JP2006299069A - Solid catalyst component for olefin polymerization, olefin polymerization catalyst and method for producing olefin polymer - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a solid catalyst component giving an olefin polymer having low powder content while keeping principal properties such as activity, stereoregularity and powder form at high level and provide an olefin polymerization catalyst and a method for producing an olefin polymer. <P>SOLUTION: The solid catalyst component for olefin polymerization is produced by repeating a supporting treatment composed of a contacting step and a washing step once or more by using (a) a halogen-containing titanium compound, (b) an alkoxy-containing magnesium compound, (c) a halogen-containing silicon compound or (d) an aromatic hydrocarbon solvent and (e) an electron-releasing compound and carrying out the washing of the catalyst component, as at least the last washing step, with a prescribed surfactant in an amount of ≥0.05 wt.% in total based on the solid catalyst component before the last washing treatment. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a solid catalyst component useful for olefin homopolymerization or copolymerization thereof, a catalyst for olefin polymerization, and a method for producing these homopolymers or copolymers.

  Conventionally, as a catalyst for homopolymerization or copolymerization of ethylene or propylene, etc., magnesium chloride or magnesium alkoxide is used as a carrier raw material for olefin polymerization catalyst, and a method of contacting titanium tetrachloride and phthalate ester has been widely implemented. Improvement of catalytic activity, improvement of stereoregularity of the resulting polymer, improvement of the powder form of the polymer, and the like have been attempted (Patent Documents 1 and 2).

  Among them, a method in which magnesium alkoxide is treated with a chlorinating agent such as silicon tetrachloride, contacted and reacted with titanium tetrachloride at a high temperature of about 125 ° C., and then washed with an inert solvent at a high temperature of about 125 ° C. (Patent Documents 3 and 4), after magnesium alkoxide is contacted with titanium tetrachloride at a high temperature of about 125 ° C. in an aromatic hydrocarbon solvent and then washed with an inert solvent at a high temperature of about 125 ° C. By the characteristic method (Patent Document 5), a powder having high activity, high stereoregularity, spherical shape and relatively narrow particle size distribution is obtained.

  However, in the above method, fine powder is generated in the obtained solid catalyst component, and the fine powder in the polymerized powder generated thereby triggers, clogging of the monomer recovery system filter of the gas apparatus, powder adhesion to the stirrer, etc. There was a case that led to trouble.

Furthermore, for fine powder removal in the catalyst, the difference in sedimentation due to particle size is utilized, the method of extracting the supernatant after stopping the stirring in the catalyst slurry, the flow rate of the rising air flow by inert gas such as nitrogen after drying the catalyst In general, there is a case where fine powder remains in the product after classification or particles other than fine powder are classified, or the accuracy and yield are insufficient in some cases.
JP 58-811 A Japanese Patent Laid-Open No. 4-130107 JP-A-11-26918 JP 2001-233879 A JP 2003-201311 A

  The present invention has been made from the above viewpoint, and solid catalyst components and olefin polymerization that give an olefin polymer with a small amount of powder fine powder while maintaining basic performance such as activity, stereoregularity, and powder shape at a high level. It is an object of the present invention to provide a catalyst for production and a method for producing an olefin polymer.

  As a result of intensive research to achieve the above object, the present inventors have found that the object can be achieved by using a solid catalyst component obtained by washing with an antistatic agent. Completed.

That is, the present invention provides the following solid catalyst component, olefin polymerization catalyst, and olefin polymer production method.
1. Using the following components (a), (b), (c) and (e), or the following components (a), (b), (d) and (e), a supporting operation comprising a contacting step and a washing step is performed. Repeat at least once,
A solid catalyst component for olefin polymerization obtained by washing at least in the final washing step using the following antistatic agent in a total amount of 0.05% by weight or more based on the solid catalyst component before the final washing.
component:
(A) halogen-containing titanium compound (b) alkoxy-containing magnesium compound (c) halogen-containing silicon compound (d) aromatic hydrocarbon solvent (e) electron donating compound antistatic agent:
1. An antistatic agent selected from anionic surfactants, cationic surfactants, nonionic surfactants, amphoteric surfactants, and mixtures thereof. The following components (a), (b), (c) and (e), or the following components (a), (b), (d) and (e) are contacted and reacted at 120 ° C. or higher and 150 ° C. or lower, Washing at 100 ° C. or higher and 150 ° C. or lower with an inert solvent to obtain a solid catalyst precursor,
The solid catalyst precursor is contacted and reacted again with the following component (a) at 120 ° C. or higher and 150 ° C. or lower,
A solid catalyst component for olefin polymerization obtained by adding the following antistatic agent in a total amount of 0.05% by weight or more to the solid catalyst precursor and washing with an inert solvent.
component:
(A) halogen-containing titanium compound (b) alkoxy-containing magnesium compound (c) halogen-containing silicon compound (d) aromatic hydrocarbon solvent (e) electron donating compound antistatic agent:
2. An antistatic agent selected from anionic surfactants, cationic surfactants, nonionic surfactants, amphoteric surfactants, and mixtures thereof. The solid catalyst component for olefin polymerization according to 1 or 2, wherein the antistatic agent is a mixture of an anionic surfactant and a cationic surfactant.
4). The solid catalyst component for olefin polymerization according to any one of 1 to 3, wherein the anionic surfactant includes a sulfur compound, and the cationic surfactant includes a nitrogen-containing polymer.
5. The alkoxy-containing magnesium compound (b) was obtained by reacting metal magnesium, alcohol, and halogen containing a halogen atom in an amount of 0.0001 gram atom or more with respect to 1 gram atom of metal magnesium and / or a halogen-containing compound. The solid catalyst component for olefin polymerization according to any one of 1 to 4, which is a catalyst.
6). The solid catalyst component for olefin polymerization according to any one of 1 to 5, wherein the halogen-containing silicon compound (c) is silicon tetrachloride.
7). An olefin polymerization catalyst comprising the following (A) and (B).
(A) Solid catalyst component for olefin polymerization according to any one of 1 to 6 (B) Organoaluminum compound The olefin polymerization catalyst according to 7, further comprising an electron donating compound (C).
A method for producing an olefin polymer, wherein an olefin is polymerized using the catalyst for olefin polymerization according to 9.7 or 8.

  According to the present invention, a solid catalyst component, an olefin polymerization catalyst, and an olefin polymer that give an olefin polymer with a small amount of powder fine powder while maintaining basic performance such as activity, stereoregularity, and powder shape at a high level. The manufacturing method of can be provided.

In the present invention, an olefin is polymerized by a catalyst containing (A) a solid catalyst component, (B) an organoaluminum compound, and, if necessary, (C) an electron donating compound.
Below, each catalyst component, a preparation method, a polymerization method, etc. are demonstrated.

[I] Each catalyst component (A) Solid catalyst component The solid catalyst component of the present invention comprises a halogen-containing titanium compound (a), an alkoxy-containing magnesium compound (b), a halogen-containing silicon compound (c), and an electron donating compound (e ). Alternatively, it is produced using a halogen-containing titanium compound (a), an alkoxy-containing magnesium compound (b), an aromatic hydrocarbon solvent (d), and an electron donating compound (e). In the manufacturing method, the supporting operation including the contact step and the cleaning step is repeated once or more, and an antistatic agent is used at least in the final cleaning step.

(A) Halogen-containing titanium compound Although there is no restriction | limiting as a halogen-containing titanium compound, The compound represented by general formula (I) can be used preferably.
Ti (OR ¹ ) _n X _4-n (I)
(In the formula, X is a halogen atom, R ¹ is a hydrocarbon group having 1 to 10 carbon atoms, and they may be the same as or different from each other. N is an integer of 1 to 4.)

In the general formula (I), X represents a halogen atom, among which a chlorine atom and a bromine atom are preferable, and a chlorine atom is particularly preferable. The hydrocarbon group for R ¹ may be a saturated group or an unsaturated group, and may be a linear group, a branched chain group, or a cyclic group. An alkyl group, an alkenyl group, a cycloalkenyl group, an aryl group, an aralkyl group, and the like are preferable, and a linear or branched alkyl group is particularly preferable. When a plurality of —OR ¹ are present, they may be the same as or different from each other. Specific examples of R ¹ include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, isobutyl group, n-pentyl group, n-hexyl group, n-heptyl group, Examples include n-octyl group, n-decyl group, allyl group, butenyl group, cyclopentyl group, cyclohexyl group, cyclohexenyl group, phenyl group, tolyl group, benzyl group, phenethyl group and the like.

  Specific examples of the halogen-containing titanium compound represented by the general formula (I) include titanium tetrachlorides such as titanium tetrachloride, titanium tetrabromide, and titanium tetraiodide; methoxy titanium trichloride, ethoxy titanium trichloride, propoxy Trihalogenated alkoxytitanium such as titanium trichloride, n-butoxytitanium trichloride, ethoxytitanium tribromide; dimethoxytitanium dichloride, diethoxytitanium dichloride, diisopropoxytitanium dichloride, di-n-propoxytitanium dichloride, diethoxytitanium dichloride Dihalogenated dialkoxy titanium such as bromide; trimethoxy titanium chloride, triethoxy titanium chloride, triisopropoxy titanium chloride, tri-n-propoxy titanium chloride, tri-n-butoxy titanium chloride, etc. It can be mentioned monohalogenated trialkoxy titanium. Among these, a high halogen-containing titanium compound, particularly titanium tetrachloride is preferable from the viewpoint of polymerization activity. These titanium compounds may be used alone or in combination of two or more.

(B) Alkoxy-containing magnesium compound Although there is no restriction | limiting as an alkoxy-containing magnesium compound, General formula (II)
MgOR ² _q R ³ _2-q (II)
An alkoxy-containing magnesium compound represented by the formula can be preferably used.

In the general formula (II), R ² and R ³ may be the same or different, R ² represents a hydrocarbon group, and R ³ represents a hydrocarbon group or a halogen atom. q shows the integer of 1-2.
Here, as the hydrocarbon group of R ² and R ³ , an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group, an aryl group, an aralkyl group, etc., and as the halogen atom of R ³ , chlorine, bromine, iodine, Fluorine etc. can be mentioned.

  Specific examples of the magnesium compound represented by the general formula (II) include dimethoxymagnesium, diethoxymagnesium, dipropoxymagnesium, dibutoxymagnesium, dihexyloxymagnesium, dioctoxymagnesium, diphenoxymagnesium, and dicyclohexyloxymagnesium. Dialkoxymagnesium, diallyloxymagnesium; alkoxyalkylmagnesium such as ethoxyethylmagnesium, phenoxymethylmagnesium, ethoxyphenylmagnesium, cyclohexyloxyphenylmagnesium, allyloxyalkylmagnesium, alkoxyallylmagnesium, allyloxyallylmagnesium; butoxymagnesium chloride , Cyclohexyloxymagnesium chloride, phenoxymagnes Um chloride, ethoxy magnesium chloride, ethoxy magnesium bromide, butoxy magnesium bromide, alkoxy magnesium halides such as ethoxy magnesium iodide, allyloxy magnesium halides; magnesium halides such as magnesium chloride, magnesium bromide, magnesium iodide, etc. .

  Among these magnesium compounds, dialkoxymagnesium can be preferably used from the viewpoint of polymerization activity and stereoregularity, and diethoxymagnesium is particularly preferable.

  From the viewpoint of the powder form, polymerization activity and stereoregularity of the resulting polymer, the production method of the alkoxy-containing magnesium compound includes a halogen atom in an amount of 0.0001 gram atom or more based on metal magnesium, alcohol, and metal magnesium. A method of reacting with a halogen and / or a halogen-containing compound is preferable. Hereinafter, this manufacturing method will be described.

  In this case, the shape of the metallic magnesium is not particularly limited. Therefore, metallic magnesium having an arbitrary particle size, such as granular magnesium, ribbon, powder, etc., can be used. Moreover, although the surface state of metallic magnesium is not limited, one in which a film such as magnesium hydroxide is not formed on the surface is preferable.

  Although the kind of alcohol is not limited, C1-C6 lower alcohol is preferable. In particular, ethanol is preferable because a solid catalyst component that significantly improves the expression of catalyst performance can be obtained. The purity and water content of the alcohol are not limited, but if an alcohol having a high water content is used, magnesium hydroxide is generated on the surface of the metal magnesium, so that it is preferable to use an alcohol having a water content of 1% or less, particularly 2000 ppm or less. . In order to obtain a better morphology, the lower the moisture content, the better, and generally 200 ppm or less is desirable.

  Although the kind of halogen is not limited, chlorine, bromine or iodine, particularly iodine is preferably used.

The kind of halogen-containing compound is not limited, and any compound containing a halogen atom can be used. In this case, the type of halogen atom is not limited, but is preferably chlorine, bromine or iodine. Of the halogen-containing compounds, a halogen-containing metal compound is particularly preferable. Specifically, MgCl ₂ , MgI ₂ , Mg (OC ₂ H ₅ ) Cl, Mg (OC ₂ H ₅ ) I, MgBr ₂ , CaCl ₂ , NaCl, KBr and the like can be preferably used as the halogen-containing compound. Among these, MgCl ₂ is particularly preferable. These states, shapes, particle sizes, and the like are not particularly limited, and may be arbitrary, for example, can be used in a solution in an alcohol solvent (for example, ethanol).

  Although it does not ask | require about the quantity of alcohol, Preferably it is 2-100 mol with respect to 1 mol of metal magnesium, Most preferably, it is 5-50 mol. If the amount of alcohol is too large, the yield of the alkoxy-containing magnesium compound (b) having a good morphology may be reduced. If the amount is too small, stirring in the reaction vessel may not be performed smoothly. However, it is not limited to the molar ratio.

  The amount of the halogen or halogen-containing compound used is 0.0001 gram atom or more, preferably 0.0005 gram atom or more, more preferably 0.001 gram atom or more with respect to 1 mol of metal magnesium. When the amount is less than 0.0001 gram atom, there is not much difference from the amount of halogen used as a reaction initiator, and when the obtained alkoxy-containing magnesium compound (b) is used as a catalyst support, the activity and the morphology of the produced polymer are poor. Become. The upper limit of the amount of halogen used is not particularly defined, but may be appropriately selected within a range in which the desired alkoxy-containing magnesium compound (b) can be obtained. Generally, it is selected in the range of less than 0.06 gram atoms.

  In the present invention, each of halogen and halogen-containing compounds may be used alone or in combination of two or more. A halogen and a halogen-containing compound may be used in combination. Thus, also when using together 2 or more types of halogen and / or a halogen containing compound, the quantity of all the halogen atoms is as above-mentioned.

  By appropriately selecting the amount of halogen and / or halogen-containing compound used, the particle size of the alkoxy-containing magnesium compound (b) can be freely controlled.

  The above reaction is usually allowed to proceed for about 1 to 30 hours until generation of hydrogen gas is not observed to obtain an alkoxy-containing magnesium compound.

  Specifically, when iodine is used as the halogen, solid iodine is charged into metal magnesium and alcohol, and then heated and reacted. Method of heating after dropwise addition of an alcohol solution of iodine in metal magnesium and alcohol And magnesium magnesium, a method of dropping an alcohol solution of iodine while heating the alcohol solution, and the like. Any of the methods is preferably carried out under an inert gas (for example, nitrogen gas, argon gas) atmosphere, optionally using an inert organic solvent (for example, a saturated hydrocarbon such as n-hexane).

  Regarding the addition of metal magnesium, alcohol and halogen, it is not necessary to add all of them from the beginning, and they may be added separately. Preferably, the entire amount of alcohol is added from the beginning, and the magnesium metal is added in several portions. In such a case, temporary mass generation of hydrogen gas can be prevented, which is highly desirable from the viewpoint of safety. Also, the reaction vessel can be downsized. Furthermore, it becomes possible to prevent entrainment of alcohol and halogen caused by a temporary large amount of hydrogen gas. The number of times of division may be determined in consideration of the scale of the reaction tank, and is not particularly limited, but is usually 5 to 10 times considering the complexity of the operation.

  Needless to say, the reaction itself may be either batch type or continuous type. Further, as a modified method, an operation in which a small amount of magnesium metal is first charged into the alcohol that has been charged in its entirety from the beginning, the product produced by the reaction is separated and removed in a separate tank, and then a small amount of metal magnesium is charged again. It is also possible to repeat.

  When the obtained alkoxy-containing magnesium compound (b) is used for the production of the next solid catalyst component (transition metal component) (A), a dried product may be used, or an inert solvent such as heptane after filtration. You may use what was washed with. In any case, the obtained alkoxy-containing magnesium compound (b) can be used in the following steps without performing a pulverizing operation or a classification operation for adjusting the particle size distribution. The alkoxy-containing magnesium compound (b) is nearly spherical and has a sharp particle size distribution. Furthermore, even if each particle is taken, the variation in sphericity is small.

  These alkoxy-containing magnesium compounds may be used alone or in combination of two or more. Further, it may be used by being supported on a support such as silica, alumina or polystyrene, or may be used as a mixture with halogen or the like.

(C) Halogen-containing silicon compound Examples of the halogen-containing silicon compound include silicon tetrachloride, silicon tetrabromide, tin tetrachloride, and hydrogen chloride. Among these, silicon tetrachloride is preferable. These compounds may be used alone or in combination of two or more.

(D) Aromatic hydrocarbon The aromatic hydrocarbon solvent is not limited, and may be any liquid as long as it is normal temperature, such as benzene, toluene, xylene, ethylbenzene, propylbenzene, and trimethylbenzene. it can. Of these, toluene, xylene, and ethylbenzene are preferably used.

(E) Electron-donating compound An electron-donating compound is used to enhance the stereoregularity of the olefin polymer. Examples of electron donating compounds include alcohols, phenols, ketones, aldehydes, carboxylic acids, malonic acids, succinic acids, esters of organic or inorganic acids, ethers such as monoethers, diethers or polyethers, etc. Examples thereof include oxygen-containing electron donors and nitrogen-containing electron donors such as ammonia, amine, nitrile and isocyanate.

  Among these, esters of polyvalent carboxylic acids are preferable, and esters of aromatic polyvalent carboxylic acids are more preferable. From the standpoint of polymerization activity, aromatic monocarboxylic acid monoesters and / or diesters are particularly preferred. In addition, an aliphatic hydrocarbon in which the organic group in the ester portion is linear, branched or cyclic is preferable. Specifically, phthalic acid, naphthalene-1,2-dicarboxylic acid, naphthalene-2,3-dicarboxylic acid, 5,6,7,8-tetrahydronaphthalene-1,2-dicarboxylic acid, 5,6,7, Methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl of dicarboxylic acids such as 8-tetrahydronaphthalene-2,3-dicarboxylic acid, indane-4,5-dicarboxylic acid, indane-5,6-dicarboxylic acid, t-butyl, n-pentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 1,1-dimethylpropyl, 1-methylpentyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, 1-ethylbutyl 2-ethylbutyl, n-hexyl, cyclohexyl, n-heptyl, n-octyl, n-nonyl, 2-methylhexyl And dialkyl esters such as syl, 3-methylhexyl, 4-methylhexyl, 2-ethylhexyl, 3-ethylhexyl, 4-ethylhexyl, 2-methylpentyl, 3-methylpentyl, 2-ethylpentyl, 3-ethylpentyl, etc. . Among these, phthalic acid diesters are preferable, and linear or branched aliphatic hydrocarbons having 4 or more carbon atoms in the organic group of the ester moiety are preferable.

  Preferred examples include di-n-butyl phthalate, diisobutyl phthalate, di-n-heptyl phthalate, diethyl phthalate and the like. In addition, these compounds may be used alone or in combination of two or more.

(B) Organoaluminum compound Although there is no restriction | limiting as an organoaluminum compound (B), The thing which has an alkyl group, a halogen atom, a hydrogen atom, an alkoxy group, an aluminoxane, and a mixture thereof can be used preferably. Specifically, trialkylaluminum such as trimethylaluminum, triethylaluminum, triisopropylaluminum, triisobutylaluminum, trioctylaluminum; dialkyl such as diethylaluminum monochloride, diisopropylaluminum monochloride, diisobutylaluminum monochloride, dioctylaluminum monochloride Examples include aluminum monochloride; alkylaluminum sesquihalides such as ethylaluminum sesquichloride; chain aluminoxanes such as methylaluminoxane. Among these organoaluminum compounds, trialkylaluminum having a lower alkyl group having 1 to 5 carbon atoms, particularly trimethylaluminum, triethylaluminum, tripropylaluminum and triisobutylaluminum are preferable. In addition, these organoaluminum compounds may be used alone or in combination of two or more.

(C) Electron-donating compound In the present invention, an electron-donating compound (C) is further used as necessary. Use of an electron donating compound is preferred because the stereoregularity of the resulting olefin polymer is improved. As the electron donating compound, an organosilicon compound having an alkoxy group, a nitrogen-containing compound, a phosphorus-containing compound, or an oxygen-containing compound can be used. Of these, an organosilicon compound having an alkoxy group is preferably used.

  Specific examples of the organosilicon compound having an alkoxy group include trimethylmethoxysilane, trimethylethoxysilane, triethylmethoxysilane, triethylethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, ethylisopropyldimethoxysilane, propylisopropyldimethoxysilane, diisopropyldimethoxy. Silane, diisobutyldimethoxysilane, isopropylisobutyldimethoxysilane, di-t-butyldimethoxysilane, t-butylmethyldimethoxysilane, t-butylethyldimethoxysilane, t-butylpropyldimethoxysilane, t-butylisopropyldimethoxysilane, t-butyl Butyldimethoxysilane, t-butylisobutyldimethoxysilane, t-butyl (s-butyl) dimethoxy Orchid, t-butylamyldimethoxysilane, t-butylhexyldimethoxysilane, t-butylheptyldimethoxysilane, t-butyloctyldimethoxysilane, t-butylnonyldimethoxysilane, t-butyldecyldimethoxysilane, t-butyl (3 3,3-trifluoromethylpropyl) dimethoxysilane, cyclohexylmethyldimethoxysilane, cyclohexylethyldimethoxysilane, cyclohexylpropyldimethoxysilane, cyclohexylisobutyldimethoxysilane, dimethoxysilane, dicyclohexyldimethoxysilane, cyclohexyl-t-butyldimethoxysilane, cyclopentylmethyldimethoxy Silane, cyclopentylethyldimethoxysilane, cyclopentylpropyldimethoxysilane, Til-t-butyldimethoxysilane, dicyclopentyldimethoxysilane, cyclopentylcyclohexyldimethoxysilane, bis (2-methylcyclopentyl) dimethoxysilane, bis (2,3-dimethylcyclopentyl) dimethoxysilane, α-naphthyl-1,1,2 -Trimethylpropyldimethoxysilane, n-tetradecanyl-1,1,2-trimethylpropyldimethyloxysilane, 1,1,2-trimethylpropylmethyldimethoxysilane, 1,1,2-trimethylpropylethyldimethoxysilane, 1,1, 2-trimethylpropylisopropyldimethoxysilane, 1,1,2-trimethylpropylcyclopentyldimethoxysilane, 1,1,2-trimethylpropylcyclohexyldimethoxysilane, 1,1,2-trimethylsilane Pyrmyristyl dimethoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, phenyltriethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, propyltrimethoxysilane, isopropyltrimethoxysilane, butyl Trimethoxysilane, butyltriethoxysilane, isobutyltrimethoxysilane, t-butyltrimethoxysilane, s-butyltrimethoxysilane, amyltrimethoxysilane, isoamyltrimethoxysilane, cyclopentyltrimethoxysilane, cyclohexyltrimethoxysilane, norbornanetri Methoxysilane, indenyltrimethoxysilane, 2-methylcyclopentyltrimethoxysilane, ethyltrii Propoxysilane, methylcyclopentyl (t-butoxy) dimethoxysilane, isopropyl (t-butoxy) dimethoxysilane, t-butyl (t-butoxy) dimethoxysilane, (isobutoxy) dimethoxysilane, t-butyl (t-butoxy) dimethoxysilane, Vinyltriethoxysilane, vinyltributoxysilane, chlorotriethoxysilane, γ-chloropropyltrimethoxysilane, γ-aminopropyltriethoxysilane, 1,1,2-trimethylpropyltrimethoxysilane, 1,1,2-trimethyl Propylisopropoxydimethoxysilane, 1,1,2-trimethylpropyl (t-butoxy) dimethoxysilane, tetramethoxysilane, tetraethoxysilane, tetrabutoxysilane, tetraisobutoxysilane, silicon Ethyl, butyl silicate, trimethyl phenoxy silane, methyl tri Lilo silane, vinyltris (beta-methoxyethoxy) silane, vinyl tris acetoxy silane, dimethyl tetraethoxy disiloxane and the like. These organosilicon compounds may be used alone or in combination of two or more.

  In addition, such an organosilicon compound may be prepared by previously reacting a silicon compound having no Si—O—C bond with an organic compound having an O—C bond, and reacting it during olefin polymerization. Alternatively, an organosilicon compound having a Si—O—C bond may be used. Specifically, for example, silicon tetrachloride is reacted with alcohol.

  Specific examples of nitrogen-containing compounds include 2,6-substituted piperidines such as 2,6-diisopropylpiperidine, 2,6-diisopropyl-4-methylpiperidine, and N-methyl2,2,6,6-tetramethylpiperidine. 2,5-substituted azolidines such as 2,5-diisopropylazolidine, N-methyl 2,2,5,5-tetramethylazolidine; N, N, N ′, N′-tetramethylmethylenediamine, N , N, N ′, N′-tetraethylmethylenediamine and the like; substituted imidazolidines such as 1,3-dibenzylimidazolidine and 1,3-dibenzyl-2-phenylimidazolidine, and the like.

  Specific examples of phosphorus-containing compounds include triethyl phosphite, tri n-propyl phosphite, triisopropyl phosphite, tri n-butyl phosphite, triisobutyl phosphite, diethyl n-butyl phosphite, diethyl phenyl phosphite and the like. Phosphites and the like.

  Specific examples of the oxygen-containing compound include 2,5-substituted tetrahydrofurans such as 2,2,5,5-tetramethyltetrahydrofuran and 2,2,5,5-tetraethyltetrahydrofuran; 1,1-dimethoxy-2,3 , 4,5-tetrachlorocyclopentadiene, 9,9-dimethoxyfluorene, dimethoxymethane derivatives such as diphenyldimethoxymethane, and the like.

[II] Preparation of solid catalyst component The solid catalyst component (A) is prepared by mixing the components (a), (b), (c) and (e) or the components (a), (b), (d) and ( Using e), the carrying operation comprising the contacting step and the washing step is repeated one or more times, and at least the final washing step is washed with an antistatic agent.
In the second and subsequent contact steps, the obtained solid catalyst component (solid catalyst precursor) is brought into contact with component (a) using at least component (a).

Suitable amounts, conditions, and procedures for each component in the contact step in the first loading operation are as follows.
The usage-amount of a halogen-containing titanium compound (a) is 0.5-100 mol normally with respect to 1 mol of magnesium of an alkoxy-containing magnesium compound (b), Preferably it is 1-50 mol.
The usage-amount of a halogen-containing silicon compound (c) is 0.01-10 mol normally with respect to 1 mol of magnesium of an alkoxy-containing magnesium compound (b), Preferably it is 0.05-1 mol.
The usage-amount of aromatic hydrocarbon (d) is 100-100,000 milliliters normally with respect to 1 mol of magnesium of an alkoxy containing magnesium compound (b), Preferably it is 500-10,000 milliliters.
The amount of the electron donating compound (e) to be used is generally 0.01 to 10 mol, preferably 0.05 to 0.15 mol, per 1 mol of magnesium of the alkoxy-containing magnesium compound (b).

  The contact temperature is usually −20 to 200 ° C., preferably 20 to 150 ° C., more preferably 120 to 150 ° C., and the contact time is usually 1 minute to 24 hours, preferably 10 minutes to 6 hours.

  The contact procedure is not particularly limited. For example, each component may be contacted in the presence of an inert solvent such as a hydrocarbon, or each component may be diluted with an inert solvent and contacted. Examples of the inert solvent include aliphatic hydrocarbons such as n-pentane, isopentane, n-hexane, n-heptane, n-octane, and isooctane; aromatic hydrocarbons such as benzene, ethylbenzene, toluene, and xylene; Can be mentioned.

The supporting operation is preferably performed twice or more so that the halogen-containing titanium compound (a) is sufficiently supported on the alkoxy-containing magnesium compound (b) as the catalyst carrier.
In the contact step in the second and subsequent loading operations, the solid catalyst component (solid catalyst precursor) obtained in the first loading operation is further brought into contact with the halogen-containing titanium compound (a). At this time, if necessary, the component (d) may also be brought into contact.
The preferred use amount, conditions and procedure of the titanium compound (a) in the contacting step in the second and subsequent loading operations are the same as in the first loading operation.

The washing step in each loading operation is washed using an inert solvent. The inert solvent may be the same as described above. The washing method is not limited, but decantation, filtration and the like are preferable. The amount of inert solvent used, the washing time, and the number of washings are not limited, but usually 100 to 100,000 milliliters, preferably 500 to 10,000 milliliters of solvent are used per mole of magnesium compound, usually 1 minute. Wash for -24 hours, preferably 10 minutes to 6 hours.
The washing temperature is preferably 100 ° C. or higher and 150 ° C. or lower. When an antistatic agent is used, it is preferably 60 ° C. or lower, particularly preferably 30 ° C. or lower.
The pressure during cleaning varies depending on the type of cleaning liquid, the cleaning temperature, and the like, but is usually 0 to 5 MPa, preferably 0 to 1 MPa. During the cleaning step, it is preferable to perform stirring from the viewpoint of cleaning uniformity and cleaning efficiency.

In the present invention, the fine powder removing process is performed using the antistatic agent in the cleaning step in the last carrying operation. The amount of the antistatic agent is 0.05% by weight or more in total with respect to the solid catalyst component before the final washing.
In the case where the cleaning process includes a plurality of cleaning operations, it is not necessary to use an antistatic agent for all cleaning operations. Further, the cleaning using the antistatic agent does not need to be performed once, and may be performed in plural.
In addition, although the antistatic agent is used at least in the cleaning process in the last carrying operation, the antistatic agent may be used in the cleaning process in the previous carrying operation or in the washing process in all carrying operations.

In the present invention, by washing with an antistatic agent, a solid catalyst component with a small amount of fine powder is obtained, and as a result, an olefin polymer with a small amount of powder fine powder can be obtained. It is considered as follows.
In the carrying operation, in order to maintain the activity and stereoregularity at a high level, impurities such as an alkoxytitanium compound floating in the slurry are sufficiently washed and removed using an inert solvent. However, at this time, the polar substance is reduced, and static electricity is likely to be generated on the wall surface of the solid catalyst component and the synthesis reactor due to stirring during washing. Due to this static electricity, fine powder particles generated during the synthesis adhere to particles having a main particle size and a vessel wall. The adhering fine powder may not be able to be removed by normal washing utilizing the sedimentation rate of the particles. However, when an antistatic agent is added, static electricity is removed by adsorbing the antistatic agent on the catalyst surface or the vessel wall, and fine powder can be removed.
In general, even if the amount of the antistatic agent added is 10% by weight, the fine powder removing effect does not increase, which is economically disadvantageous. In addition, depending on the type of antistatic agent, when added in a large amount, the activity and stereoregularity of the solid catalyst component may be lowered.

  In order to uniformly disperse the antistatic agent in the system, it is preferable to disperse it in a solvent inert to the solid catalyst component. Further, when a large amount of antistatic agent is added, it may be better to perform additional washing with a neat inert solvent for the above reasons.

The antistatic agent used in the present invention is selected from an anionic surfactant, a cationic surfactant, a nonionic surfactant, an amphoteric surfactant, and a mixture thereof.
Examples of anionic surfactants include fatty acid salts, higher alcohol sulfate esters, aliphatic alcohol phosphate esters, fatty acid amide sulfonates, alkylallyl sulfonates, and cationic surfactants include aliphatic amine salts, Quaternary ammonium salts, alkyl pyridium salts, nonionic surfactants include polyoxyethylene alkyl ethers, polyoxyethylene alkyl esters, sorbitan alkyl esters, amphoteric surfactants such as imidazoline derivatives, Higher alkylamines and the like can be mentioned, and among these, nitrogen-containing polymers and / or sulfur compounds (for example, STADIS-425, Maruwa Bussan Co., Ltd.) are preferable.

  In addition, the obtained solid catalyst component can also be preserve | saved in inert solvents, such as a dry state or hydrocarbon.

[III] Polymerization Although there is no restriction | limiting about the usage-amount of a catalyst component, Usually, a solid catalyst component (A) is 0.00005-1 mmol per liter of reaction volume in conversion of a titanium atom, The organoaluminum compound (B) has an aluminum / titanium atomic ratio of usually 1 to 1000, preferably 10 to 500. When this atomic ratio deviates from the above range, the catalyst activity may be insufficient. When an electron donating compound is used, the molar ratio of the electron donating compound (C) / organoaluminum compound (B) is usually 0.001 to 5.0, preferably 0.01 to 2.0. Preferably it is 0.05-1.0. If this molar ratio is outside the above range, sufficient catalytic activity and stereoregularity may not be obtained. However, when prepolymerization is performed, it can be further reduced.

As the olefin used in the present invention, the general formula (III)
R ² —CH═CH ₂ (III)
Α-olefins represented by the formula are preferred. In the general formula (III), R ² is a hydrogen atom or a hydrocarbon group. The hydrocarbon group may be a saturated group or an unsaturated group, and may be linear, branched, or cyclic. Specifically, ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-decene, 3-methyl-1-pentene, 4-methyl-1-pentene, vinylcyclohexane , Butadiene, isoprene, piperylene and the like. These olefins may be used alone or in combination of two or more. Of these olefins, ethylene and propylene are preferred.

  In the polymerization of olefins in the present invention, from the viewpoint of polymerization activity, stereoregularity, and polymer powder form, the olefin may be preliminarily polymerized first and then the main polymerization may be performed as desired. In this case, the olefin is usually added in the presence of a catalyst obtained by mixing the solid catalyst component (A), the organoaluminum compound (B) and, if necessary, the electron donating compound (C) in a predetermined ratio. Prepolymerization is performed at 0 to 100 ° C. and normal pressure to about 5 MPa, and then the olefin is main-polymerized in the presence of a catalyst and a prepolymerized product.

  There is no particular limitation on the polymerization mode in this main polymerization, and any of solution polymerization, slurry polymerization, gas phase polymerization, bulk polymerization, etc. can be applied, and further, both batch polymerization and continuous polymerization can be applied, Two-stage polymerization and multistage polymerization under different conditions are also applicable.

  The polymerization pressure is not particularly limited, and from the viewpoint of polymerization activity, usually atmospheric pressure to 8 MPa, preferably 0.2 to 5 MPa, and the polymerization temperature is appropriately selected in the range of usually 0 to 200 ° C., preferably 30 to 100 ° C. It is. The polymerization time depends on the type of olefin used as a raw material and the polymerization temperature, and cannot be determined unconditionally, but is usually 5 minutes to 20 hours, preferably about 10 minutes to 10 hours.

  The molecular weight can be adjusted by adding a chain transfer agent, preferably hydrogen. Further, an inert gas such as nitrogen may be present.

  In the present invention, the component (A) and the component (B), and optionally the component (C) may be mixed in a predetermined ratio and brought into contact with each other, and then the olefin may be immediately introduced to carry out the polymerization. After contact, after aging for about 0.2 to 3 hours, polymerization may be carried out by introducing olefin. Furthermore, these catalyst components can be supplied suspended in an inert solvent or olefin.

  The post-treatment after the polymerization can be performed by a conventional method. That is, in the gas phase polymerization method, after polymerization, a nitrogen gas stream or the like may be passed through the polymer powder derived from the polymerization vessel in order to remove olefins contained therein. Accordingly, pelletization may be performed by an extruder, and in this case, a small amount of water, alcohol, or the like may be added in order to completely deactivate the catalyst. In the bulk polymerization method, after polymerization, the monomer is completely separated from the polymer derived from the polymerization vessel, and then pelletized.

  In the examples and comparative examples, the characteristics of the solid catalyst component and the polymer were determined as follows. The results are shown in Tables 1 and 2.

(1) Average particle diameter (D ₅₀ ), 10% particle diameter (D ₁₀ ) and 90% particle diameter (D ₉₀ ) of the magnesium compound
The particle size was measured by the light scattering method in a state where the magnesium compound was suspended in the hydrocarbon, the particle size distribution obtained from this was plotted on a lognormal probability paper, and the 50% particle size was the average particle size (D ₅₀ ).
The 10% particle diameter (D ₁₀ ) and 90% particle diameter (D ₉₀ ) were also determined in the same manner.

(2) Amount of fine powder of solid catalyst component (≦ 10 μm)
Based on the particle size distribution obtained in (1) above, the weight of particles of 10 μm or less was defined as the amount of fine powder.

(3) Particle size distribution index (P) of the solid catalyst component
Using the 90% particle diameter (D ₉₀ ) and 10% particle diameter (D ₁₀ ) determined in (1) above, the calculation was performed according to the following formula.
P = D ₉₀ / D ₁₀

(4) Ti loading amount of solid catalyst component After the solid catalyst component was sufficiently dried, it was precisely weighed and sufficiently deashed using 3N-sulfuric acid. Thereafter, the insoluble matter was filtered, phosphoric acid was added as a masking agent to the filtrate, and 3% hydrogen peroxide solution was further added to cause color development. The absorbance at 420 nm of the solution was measured by FT-IR to obtain the Ti concentration, and the Ti loading was calculated.

(5) Stereoregularity of polymer [mmmm]
The polymer was dissolved in 1,2,4-trichlorobenzene, and the methyl group signal measured by ¹³ C-NMR (EX-400 manufactured by JEOL Ltd.) at 130 ° C. by proton decoupling method was used. And quantified. The isotactic pentad fraction [mmmm] used in the present invention is measured by a ¹³ C nuclear magnetic resonance spectrum proposed in “Macromolecules, 6, 925 (1973)” by A. Zambelli et al. Means the isotactic fraction of pentad units in the polypropylene molecular chain. In addition, the method for determining the assignment of peaks in the measurement of the ¹³ C nuclear magnetic resonance spectrum was in accordance with the assignment proposed in “Macromolecules, 8, 687 (1975)” by A. Zambelli and the like.

(6) Average particle diameter (D ₅₀ ′), 90% particle diameter (D ₉₀ ′) and 10% particle diameter (D ₁₀ ′) of the polymer powder
The particle size distribution of the polymer powder measured using a standard sieve was plotted on log-normal probability paper, and the 50% particle size was defined as the average particle size (D ₅₀ ′).
90% particle diameter _{(D 90} ') and 10% particle diameter _{(D 10')} was also determined in the same manner.

(7) Fine powder amount of polymer powder (≦ 250 μm)
Based on the particle size distribution determined by the method (6) above, the weight of particles of 250 μm or less was defined as the fine powder amount.

(8) Coarse powder amount (≧ 2830 μm) of polymer powder
Based on the particle size distribution obtained by the method (6) above, the weight of particles of 2830 μm or more was defined as a fine powder.

(9) Particle size distribution index (P ′) of polymer powder
Using the 90% particle diameter (D ₉₀ ′) and 10% particle diameter (D ₁₀ ′) determined in (6) above, the calculation was performed according to the following formula.
P ′ = D ₉₀ ′ / D ₁₀ ′

(10) Polymerization induction period Polymerization was carried out by continuously supplying propylene so that the pressure was constant, and the flow rate of propylene (polymerization reaction rate) supplied to the polymerization vessel was recorded. When the polymerization time is plotted on the horizontal axis and the propylene flow rate is plotted on the vertical axis, a curve having a maximum value (polymerization rate curve) is obtained. The polymerization time until reaching the maximum value is defined as the polymerization induction period. It is considered that the longer this time is, the milder the heat storage due to the heat of polymerization of the resulting polymer powder is, and the occurrence of lump (coarse powder) is suppressed by the heat fusion of the polymer powder.

[Example 1]
(1) Preparation of alkoxy-containing magnesium compound 232 ml (3.95 mol) of ethanol dehydrated in a three-neck flask with a stirrer having an internal volume of 0.5 liter substituted with nitrogen, 0.24 g (1.9 mg) of iodine Atom) and 12 g (0.49 mol) of metallic magnesium were added, and the reaction was stirred (525 rpm) at 78 ° C. until no hydrogen was generated from the system to obtain an alkoxy-containing magnesium compound.

(2) Preparation of solid catalyst component 16 ml of the alkoxy-containing magnesium compound obtained in the above (1) and 80 ml of dehydrated octane were added to a 0.5-liter flask equipped with a stirrer and substituted with nitrogen. Heated to 40 ° C., 2.4 ml (23 mmol) of silicon tetrachloride was added, stirred for 20 minutes, and 3.4 ml (13 mmol) of dinormal butyl phthalate was added. The temperature of the solution was raised to 70 ° C., and 77 ml (0.70 mol) of titanium tetrachloride was subsequently added dropwise using a dropping funnel. The internal temperature was 125 ° C. and the mixture was stirred for 1 hour to cause a contact reaction. Thereafter, washing was performed 7 times at 125 ° C. using 100 ml of dehydrated octane.
Further, 122 ml (1.11 mol) of titanium tetrachloride was added, the internal temperature was 125 ° C., and the mixture was stirred for 2 hours to carry out a second contact reaction. Thereafter, washing was performed 4 times with 100 ml of dehydrated octane at 125 ° C. to obtain 18 g of a solid catalyst component.

(3) Fine powder removal treatment of solid catalyst component STADIS-425 (Maruwa Bussan Co., Ltd., nitrogen-containing polymer and sulfur compound: 30 w%, kerosene: 60 w%, toluene: 10 w%) 300 ppm by weight Using 400 ml of dehydrated heptane (antistatic agent as a solid component excluding solvent: 0.036 g) contained, the solid catalyst component obtained in (2) above was washed three times at room temperature (solid Total antistatic agent (solid component) added per catalyst component: 0.6% by weight).

(4) Propylene Polymerization A stainless steel autoclave with a stirrer with an internal volume of 1 liter was sufficiently dried, and after substitution with nitrogen, 400 ml of heptane dehydrated inside was added. Further, 2.0 mmol of triethylaluminum and then 0.25 mmol of dicyclopentyldimethoxysilane were added, 0.0025 mmol of the solid catalyst component prepared in the above (2) was added per Ti, 0.1 MPa of hydrogen was introduced, and then Propylene was introduced. Polymerization was carried out at a total pressure of 0.8 MPa and a temperature of 80 ° C. for 1 hour. Thereafter, the temperature was lowered and the pressure was removed, the contents were taken out, put into 2 liters of methanol, and then vacuum-dried to obtain polypropylene.

(5) Measurement of polymerization induction period A stainless steel autoclave with a stirrer having an internal volume of 1 liter was sufficiently dried, and after purging with nitrogen, 400 ml of heptane dehydrated at room temperature was added. Further, 2.0 mmol of triethylaluminum and subsequently 0.25 mmol of dicyclopentyldimethoxysilane were added, and 0.1 MPa of hydrogen was introduced. Subsequently, propylene was introduced to bring the total pressure to 0.8 MPa and the temperature was raised to 80 ° C. Then, 0.0025 mmol of the solid catalyst component prepared in the above (2) was injected under pressure of Ti at 80 ° C., 1 Polymerization was carried out for a time, and the propylene consumption was recorded and the polymerization induction period was measured.

[Example 2]
(1) Preparation of alkoxy-containing magnesium compound [Example 1] The same procedure as in (1) was performed.
(2) Preparation of solid catalyst component [Example 1] The same procedure as in (2) was performed.
(3) Fine powder removal treatment of solid catalyst component [Execution except that the concentration of STADIS-425 in heptane was 1500 ppm (total amount of antistatic agent (solid component) added per solid catalyst component: 3.0 wt%)) Example 1] Performed in the same manner as (3).
(4) Propylene polymerization [Example 1] The same procedure as in (4) was performed.
(5) Measurement of polymerization induction period [Example 1] The same procedure as in (5) was performed.

Example 3
(1) Preparation of alkoxy-containing magnesium compound [Example 1] The same procedure as in (1) was performed.
(2) Preparation of solid catalyst component [Example 1] The same procedure as in (2) was performed.
(3) Fine powder removal treatment of solid catalyst component [Execution except that the concentration of STADIS-425 in heptane was 45 ppm (total amount of antistatic agent (solid component) added per solid catalyst component: 0.09 wt%)) Example 1] Performed in the same manner as (3).
(4) Propylene polymerization [Example 1] The same procedure as in (4) was performed.
(5) Measurement of polymerization induction period [Example 1] The same procedure as in (5) was performed.

Example 4
(1) Preparation of alkoxy-containing magnesium compound [Example 1] The same procedure as in (1) was performed.
(2) Preparation of solid catalyst component [Example 1] The same procedure as in (2) was performed.
(3) Fine powder removal treatment of solid catalyst component [Example 2] The same procedure as in (3) was conducted, except that after treatment with an antistatic agent, washing was further performed once with 400 ml of dehydrated heptane at room temperature.
(4) Propylene polymerization [Example 1] The same procedure as in (4) was performed.

Example 5
(1) Preparation of alkoxy-containing magnesium compound [Example 1] The same procedure as in (1) was performed.
(2) Preparation of solid catalyst component [Example 1] The same procedure as in (1) was carried out except that the octane washing temperature after the second reaction with titanium tetrachloride was room temperature.
(3) Fine powder removal treatment of solid catalyst component [Example 1] The same procedure as in (3) was performed.
(4) Propylene polymerization Example 1 except that cyclohexylmethyldimethoxysilane was used instead of dicyclopentyldimethoxysilane, the amount of the solid catalyst component was 0.005 mmol per Ti, and the hydrogen pressure was 0.05 MPa. ).

Example 6
(1) Preparation of alkoxy-containing magnesium compound [Example 1] The same procedure as in (1) was performed.
(2) Preparation of solid catalyst component [Example 5] The same procedure as in (2) was performed.
(3) Solid catalyst component fine powder removal treatment The same procedure as in Example 1 (3) was conducted, except that the solid catalyst component was treated with an antistatic agent and then washed twice with 400 ml of dehydrated heptane at room temperature.
(4) Propylene polymerization [Example 5] The same procedure as in (4) was performed.

Example 7
(1) Preparation of alkoxy-containing magnesium compound [Example 1] The same procedure as in (1) was performed.
(2) Preparation of solid catalyst component A three-necked flask with a stirrer having an internal volume of 0.5 liter was replaced with nitrogen gas, and then dehydrated ethylbenzene was 128 ml, and the alkoxy-containing magnesium compound obtained in (1) above. 16 g was added. 64 ml of titanium tetrachloride was added dropwise at 5 ° C., and the temperature was raised to 90 ° C., and then 4.3 ml of dibutyl phthalate was added. The temperature of this solution was further raised, and a contact operation was performed by stirring for 2 hours at an internal temperature of 125 ° C. Then, stirring was stopped, solid was settled, and the supernatant liquid was extracted. 240 ml of dehydrated ethylbenzene was added and washed twice at 125 ° C.
Furthermore, 96 ml of dehydrated ethylbenzene and 64 ml of titanium tetrachloride were added, and the contact operation was performed by stirring at an internal temperature of 125 ° C. for 2 hours. 240 ml of dehydrated ethylbenzene was added and washed twice at 125 ° C. to obtain a solid catalyst component.
(3) Fine powder removal treatment of solid catalyst component The concentration of STAD-425 in heptane is 2000 ppm (total amount of antistatic agent (solid component) added per solid catalyst component: 4.0 wt%), and the treatment frequency is 4 times. Example 1 was performed in the same manner as [Example 1] (3).
(4) Propylene polymerization [Example 1] The same procedure as in (4) was performed.
(5) Measurement of polymerization induction period [Example 1] The same procedure as in (5) was performed.

[Comparative Example 1]
(1) Preparation of alkoxy-containing magnesium compound [Example 1] The same procedure as in (1) was performed.
(2) Preparation of solid catalyst component [Example 1] The same procedure as in (2) was performed.
(3) Fine powder removal treatment of solid catalyst component The same procedure as in [Example 1] (3) was carried out except that the treatment with an antistatic agent was not carried out, but washing was carried out three times with 400 ml of dehydrated heptane at room temperature.
(4) Propylene polymerization [Example 1] The same procedure as in (4) was performed.
(5) Measurement of polymerization induction period [Example 1] The same procedure as in (5) was performed.

[Comparative Example 2]
(1) Preparation of alkoxy-containing magnesium compound [Example 1] The same procedure as in (1) was performed.
(2) Preparation of solid catalyst component [Example 1] The same procedure as in (2) was performed.
(3) Fine powder removal treatment of solid catalyst component [Execution except that the concentration of STADIS-425 in heptane was 15 ppm (total amount of antistatic agent (solid component) added per solid catalyst component: 0.03% by weight)) Example 1] Performed in the same manner as (3).
(4) Propylene polymerization [Example 1] The same procedure as in (4) was performed.
(5) Measurement of polymerization induction period [Example 1] The same procedure as in (5) was performed.

[Comparative Example 3]
(1) Preparation of alkoxy-containing magnesium compound [Example 1] The same procedure as in (1) was performed.
(2) Preparation of solid catalyst component and treatment thereof A nitrogen-substituted three-necked flask with an internal volume of 0.5 liters containing 16 g of alkoxy-containing magnesium compound obtained in (1) above and 2000 ppm of STADIS-425 is contained. 80 ml of dehydrated octane (total amount of antistatic agent (solid component) added per solid catalyst component: 1.07 wt%) was added. Heated to 40 ° C., 2.4 ml (23 mmol) of silicon tetrachloride was added, stirred for 20 minutes, and 3.4 ml (13 mmol) of dinormal butyl phthalate was added. The temperature of the solution was raised to 70 ° C., and 77 ml (0.70 mol) of titanium tetrachloride was subsequently added dropwise using a dropping funnel. The internal temperature was set to 125 ° C. and the mixture was stirred for 1 hour to carry out the loading operation. Thereafter, washing was performed 7 times at 125 ° C. using 100 ml of dehydrated octane.
Further, 122 ml (1.11 mol) of titanium tetrachloride was added, the internal temperature was set to 125 ° C., and the mixture was stirred for 2 hours to carry out the second loading operation. Thereafter, washing was performed 4 times with 100 ml of dehydrated octane at 125 ° C. to obtain 18 g of a solid catalyst component.
(3) Propylene polymerization [Example 1] The same procedure as in (3) was performed.

[Comparative Example 4]
(1) Preparation of alkoxy-containing magnesium compound [Example 1] The same procedure as in (1) was performed.
(2) Preparation of solid catalyst component and its treatment 16 g of alkoxy-containing magnesium compound obtained in (1) above was added to a three-necked flask with a stirrer having an internal volume of 0.5 liter substituted with nitrogen and 80 dehydrated octane. Milliliter was added. Heated to 40 ° C., 2.4 ml (23 mmol) of silicon tetrachloride was added, stirred for 20 minutes, and 3.4 ml (13 mmol) of dinormal butyl phthalate was added. The temperature of the solution was raised to 70 ° C., and 77 ml (0.70 mol) of titanium tetrachloride was subsequently added dropwise using a dropping funnel. The internal temperature was set to 125 ° C. and the mixture was stirred for 1 hour to carry out the loading operation. Thereafter, washing was performed 7 times at 125 ° C. using 100 ml of dehydrated octane.
After washing, 80 ml of dehydrated octane containing 2000 ppm of STADIS-425 (total amount of antistatic agent (solid component) added per solid catalyst composition: 1.07 wt%) was added. Further, 122 ml (1.11 mol) of titanium tetrachloride was added, the internal temperature was set to 125 ° C., and the mixture was stirred for 2 hours to carry out the second loading operation. Thereafter, washing was performed 4 times with 100 ml of dehydrated octane at 125 ° C. to obtain 18 g of a solid catalyst component.
(3) Propylene polymerization [Example 1] The same procedure as in (3) was performed.

[Comparative Example 5]
(1) Preparation of alkoxy-containing magnesium compound [Example 1] The same procedure as in (1) was performed.
(2) Preparation of solid catalyst component [Example 5] The same procedure as in (2) was performed.
(3) Fine powder removal treatment of solid catalyst component [Example 5] The same procedure as in (3) was carried out except that the treatment was not carried out with an antistatic agent and washing was carried out three times with 400 ml of dehydrated heptane at room temperature.
(4) Propylene polymerization [Example 5] The same procedure as in (4) was performed.

[Comparative Example 6]
(1) Preparation of alkoxy-containing magnesium compound [Example 1] The same procedure as in (1) was performed.
(2) Preparation of solid catalyst component [Example 7] The same procedure as in (2) was performed.
(3) Fine powder removal treatment of solid catalyst component [Example 7] The same procedure as in (3) was conducted, except that the treatment was not performed with an antistatic agent and washing was performed 4 times with 400 ml of dehydrated heptane.
(4) Propylene polymerization [Example 1] The same procedure as in (4) was performed.
(5) Measurement of polymerization induction period [Example 1] The same procedure as in (5) was performed.

  The solid catalyst component of the present invention can be used in a catalyst for olefin polymerization and a method for producing an olefin polymer.

It is a figure which shows the manufacturing method of the catalyst for olefin polymerization concerning one Embodiment of this invention.

Claims (9)

Using the following components (a), (b), (c) and (e), or the following components (a), (b), (d) and (e), a supporting operation comprising a contacting step and a washing step is performed. Repeat at least once,
A solid catalyst component for olefin polymerization obtained by washing at least in the final washing step using the following antistatic agent in a total amount of 0.05% by weight or more based on the solid catalyst component before the final washing.
component:
(A) halogen-containing titanium compound (b) alkoxy-containing magnesium compound (c) halogen-containing silicon compound (d) aromatic hydrocarbon solvent (e) electron donating compound antistatic agent:
Antistatic agent selected from anionic surfactants, cationic surfactants, nonionic surfactants, amphoteric surfactants, and mixtures thereof The following components (a), (b), (c) and (e), or the following components (a), (b), (d) and (e) are contacted and reacted at 120 ° C. or higher and 150 ° C. or lower, Washing at 100 ° C. or higher and 150 ° C. or lower with an inert solvent to obtain a solid catalyst precursor,
The solid catalyst precursor is contacted and reacted again with the following component (a) at 120 ° C. or higher and 150 ° C. or lower,
A solid catalyst component for olefin polymerization obtained by adding the following antistatic agent in a total amount of 0.05% by weight or more to the solid catalyst precursor and washing with an inert solvent.
component:
(A) halogen-containing titanium compound (b) alkoxy-containing magnesium compound (c) halogen-containing silicon compound (d) aromatic hydrocarbon solvent (e) electron donating compound antistatic agent:
Antistatic agent selected from anionic surfactants, cationic surfactants, nonionic surfactants, amphoteric surfactants, and mixtures thereof   The solid catalyst component for olefin polymerization according to claim 1 or 2, wherein the antistatic agent is a mixture of an anionic surfactant and a cationic surfactant.   The solid catalyst component for olefin polymerization according to any one of claims 1 to 3, wherein the anionic surfactant includes a sulfur compound, and the cationic surfactant includes a nitrogen-containing polymer.   The alkoxy-containing magnesium compound (b) was obtained by reacting metal magnesium, alcohol, and halogen containing a halogen atom in an amount of 0.0001 gram atom or more with respect to 1 gram atom of metal magnesium and / or a halogen-containing compound. The solid catalyst component for olefin polymerization according to any one of claims 1 to 4.   The solid catalyst component for olefin polymerization according to any one of claims 1 to 5, wherein the halogen-containing silicon compound (c) is silicon tetrachloride. An olefin polymerization catalyst comprising the following (A) and (B).
(A) Solid catalyst component for olefin polymerization according to any one of claims 1 to 6 (B) Organoaluminum compound   The olefin polymerization catalyst according to claim 7, further comprising an electron donating compound (C). The manufacturing method of the olefin polymer which superposes | polymerizes an olefin using the catalyst for olefin polymerization of Claim 7 or 8.

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