylaluminum was supplied at a supply rate of 10 mmol / hr to the polymerization reactor, and an average of 21.0 kg / h of ethylene-1-hexene was added. A polymer was produced. The scattering rate was 1.1 wtppm, and almost no lumps were generated. The density of the obtained ethylene-1-hexene copolymer was 920.2 kg / m ³ and the MFR was 0.54 g / 10 min.

  After several months of operation, the inside of the reactor was inspected for openness, but almost no fouling in the enlarged part was observed.

[Example 2]
(1) Fine powder removal process The prepolymerization catalyst was obtained by the method similar to Example 1 (1) (2). The prepolymerization amount of the ethylene polymer in the prepolymerization catalyst was 28.2 g per 1 g of the olefin polymerization catalyst component.

  As a result of measuring the particle size distribution, the ratio of particles having an average particle size of 152 μm and 99 μm or less of the prepolymerized catalyst was 9.5 wt%.

  In a non-liner type high boulder manufactured by Toyo Hitech Co., Ltd. equipped with a mesh with a mesh size of 132 μm, the prepolymerized catalyst obtained in Example 2 (1) above was placed in a nitrogen atmosphere to remove fine powder. As a result, a prepolymerized catalyst for olefin polymerization was obtained.

  As a result of the particle size distribution measurement, the ratio of particles having an average particle diameter of 187 μm and 122 μm or less was 4.5 wt%, and the ratio of particles having a particle diameter of 99 μm or less was 0.7 wt%.

(2) Fluidized bed gas phase polymerization (inner diameter is 50 cm) using a fluidized bed type continuous gas phase polymerization reactor, polymerization temperature: 87 ° C., pressure: 2.0 MPaG, hold-up amount: 80 kg, gas composition: ethylene 85.5 mol%, hydrogen 1.0 mol%, 1-hexene 1.0 mol%, nitrogen 12.2 mol%, hexane 0.3 mol%, circulation gas flow rate: co-reduction of ethylene and 1-hexene under the polymerization conditions of 50 cm / sec. Polymerization was performed.

During the polymerization, the prepolymerization catalyst for olefin polymerization obtained in Example 2 (1) was supplied at a supply amount of 46 g / hr. During the polymerization, triethylamine was supplied at a supply rate of 0.3 mmol / hr and triisobutylaluminum was supplied at a supply rate of 10 mmol / hr to the polymerization reactor, and an average of 22.0 kg / h of ethylene-1-hexene was added. A polymer was produced. The scattering rate was 2.7 wtppm, and almost no lumps were generated. The density of the obtained ethylene-1-hexene copolymer was 921.0 kg / m ³ , and the MFR was 0.5 g / 10 min.

  After several months of operation, the inside of the reactor was inspected for openness, but almost no fouling in the enlarged part was observed.

[Comparative Example 1]
(1) Preparation of prepolymerized catalyst A prepolymerized catalyst was obtained in the same manner as in Example 1 (1) and (2). The prepolymerization amount of the ethylene polymer in the prepolymerization catalyst was 26.9 g per 1 g of the promoter component.

  As a result of the particle size distribution measurement, the ratio of the average particle size of 149 μm and 97 μm or less was 8.2 wt%.

(2) Fluidized bed gas phase polymerization (inner diameter is 50 cm) using a fluidized bed type continuous gas phase polymerization reactor, polymerization temperature: 87 ° C., pressure: 2.0 MPaG, hold-up amount: 80 kg, gas composition: ethylene 86.7 mol%, hydrogen 0.9 mol%, 1-hexene 1.0 mol%, nitrogen 11.1 mol%, hexane 0.3 mol%, circulation gas flow rate: co-reduction of ethylene and 1-hexene under the polymerization conditions of 50 cm / sec. Polymerization was performed.

  During the polymerization, the prepolymerized catalyst of Comparative Example 1 (1) was supplied at a supply rate of 24 g / hr. During the polymerization, triethylamine was supplied at a supply rate of 0.3 mmol / hr and triisobutylaluminum was supplied at a supply rate of 10 mmol / hr to the polymerization reactor, and an average of 19.0 kg / h of ethylene-1-hexene was added. A polymer was produced. The scattering rate was 72 wtppm, the generation of lumps, and the average coarse particle rate was 15 wtppm. The resulting ethylene-1-hexene copolymer had a density of 920.6 kg / m @ 3 and an MFR of 0.45 g / 10 min.

  After the operation for 3 weeks, the operation was stopped by blocking the product powder extraction line. An open inspection of the tank was conducted, but a lot of fouling was observed in the enlarged part.

  According to the present invention, since a prepolymerization catalyst for olefin polymerization with a small content of fine particles can be produced, it can be suitably used in the field of continuous polymerization of olefin polymers.

1 Classifier 2 Suction port 3 Fan 4 Screen for sorting (porous material for sorting)
5 Discharge port 6 Take-out port

Claims (5)

  A method for producing a prepolymerized catalyst for olefin polymerization, comprising a fine powder removing step of removing fine prepolymerized catalyst particles for olefin polymerization from an aggregate of prepolymerized catalyst particles for olefin polymerization in which olefin is prepolymerized.   In the fine powder removing step, the preliminarily polymerized catalyst particles for olefin polymerization are removed by passing the dried aggregate through a porous body for separation through which the prepolymerized catalyst particles for olefin polymerization are passed. Item 2. A method for producing a prepolymerization catalyst for olefin polymerization according to Item 1.   The olefin according to claim 1 or 2, wherein the aggregate is obtained by prepolymerizing an olefin with a catalyst component for olefin polymerization formed by contacting a promoter component, a metallocene compound, and an organoaluminum compound. A method for producing a prepolymerization catalyst for polymerization. The said prepolymerization catalyst particle for minute olefin polymerization is a prepolymerization catalyst particle for olefin polymerization which has a particle size below R represented by following formula (1). Of producing a prepolymerized catalyst for olefin polymerization.
R = (Average particle diameter of prepolymerized catalyst particles for olefin polymerization in the aggregate) × 0.65 (1)   The manufacturing method of an olefin polymer which superposes | polymerizes an olefin using the prepolymerization catalyst for olefin polymerization manufactured by the manufacturing method of any one of Claims 1-4.

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