JP2005281682A - Solid catalyst component and catalyst for olefin polymerization - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a novel solid catalyst component and catalyst for olefin polymerization which is capable of obtaining an olefin polymer with a wide molecular weight distribution at a high yield, when it is employed for an olefin polymerization, while retaining the polymerization activity and the stereoregularity at a high level. <P>SOLUTION: The solid catalyst component for olefin polymerization, having two or more solid components containing magnesium, titanium, and a halogen, or an electron-donating compound, is obtained by mixing two or more solid components having a different weight content ratio of the electron-donating compound mutually, and the catalyst is formed from the catalyst component, an organoaluminum compound, and an external electron-donating compound. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a solid catalyst component for olefin polymerization and an olefin polymerization catalyst formed using the solid catalyst component, and further, the polymerization activity is remarkably maintained while maintaining the high degree of stereoregularity of the olefin polymer. The present invention relates to a solid catalyst component for polymerization of olefins and a catalyst capable of obtaining a high olefin polymer having a wide molecular weight distribution in a high yield.

  Conventionally, in the polymerization of olefins, olefins are present in the presence of a solid catalyst component containing magnesium, titanium, an electron donating compound, and halogen as essential components, an organoaluminum compound and an organosilicon compound. Many olefin polymerization methods for polymerizing or copolymerizing olefins have been proposed.

  For example, Patent Document 1 (Japanese Patent Laid-Open No. 57-63310) and Patent Document 2 (Japanese Patent Laid-Open No. 57-63311) disclose a solid catalyst component containing a magnesium compound, a titanium compound and an electron donor, and an organic compound. There has been proposed a method of polymerizing an olefin having 3 or more carbon atoms using a catalyst comprising a combination of an aluminum compound and an organosilicon compound having a Si—O—C bond. However, these methods are not always satisfactory to obtain a highly stereoregular polymer in a high yield, and further improvement has been desired.

  On the other hand, in Patent Document 3 (Japanese Patent Laid-Open No. 63-3010), a product obtained by contacting dialkoxymagnesium, aromatic dicarboxylic acid diester, aromatic hydrocarbon and titanium halogen compound is heated in a powder state. A solid catalyst component prepared by doing so, a catalyst for olefin polymerization comprising an organoaluminum compound and an organosilicon compound, and a method for polymerizing olefins in the presence of the catalyst have been proposed.

  Moreover, in patent document 4 (Unexamined-Japanese-Patent No. 1-315406), titanium tetrachloride is made to contact the suspension formed with diethoxymagnesium and alkylbenzene, and it is made to react by adding phthalic acid dichloride then. A solid catalyst component prepared by obtaining a solid product and further contacting the solid product with titanium tetrachloride in the presence of an alkylbenzene; and a catalyst for olefin polymerization comprising an organoaluminum compound and an organosilicon compound; A method for polymerizing olefins in the presence of the catalyst has been proposed.

  Furthermore, in Patent Document 5 (Japanese Patent Laid-Open No. 2-84404), a solid titanium catalyst component, an organoaluminum compound, containing magnesium, titanium and halogen as essential components produced by bringing a magnesium compound into contact with a titanium compound. Olefin polymerization catalyst formed from catalyst component and organosilicon compound catalyst component containing cyclopentyl group, cyclopentenyl group, cyclopentadienyl group or derivatives thereof, and olefin for polymerizing or copolymerizing olefin in the presence of the catalyst A polymerization method has been proposed.

  Each of the above prior arts has a high activity capable of omitting the so-called demineralization step for removing catalyst residues such as chlorine and titanium remaining in the produced polymer, and also has a stereoregularity weight. The focus is on improving the yield of coalescence and increasing the sustainability of the catalytic activity during polymerization, each with excellent results.

  However, in recent years, an olefin polymer obtained by a polymerization reaction using such a highly active catalyst component and an olefin polymerization catalyst composed of an organoaluminum compound and an organosilicon compound is an organic aluminum compound. Compared to the olefin polymer obtained by a polymerization reaction using an olefin polymerization catalyst combined with an electron donating compound as a third component, which is used as required, its molecular weight distribution is narrow, and therefore the polymer Therefore, there is a problem that the use is limited to some extent, for example, the moldability or appearance of polyolefin as a final product is impaired.

  As one means for solving such problems, various attempts have been made, for example, by obtaining a polyolefin having a wide molecular weight distribution by adopting a multistage polymerization method. However, the multi-stage polymerization method is not preferable in terms of cost, such as carrying out complicated polymerization operations in duplicate or recovering a chelating agent used during polymerization.

  Therefore, in Patent Document 6 (JP-A-3-7703), a solid titanium catalyst component containing magnesium, titanium, halogen and an electron donor as essential components, an organoaluminum compound, and at least two or more types of electron donors ( There has been proposed a method of polymerizing olefins in the presence of an olefin polymerization catalyst formed from an organosilicon compound. Further, in Patent Document 7 (Japanese Patent Application Laid-Open No. 10-218926), a catalyst solid component, an organoaluminum compound component, and a specific polycyclic amino group-containing organic, which essentially contain magnesium, titanium, a halogen element and an electron donor. There has been proposed a method for polymerizing an α-olefin in the presence of a catalyst comprising a silicon compound component.

According to the above polymerization method, it is said that a polyolefin having a broad target molecular weight distribution can be obtained without complicated multi-stage polymerization, but the actual situation is that few catalysts exhibit such effects.
JP 57-63310 A JP-A-57-63311 JP-A 63-3010 JP-A-1-315406 JP-A-2-84404 Japanese Patent Laid-Open No. 3-7703 Japanese Patent Laid-Open No. 10-218926

  That is, an object of the present invention is to provide a novel olefin polymer having a wide molecular weight distribution in a high yield while maintaining high polymerization activity and stereoregularity of the olefin polymer when olefins are polymerized. An object of the present invention is to provide a solid catalyst component and a catalyst for olefin polymerization.

  As a result of intensive studies, the present inventors have found that two or more solid components containing magnesium, titanium and halogen or an electron donating compound, and having two or more different weight contents of the electron donating compound. The catalyst using the solid catalyst component obtained by mixing the solid components of the present invention has found that the polymerization activity is remarkably increased and a polymer having a wide molecular weight distribution while maintaining a high degree of stereoregularity can be obtained. The invention has been completed.

  That is, the present invention is a mixture of two or more solid components containing magnesium, titanium and halogen or an electron donating compound, each having a different weight content of the electron donating compound. The present invention provides a solid catalyst component for olefin polymerization, which is obtained.

Moreover, this invention is formed from the following (A), (B) and (C) component, The catalyst for olefin polymerization characterized by the above-mentioned.
(A) the solid catalyst component for olefin polymerization,
(B) the following general formula (1);
R ¹ _q AlY _3-q (1)
(Wherein R ¹ is an alkyl group having 1 to 4 carbon atoms, Y represents a hydrogen atom or a halogen atom, q is a real number of 0 <q ≦ 3), and (C) External electron donating compound.

  INDUSTRIAL APPLICABILITY The present invention can provide a novel solid catalyst component and a catalyst for olefin polymerization that can obtain a polymer having a wide molecular weight distribution while maintaining a high level of stereoregularity with a significantly high polymerization activity. Accordingly, it has become possible to efficiently produce a polymer having excellent moldability.

  The solid component constituting the solid catalyst component (A) of the present invention (hereinafter sometimes referred to as “component (A)”) contains magnesium, titanium and a halogen or an electron-donating compound. Component (i) "), a titanium compound (sometimes simply referred to as" component (ii) "), or a magnesium compound, a titanium compound and an electron donating compound (simply" component "). (Iii) ").) May be prepared by contacting.

  Examples of the magnesium compound used for the solid component include dihalogenated magnesium, dialkylmagnesium, halogenated alkylmagnesium, dialkoxymagnesium, diaryloxymagnesium, halogenated alkoxymagnesium, and fatty acid magnesium. Among these magnesium compounds, dialkoxymagnesium is preferable, and specific examples include dimethoxymagnesium, diethoxymagnesium, dipropoxymagnesium, dibutoxymagnesium, ethoxymethoxymagnesium, ethoxypropoxymagnesium, butoxyethoxymagnesium, and the like. Magnesium is particularly preferred. These dialkoxymagnesium may be obtained by reacting metal magnesium with alcohol in the presence of halogen or a halogen-containing metal compound. Moreover, said dialkoxy magnesium can also be used individually or in combination of 2 or more types.

  Furthermore, dialkoxymagnesium suitably used in the preparation of the solid component is in the form of granules or powder, and the shape thereof may be indefinite or spherical. For example, when spherical dialkoxymagnesium is used, a polymer powder having a better particle shape and a narrow particle size distribution can be obtained, and the handling operability of the produced polymer powder during the polymerization operation is improved. Problems such as blockage caused by the contained fine powder are solved.

  The spherical dialkoxymagnesium does not necessarily need to be a true sphere, and an elliptical or potato-shaped one can also be used. Specifically, the particle shape is such that the ratio (l / w) of the major axis diameter l to the minor axis diameter w is 3 or less, preferably 1 to 2, more preferably 1 to 1.5. .

  The dialkoxymagnesium having an average particle size of 1 to 200 μm can be used. Preferably it is 5 to 150 μm. In the case of spherical dialkoxymagnesium, the average particle diameter is 1 to 100 μm, preferably 5 to 50 μm, and more preferably 10 to 40 μm. As for the particle size, it is desirable to use one having a small particle size distribution and a small amount of fine powder and coarse powder. Specifically, the particle size of 5 μm or less is 20% or less, preferably 10% or less. On the other hand, the particle size of 100 μm or more is 10% or less, preferably 5% or less. Further, when the particle size distribution is expressed by ln (D90 / D10) (where D90 is the cumulative particle size and the particle size at 90%, D10 is the cumulative particle size and the particle size at 10%), it is preferably 3 or less, preferably 2 or less.

  For example, JP-A-58-41832, JP-A-62-51633, JP-A-3-74341, JP-A-4-368391, JP-A-4-36891 can be used for producing spherical dialkoxymagnesium as described above. It is illustrated in the 8-73388 gazette etc.

The titanium compound used for the preparation of the solid component in the present invention is a tetravalent titanium halogen compound, and has the general formula Ti (OR ⁴ ) _n X _4-n (wherein R ⁴ is an alkyl group having 1 to ⁴ carbon atoms). X represents a halogen atom, and n is an integer of 0 ≦ n ≦ 4.) A compound selected from the group consisting of titanium halides and alkoxytitanium halides represented by the following formula:

  Specifically, titanium tetrachloride such as titanium tetrachloride, titanium tetrabromide and titanium tetraiodide as titanium halide, methoxytitanium trichloride, ethoxytitanium trichloride, propoxytitanium trichloride, n-butoxytitanium trichloride as alkoxytitanium halide. Examples include chloride, dimethoxy titanium dichloride, diethoxy titanium dichloride, dipropoxy titanium dichloride, di-n-butoxy titanium dichloride, trimethoxy titanium chloride, triethoxy titanium chloride, tripropoxy titanium chloride, tri-n-butoxy titanium chloride. The Of these, titanium tetrahalide is preferable, and titanium tetrachloride is particularly preferable. These titanium compounds can be used alone or in combination of two or more.

  The solid component may contain an electron donating compound and is an organic compound containing an oxygen atom or a nitrogen atom. For example, alcohols, phenols, ethers, esters, ketones, acid halides, Examples include aldehydes, amines, amides, nitriles, isocyanates, and organosilicon compounds containing a Si—O—C bond.

  Specifically, alcohols such as methanol, ethanol, n-propanol and 2-ethylhexanol, phenols such as phenol and cresol, methyl ether, ethyl ether, propyl ether, butyl ether, amyl ether, diphenyl ether, 9,9- Ethers such as bis (methoxymethyl) fluorene and 2-isopropyl-2-isopentyl-1,3-dimethoxypropane, methyl formate, ethyl acetate, vinyl acetate, propyl acetate, octyl acetate, cyclohexyl acetate, ethyl propionate, ethyl butyrate , Methyl benzoate, ethyl benzoate, propyl benzoate, butyl benzoate, octyl benzoate, cyclohexyl benzoate, phenyl benzoate, methyl p-toluate, ethyl p-toluate, methyl anisate, anisic acid Monocarboxylic acid esters such as chill, malonic acid diester, malonic acid diester derivative, dimethyl adipate, diethyl adipate, dipropyl adipate, dibutyl adipate, diisodecyl adipate, dioctyl adipate, maleic acid diester derivative, maleic acid diester derivative , Dicarboxylic acid diesters such as phthalic acid diester, ketones such as acetone, methyl ethyl ketone, methyl butyl ketone, acetophenone, benzophenone, acid halides such as phthalic dichloride, terephthalic acid dichloride, acetaldehyde, propionaldehyde, octylaldehyde, benzaldehyde, etc. Aldehydes, amines such as methylamine, ethylamine, tributylamine, piperidine, aniline, pyridine, oleic amide Amides such as stearamide, nitriles such as acetonitrile, benzonitrile and tolunitrile, isocyanates such as methyl isocyanate and ethyl isocyanate, phenylalkoxysilane, alkylalkoxysilane, phenylalkylalkoxysilane, cycloalkylalkoxysilane, cyclo An organosilicon compound containing a Si—O—C bond such as alkylalkylalkoxysilane can be given.

  Of the above electron donating compounds, esters, particularly dicarboxylic acid diesters, are preferably used. This is preferable in terms of improving the activity against hydrogen. Among these, specific examples of phthalic acid diesters include dimethyl phthalate, diethyl phthalate, di-n-propyl phthalate, di-iso-propyl phthalate, di-n-butyl phthalate, di-iso-phthalate. Butyl, ethyl methyl phthalate, methyl phthalate (iso-propyl), ethyl phthalate (n-propyl), ethyl phthalate (n-butyl), ethyl phthalate (iso-butyl), di-n-pentyl phthalate Di-iso-pentyl phthalate, di-neo-pentyl phthalate, dihexyl phthalate, di-n-heptyl phthalate, di-n-octyl phthalate, bis (2,2-dimethylhexyl) phthalate, phthalate Bis (2-ethylhexyl) acid, di-n-nonyl phthalate, di-iso-decyl phthalate, bis (2,2-dimethylheptyl phthalate) ), N-butyl phthalate (iso-hexyl), n-butyl phthalate (2-ethylhexyl), n-pentylhexyl phthalate, n-pentyl phthalate (iso-hexyl), iso-pentyl phthalate (heptyl) ), N-pentyl (2-ethylhexyl) phthalate, n-pentyl phthalate (iso-nonyl), iso-pentyl phthalate (n-decyl), n-pentylundecyl phthalate, iso-pentyl phthalate (iso) -Hexyl), n-hexyl phthalate (2,2-dimethylhexyl), n-hexyl phthalate (2-ethylhexyl), n-hexyl phthalate (iso-nonyl), n-hexyl phthalate (n-decyl) N-heptyl phthalate (2-ethylhexyl), n-heptyl phthalate (iso-nonyl), n-phthalate Heptyl (neo-decyl) are exemplified phthalate 2-ethylhexyl (an iso-nonyl) is, these one or more kinds are used.

Moreover, as a phthalic-acid diester derivative, following General formula (3);
(R ⁵ ) _l C ₆ H ₄ (COOR ⁶ ) (COOR ⁷ ) (3)
(In the formula, R ⁵ represents an alkyl group having 1 to 8 carbon atoms or a halogen atom, R ⁶ and R ⁷ represent an alkyl group having 1 to 12 carbon atoms, and R ⁶ and R ⁷ may be the same or different. The number 1 of the substituent R ⁵ may be 1 or 2, and when 1 is 2, R ⁵ may be the same or different.

In the general formula (3), the alkyl group having 1 to 8 carbon atoms of R ⁵ is specifically a methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, t-butyl. Group, n-pentyl group, isopentyl group, neopentyl group, n-hexyl group, isohexyl group, 2,2-dimethylbutyl group, 2,2-dimethylpentyl group, isooctyl group, 2,2-dimethylhexyl group, The halogen atom of R ⁵ is a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom. R ⁵ is preferably a methyl group, a bromine atom or a fluorine atom, more preferably a methyl group or a bromine atom.

In the general formula (3), R ⁶ and R ⁷ are methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, t-butyl group, n-pentyl group, isopentyl group, neopentyl group. Group, n-hexyl group, isohexyl group, 2,2-dimethylbutyl group, 2,2-dimethylpentyl group, or isooctyl group, 2,2-dimethylhexyl group, n-nonyl group, isononyl group, n-decyl group , Isodecyl group and n-dodecyl group. Among these, an ethyl group, an n-butyl group, an isobutyl group, a t-butyl group, a neopentyl group, an isohexyl group, and an isooctyl group are preferable, and an ethyl group, an n-butyl group, and a neopentyl group are particularly preferable. The number l of the substituent R ⁵ is 1 or 2, and when l is 2, R ⁵ may be the same or different. When l is 1, R ⁵ is substituted with a hydrogen atom at the 3-position, 4-position or 5-position of the phthalate derivative of the above general formula (3). When l is 2, R ⁵ is 4-position and Substitution with a hydrogen atom at the 5-position is preferred.

  Examples of the phthalic acid diester derivative represented by the general formula (3) include diethyl 4-methylphthalate, di-n-butyl 4-methylphthalate, diisobutyl 4-methylphthalate, dineopentyl 4-bromophthalate, and diethyl 4-bromophthalate. , 4-bromophthalate di-n-butyl, 4-bromophthalate diisobutyl, 4-methylphthalate dineopentyl, 4,5-dimethylphthalate dineopentyl, 4-methylphthalate dineopentyl, 4-ethylphthalate dineopentyl, 4-methylphthalate-t -Butyl neopentyl, 4-ethyl phthalate-t-butyl neopentyl, dineopentyl 4,5-dimethylphthalate, dineopentyl 4,5-diethyl phthalate, 4,5-dimethyl phthalate-t-butyl neopentyl, 4, 5-diethylphthalic acid t- butyl neopentyl, 3-fluoro-phthalic acid dineopentyl, 3-chlorophthalic acid dineopentyl, 4-chlorophthalic acid dineopentyl, include 4-bromophthalic acid dineopentyl.

  Examples of malonic acid diesters include diethyl malonate, dipropyl malonate, dibutyl malonate, diisobutyl malonate, dipentyl malonate, dineopentyl malonate, and the like. Among these, diethyl malonate, dibutyl malonate, and Diisobutyl malonate is particularly preferred.

  Malonic acid diester derivatives include diethyl isopropyl bromomalonate, diethyl butyl bromomalonate, diethyl isobutyl bromomalonate, diethyl diisopropyl malonate, diethyl dibutyl malonate, diethyl diisobutyl malonate, diethyl diisopentyl malonate, isopropyl isobutyl malon Examples include diethyl acid, isopropyl isopentyl malonate dimethyl, diethyl (3-chloro-n-propyl) malonate, diethyl bis (3-bromo-n-propyl) malonate, and among these, diisobutylmalon Particularly preferred are diethyl acid and diethyl dibutylmalonate.

  Examples of maleic acid diesters include diethyl maleate, dipropyl maleate, dibutyl maleate, diisobutyl maleate, dipentyl maleate, dineopentyl maleate, dihexyl maleate, dioctyl maleate, and the like. Particularly preferred are diethyl acid, dibutyl maleate, and diisobutyl maleate.

  Maleic acid diester derivatives include diethyl isopropyl bromomaleate, diethyl butyl bromomaleate, diethyl isobutyl bromomaleate, diethyl diisopropyl maleate, diethyl dibutyl maleate, diethyl diisobutyl maleate, diethyl diisopentyl maleate, isopropyl isobutyl maleate Illustrative examples include diethyl acid, isopropyl isopentyl maleate, diethyl (3-chloro-n-propyl) maleate, diethyl bis (3-bromo-n-propyl) maleate, dibutyl dimethylmaleate, and dibutyl diethylmaleate. Among these, dibutyl dimethyl maleate, dibutyl diethyl maleate and diethyl diisobutyl maleate are particularly preferred.

  In the present invention, the components (i) and (ii) or the components (i), (ii), and (iii) are contacted to prepare a solid component. In this case, the presence of an aromatic hydrocarbon compound is present. The method of preparing the solid component by contacting under is a preferred embodiment. Specifically, aromatic hydrocarbon compounds having a boiling point of 50 to 150 ° C. such as toluene, xylene, and ethylbenzene are preferably used as the aromatic hydrocarbon compound. Moreover, these may be used independently or may be used in mixture of 2 or more types.

  In the present invention, the above components (i) and (ii) or the above components (i), (ii) and (iii) are brought into contact with each other, and two solid components having different weight contents of the electron donating compound (iii) are obtained. Two or more species, preferably two species, are prepared and mixed. When two solid components having different weight contents of the electron donating compound are mixed to prepare a solid catalyst component, the electron donation in the solid component (a) having a lower weight content of the electron donating compound in the solid component. Da is 0 or Db, where Da is the weight content of the active compound and Da is the weight content of the electron donating compound in the solid component (b) having a higher weight content of the electron donating compound in the solid component. The ratio Da / Db of the smaller, electron-donating compound weight content is 0 ≦ Da / Db <1, preferably 0 ≦ Da / Db <0.5, more preferably 0 ≦ Da / Db <0. 3.

  Below, the preparation method of the solid component of this invention is described. Specifically, the magnesium compound (i) is suspended in an alcohol, a halogenated hydrocarbon solvent, a tetravalent titanium halogen compound (ii) or an aromatic hydrocarbon compound, and an electron such as phthalic acid diester is used as necessary. Examples thereof include a method of obtaining a solid component by contacting a donor compound (iii) and / or a tetravalent titanium halogen compound (ii). In the method, a spherical solid catalyst component having a sharp particle size distribution can be obtained by using a spherical magnesium compound, and without using the spherical magnesium compound, for example, a solution or suspension can be obtained using a spray device. By forming particles by a so-called spray drying method in which the liquid is sprayed and dried, a solid catalyst component having a spherical shape and a sharp particle size distribution can be obtained.

  The contact of each component is performed with stirring in a container equipped with a stirrer in an inert gas atmosphere and in a state where moisture and the like are removed. The contact temperature is the temperature at the time of contact of each component, and may be the same temperature as the reaction temperature or a different temperature. The contact temperature may be a relatively low temperature range around room temperature when the mixture is simply brought into contact with stirring and mixed, or dispersed or suspended for modification, but the product is allowed to react after contact. When obtaining, the temperature range of 40-130 degreeC is preferable. If the temperature during the reaction is less than 40 ° C., the reaction does not proceed sufficiently, resulting in insufficient performance of the prepared solid component, and if it exceeds 130 ° C., the evaporation of the solvent used becomes remarkable. , It becomes difficult to control the reaction. The reaction time is 1 minute or longer, preferably 10 minutes or longer, more preferably 30 minutes or longer.

  As a preferred method for preparing the solid component (b) having a high weight content of the electron donating compound (iii), the component (i) is suspended in an aromatic hydrocarbon compound, and then the component (ii) is contacted. Method of preparing solid component (b) by contacting and reacting component (iii), or component (i) suspended in an aromatic hydrocarbon compound and then contacting component (iii) A method of preparing the solid component (b) by bringing (ii) into contact with each other and reacting them can be mentioned.

  Moreover, as a preferable preparation method of the solid component (a) having a lower weight content of the electron donating compound (iii), the amount of the component (iii) to be contacted in the preparation of the solid component (b) is reduced. Alternatively, the solid component (a) is prepared without using any component (iii). Specifically, a method of preparing the solid component (a) by suspending the component (i) in an aromatic hydrocarbon compound and then bringing the component (ii) into contact with each other and reacting them can be mentioned. Furthermore, after the solid component (b) is prepared, the electron donating compound (iii) contained in the solid component (b) is extracted by various methods to reduce or remove the electron donating compound (iii). Thus, the solid component (a) may be prepared. As an extraction method, the solid component (b) is suspended in an organic solvent and heated, or an organosilicon compound, an organoaluminum compound, an aluminum halide compound, or a halogenated organoaluminum compound is added to the suspension. And processing method.

Below, the preferable contact order at the time of preparing the solid component of this invention using the electron-donating compound (iii) is illustrated more concretely.
(1) (i) → (ii) → (iii) → << intermediate washing → (ii) >> → final washing → solid component (2) (i) → (iii) → (ii) → << intermediate washing → (ii ) >> Final washing → Solid component (3) (i) → (ii) → (iii) → << Intermediate washing → (ii) → (iii) >> → Final washing → Solid component (4) (i) → (ii ) → (iii) → << intermediate washing → (iii) → (ii) >> → final washing → solid component (5) (i) → (iii) → (ii) → << intermediate washing → (ii) → (iii) >> → Final washing → Solid component (6) (i) → (iii) → (ii) → << Intermediate washing → (iii) → (ii) >> → Final washing → Solid component In each of the above contact methods, About the process in a bracket | parenthesis (<<), activity improves further by repeating several times as needed. In addition, the component (ii) used in the step in <> may be newly added or may be the residue of the previous step. In addition to the washing steps shown in (1) to (6) above, the product obtained in each contact stage can be washed with a hydrocarbon compound that is liquid at room temperature.

  Based on the above, as a particularly preferred preparation method of the solid component using the electron donating compound (iii) in the present application, dialkoxymagnesium (i) is suspended in an aromatic hydrocarbon compound having a boiling point of 50 to 150 ° C., and then After the tetravalent titanium halogen compound (ii) is brought into contact with this suspension, a reaction treatment is performed. At this time, before or after the tetravalent titanium halogen compound (ii) is brought into contact with the suspension, if necessary, one or more electron donating compounds (iii) such as dibutyl phthalate are added. -20-130 degreeC, a reaction process is performed and a solid reaction product (1) is obtained. At this time, it is desirable to carry out the aging reaction at a low temperature before or after contacting one or more of the electron donating compounds (iii). After washing this solid reaction product (1) with a liquid hydrocarbon compound at room temperature (intermediate washing), tetravalent titanium halogen compound (ii) is again added to -20 to 100 in the presence of the aromatic hydrocarbon compound. The reaction treatment is performed by contacting at 0 ° C. to obtain a solid reaction product (2). If necessary, intermediate cleaning and reaction treatment may be repeated a plurality of times. Next, the solid reaction product (2) is washed with a hydrocarbon compound that is liquid at room temperature (final washing) to obtain a solid component.

Preferred conditions for the above treatment or washing are as follows.
Low temperature aging reaction: −20 to 70 ° C., preferably −10 to 60 ° C., more preferably 0 to 30 ° C., 1 minute to 6 hours, preferably 5 minutes to 4 hours, particularly preferably 10 minutes to 3 hours. .
Reaction treatment: 40 to 130 ° C., preferably 70 to 120 ° C., particularly preferably 80 to 115 ° C., 0.5 to 6 hours, preferably 0.5 to 5 hours, particularly preferably 1 to 4 hours.
Washing: 0 to 110 ° C., preferably 30 to 100 ° C., particularly preferably 30 to 90 ° C., 1 to 20 times, preferably 1 to 15 times, particularly preferably 1 to 10 times.
The hydrocarbon compound used for washing is preferably an aromatic or saturated hydrocarbon compound that is liquid at room temperature. Specifically, toluene, xylene, ethylbenzene, etc. as the aromatic hydrocarbon compound, and hexane as the saturated hydrocarbon compound. , Heptane, cyclohexane and the like. Preferably, an aromatic hydrocarbon compound is used in the intermediate cleaning, and a saturated hydrocarbon compound is used in the final cleaning.

  The amount of each component used in preparing the solid component varies depending on the preparation method, and thus cannot be specified unconditionally. For example, the tetravalent titanium halogen compound (ii) is 0.5 per mol of the magnesium compound (i). To 100 mol, preferably 0.5 to 50 mol, more preferably 1 to 10 mol, and the aromatic hydrocarbon compound is 0.001 to 500 mol, preferably 0.001 to 100 mol, more preferably 0.00. 005 to 10 mol.

  Further, the electron donating compound (iii) varies depending on the amount finally contained in the solid component, but 0.01 to 10 mol, preferably 0.01 to 1 mol, per mol of the magnesium compound (i). Preferably it is 0.02-0.6 mol.

  Further, the weight content of titanium, magnesium and halogen atoms in the solid component in the present invention is not particularly specified, but preferably titanium is 1.0 to 8.0% by weight, preferably 2.0 to 8.0% by weight. More preferably 3.0 to 8.0% by weight, magnesium 10 to 70% by weight, more preferably 10 to 50% by weight, particularly preferably 15 to 40% by weight, still more preferably 15 to 25% by weight, halogen An atom is 20 to 85% by weight, more preferably 30 to 85% by weight, particularly preferably 40 to 80% by weight, and further preferably 45 to 75% by weight.

  As for the electron donating compound, the weight content of the electron donating compound in the solid component (a) in which the weight content of the electron donating compound in the solid component is smaller is 0 to 10% by weight, preferably 0. Db is the weight content of the electron donating compound in the solid component (b), which is ˜5 wt%, more preferably 0 to 3 wt%, and the weight content of the electron donating compound in the solid component is larger. It is 1 to 30% by weight, more preferably 5 to 25% by weight, particularly preferably 8 to 20% by weight.

  The solid catalyst component (A) of the present invention is prepared by mixing solid components having different weight contents of two or more electron donating compounds, such as the solid component (a) and the solid component (b). Specifically, it is prepared by carrying out a post-treatment after bringing these into contact with each other. More specifically, it is carried out using a Nauter mixer, a V-type mixer, a vibration mill, a ball mill, a tank equipped with a stirrer or a reactor.

  This contact mixing is performed in the presence or absence of an organic solvent. Examples of the organic solvent used include saturated hydrocarbons such as hexane, heptane, and cyclohexane, aromatic hydrocarbons such as benzene, toluene, xylene, and ethylbenzene, and ortho Halogenated hydrocarbons such as dichlorobenzene, methylene chloride, carbon tetrachloride, dichloroethane and the like.

  There is no particular limitation on the temperature when two or more kinds of solid components having different electron-donating compound weight contents in the presence or absence of an organic solvent are contact-mixed, but usually in the range of 0 to 150 ° C. Yes, preferably at 0 to 120 ° C. for 1 minute to 10 hours, preferably 5 minutes to 5 hours. In this contact mixing, a so-called heat treatment in which the treatment is performed at room temperature or higher is also one preferred embodiment. When the solid catalyst component (A) obtained by this heat treatment is used for olefin polymerization, excessive heat generation at the initial stage of the polymerization can be suppressed, and as a result, a polymer with less fine powder and high bulk specific gravity can be obtained in high yield. be able to. This heating condition is usually set in a temperature range of 50 to 150 ° C., preferably 80 to 100 ° C., and a treatment time of 1 minute to 5 hours, preferably 5 minutes to 3 hours.

  The mixing ratio when mixing two or more solid components having different weight contents of the electron donating compound is arbitrary. For example, the solid component (a) and the solid component (b) can be mixed in two types as described above. When the ratio of the weight content of each electron donating compound is 0 ≦ Da / Db <0.5, the weight ratio (a) :( b) = 1: 99 of the solid component (a) and the solid component (b). Mix to ~ 99: 1. A more preferable range of the weight ratio is 5:95 to 50:50, and a more preferable range is 10:90 to 30:70.

  Further, as described above, two or more kinds of solid components having different electron-donating compound weight contents are contact-mixed, and then component (ii) or component (iii) used for the preparation of the solid component again is mixed with the mixture. Preparation of the solid catalyst component (A) by treatment by contact is also one of preferred embodiments for obtaining a polymer having a predetermined polymerization activity, stereoregularity or crystallinity in a high yield.

  The following is the order in which components (ii) and (iii) are contact-treated with a mixture obtained by contacting and mixing solid components having different weight contents of the two types of electron-donating compounds, solid component (a) and solid component (b). Although there is no restriction | limiting in particular, Although it is arbitrary, it will become as follows when the contact order is illustrated.

1. Contact component (ii) with a mixture obtained by contacting and mixing solid component (a) and solid component (b).
2. The components (ii) and (iii) are brought into contact with a mixture obtained by contacting and mixing the solid component (a) and the solid component (b).
3. After contacting component (ii) with the mixture obtained by contacting and mixing solid component (a) and solid component (b), contact component (iii).
After contacting component (iii) with the mixture obtained by contacting and mixing solid component (a) and solid component (b), component (ii) is contacted.

  Conditions such as the temperature, contact time, and quantity ratio with the mixture when the components are brought into contact with the mixture obtained by contacting and mixing the solid component (a) and the solid component (b) as described above, and the amount ratio with the mixture are arbitrary and are particularly limited. Rather, the same conditions as in the method for preparing the solid component (a) or the solid component (b) described above can be employed.

  A specific example of preparing the solid catalyst component (A) by bringing each component into contact with a mixture obtained by contacting and mixing the solid component (a) and the solid component (b) is as follows.

  The solid component (a) and the solid component (b) are mixed with an aromatic hydrocarbon such as toluene in a temperature range of −10 to 99: 1 at a ratio of the weight ratio of (a) :( b) of 1:99 to 99: 1. Suspend at ˜30 ° C. and add titanium tetrachloride as component (ii) to the suspension. In this case, the amount of titanium tetrachloride is preferably ½ or less by volume ratio with respect to the solvent in which the solid component (a) and the solid component (b) are suspended. The suspension is heated and held at a temperature range of 90 to 120 ° C. for 30 minutes to 3 hours to obtain a solid product. Finally, the solid product is washed with heptane to obtain a solid catalyst component (A).

  Thus, the solid catalyst component of the present invention which is a mixture obtained by contacting and mixing the solid component (a) and the solid component (b) having different electron-donating compound content and Ti content is the catalyst in the final solid catalyst component. The presence of active sites is diverse, and the effect of improving the catalytic activity due to the interaction between these various active sites and the broadening of the molecular weight distribution of the resulting polymer are manifested. On the other hand, the solid catalyst component prepared by contacting the component (i), the component (ii), and the component (iii) is uniformly distributed with the electron donating compound and Ti as a whole, There is not much diversity in the catalytic activity point, and as a result, the effect of the present invention cannot be obtained.

  The solid catalyst component (A) of the present invention obtained above is used as a polymerization catalyst in combination with the components (B) and (C) described below when subjected to the polymerization reaction of olefins.

  As the organoaluminum compound (B) used in forming the olefin polymerization catalyst of the present invention, an organoaluminum compound represented by the above general formula (1) is used. Examples of the organoaluminum compound (B) include triethylaluminum, diethylaluminum chloride, tri-iso-butylaluminum, diethylaluminum bromide, ethylaluminum sesquichloride, ethylaluminum hydride, and the like, one or more of them. Can be used. Triethylaluminum and tri-iso-butylaluminum are preferable.

  The external electron donating compound (C) (hereinafter sometimes referred to as “component (C)”) used in forming the olefin polymerization catalyst of the present invention is an organic compound containing an oxygen atom or a nitrogen atom. For example, alcohols, phenols, ethers, esters, ketones, acid halides, aldehydes, amines, amides, nitriles, isocyanates, organosilicon compounds containing Si—O—C bonds, etc. Is mentioned. Among them, polyethers such as 9,9-bis (methoxymethyl) fluorene, 2-isopropyl-2-isopentyl-1,3-dimethoxypropane, esters such as methyl benzoate, ethyl benzoate and paraethoxyethyl benzoate, It is also an organosilicon compound.

As said organosilicon compound, following General formula (2);
R ² _r Si (OR ³ ) _4-r (2)
(Wherein, R ² is an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group, a phenyl group, a vinyl group, an allyl group, in any of the aralkyl groups may be the same or different .R ³ is carbon atoms of 1 4 is an alkyl group, a cycloalkyl group, a phenyl group, a vinyl group, an allyl group, or an aralkyl group, which may be the same or different (r is an integer of 0 or 1 to 3). Used. Examples of such an organosilicon compound include phenylalkoxysilane, alkylalkoxysilane, phenylalkylalkoxysilane, cycloalkylalkoxysilane, and cycloalkylalkylalkoxysilane.

  Specific examples of the organosilicon compound include trimethylmethoxysilane, trimethylethoxysilane, tri-n-propylmethoxysilane, tri-n-propylethoxysilane, tri-n-butylmethoxysilane, tri-iso-butylmethoxy. Silane, tri-t-butylmethoxysilane, tri-n-butylethoxysilane, tricyclohexylmethoxysilane, tricyclohexylethoxysilane, cyclohexyldimethylmethoxysilane, cyclohexyldiethylmethoxysilane, cyclohexyldiethylethoxysilane, dimethyldimethoxysilane, dimethyldiethoxy Silane, di-n-propyldimethoxysilane, di-iso-propyldimethoxysilane, di-n-propyldiethoxysilane, di-iso-propyldiethoxy Lan, di-n-butyldimethoxysilane, di-iso-butyldimethoxysilane, di-t-butyldimethoxysilane, di-n-butyldiethoxysilane, n-butylmethyldimethoxysilane, bis (2-ethylhexyl) dimethoxysilane Bis (2-ethylhexyl) diethoxysilane, dicyclopentyldimethoxysilane, dicyclopentyldiethoxysilane, dicyclohexyldimethoxysilane, dicyclohexyldiethoxysilane, bis (3-methylcyclohexyl) dimethoxysilane, bis (4-methylcyclohexyl) dimethoxysilane Bis (3,5-dimethylcyclohexyl) dimethoxysilane, cyclohexylcyclopentyldimethoxysilane, cyclohexylcyclopentyldiethoxysilane, cyclohexylcyclopenty Dipropoxysilane, 3-methylcyclohexylcyclopentyldimethoxysilane, 4-methylcyclohexylcyclopentyldimethoxysilane, 3,5-dimethylcyclohexylcyclopentyldimethoxysilane, 3-methylcyclohexylcyclohexyldimethoxysilane, 4-methylcyclohexylcyclohexyldimethoxysilane, 3,5- Dimethylcyclohexylcyclohexyldimethoxysilane, cyclopentylmethyldimethoxysilane, cyclopentylmethyldiethoxysilane, cyclopentylethyldiethoxysilane, cyclopentyl (iso-propyl) dimethoxysilane, cyclopentyl (iso-butyl) dimethoxysilane, cyclohexylmethyldimethoxysilane, cyclohexylmethyldiethoxy Silane, cyclohexyl Tildimethoxysilane, cyclohexylethyldiethoxysilane, cyclohexyl (n-propyl) dimethoxysilane, cyclohexyl (iso-propyl) dimethoxysilane, cyclohexyl (n-propyl) diethoxysilane, cyclohexyl (iso-butyl) dimethoxysilane, cyclohexyl (n -Butyl) diethoxysilane, cyclohexyl (n-pentyl) dimethoxysilane, cyclohexyl (n-pentyl) diethoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, phenylmethyldimethoxysilane, phenylmethyldiethoxysilane, phenylethyldimethoxysilane , Phenylethyldiethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyl Rutriethoxysilane, n-propyltrimethoxysilane, iso-propyltrimethoxysilane, n-propyltriethoxysilane, iso-propyltriethoxysilane, n-butyltrimethoxysilane, iso-butyltrimethoxysilane, t-butyltri Methoxysilane, n-butyltriethoxysilane, 2-ethylhexyltrimethoxysilane, 2-ethylhexyltriethoxysilane, cyclopentyltrimethoxysilane, cyclopentyltriethoxysilane, cyclohexyltrimethoxysilane, cyclohexyltriethoxysilane, vinyltrimethoxysilane, vinyl Triethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, te A tributoxysilane etc. can be mentioned. Among the above, di-n-propyldimethoxysilane, di-iso-propyldimethoxysilane, di-n-butyldimethoxysilane, di-iso-butyldimethoxysilane, di-t-butyldimethoxysilane, di-n-butyldi Ethoxysilane, t-butyltrimethoxysilane, dicyclohexyldimethoxysilane, dicyclohexyldiethoxysilane, cyclohexylmethyldimethoxysilane, cyclohexylmethyldiethoxysilane, cyclohexylethyldimethoxysilane, cyclohexylethyldiethoxysilane, dicyclopentyldimethoxysilane, dicyclopentyldiethoxy Silane, cyclopentylmethyldimethoxysilane, cyclopentylmethyldiethoxysilane, cyclopentylethyldiethoxysilane, cyclohexylsilane Lopentyldimethoxysilane, cyclohexylcyclopentyldiethoxysilane, 3-methylcyclohexylcyclopentyldimethoxysilane, 4-methylcyclohexylcyclopentyldimethoxysilane, 3,5-dimethylcyclohexylcyclopentyldimethoxysilane are preferably used, and the organosilicon compound (C) is 1 It can be used in combination of two or more species.

  Next, the catalyst for olefin polymerization of the present invention is formed from containing the above-described solid catalyst component (A), component (B), and component (C) for olefin polymerization, and in the presence of the catalyst, Polymerization or copolymerization is performed. Examples of olefins include ethylene, propylene, 1-butene, 1-pentene, 4-methyl-1-pentene, and vinylcyclohexane. These olefins can be used alone or in combination of two or more. In particular, ethylene, propylene and 1-butene are preferably used. Particularly preferred is propylene. In the case of polymerization of propylene, copolymerization with other olefins can also be performed. Examples of olefins to be copolymerized include ethylene, 1-butene, 1-pentene, 4-methyl-1-pentene, vinylcyclohexane, and the like, and these olefins can be used alone or in combination of two or more. In particular, ethylene and 1-butene are preferably used.

  The amount of each component used is arbitrary as long as it does not affect the effect of the present invention, and is not particularly limited. Usually, the organoaluminum compound (B) is titanium in the solid catalyst component (A). It is used in the range of 1 to 2000 mol, preferably 50 to 1000 mol, per mol of atoms. The organosilicon compound (C) is used in an amount of 0.002 to 10 mol, preferably 0.01 to 2 mol, particularly preferably 0.01 to 0.5 mol, per 1 mol of the component (B).

  The order of contacting the components is arbitrary, but the organoaluminum compound (B) is first charged into the polymerization system, then the external electron-donating compound (C) is contacted, and then the solid catalyst component (A ) Is desirable.

  The polymerization method in the present invention can be carried out in the presence or absence of an organic solvent, and the olefin monomer such as propylene can be used in any state of gas and liquid. The polymerization temperature is 200 ° C. or lower, preferably 100 ° C. or lower, and the polymerization pressure is 10 MPa or lower, preferably 5 MPa or lower. Moreover, any of a continuous polymerization method and a batch type polymerization method is possible. Furthermore, the polymerization reaction may be performed in one stage or in two or more stages.

  Furthermore, in the present invention, when the olefin is polymerized using the catalyst formed from the solid catalyst component (A), the component (B), and the component (C) for olefin polymerization (also referred to as main polymerization). In order to further improve the catalytic activity, stereoregularity, particle properties of the polymer to be produced, etc., it is desirable to perform prepolymerization prior to the main polymerization. In the prepolymerization, the same olefins as in the main polymerization or monomers such as styrene can be used.

  In carrying out the prepolymerization, the order of contacting the respective components and monomers is arbitrary, but preferably, the component (B) is first charged into the prepolymerization system set to an inert gas atmosphere or an olefin gas atmosphere, and then the olefin. After contacting the solid catalyst component (A) for homopolymerization, an olefin such as propylene and / or one or more other olefins are contacted. When the prepolymerization is performed by combining the component (C), the component (B) is first charged into the prepolymerization system set to an inert gas atmosphere or an olefin gas atmosphere, and then the component (C) is contacted. A method of contacting an olefin such as propylene and / or one or other two or more olefins after contacting the solid catalyst component (A) for olefin polymerization is desirable.

  When olefins are polymerized in the presence of an olefin polymerization catalyst formed by the present invention, a broad molecular weight distribution is maintained while maintaining a high degree of polymerization activity and stereoregularity compared to the case of using conventional catalysts. The polymer can be obtained with good yield.

  Hereinafter, the present invention will be specifically described based on examples. However, the scope of the present invention is not limited to these examples.

The xylene-soluble component (XS) of the polymer was measured by the following method.
Method for measuring xylene-soluble component: 4.0 g of the polymer was charged into 200 ml of para-xylene, and the polymer was dissolved at a boiling point (138 ° C.) over 2 hours. Thereafter, the mixture was cooled to 23 ° C., and the dissolved component and the insoluble component were separated by filtration. The dissolved component was dried by heating, and the resulting polymer was defined as xylene-soluble component (XS) (% by weight).

In addition, the molecular weight distribution of the polymer is a ratio Mw / weight average molecular weight Mw and number average molecular weight Mn obtained by measurement under the following conditions using a cross-fractionation chromatograph (CFC) (CFC T-150B manufactured by Mitsubishi Chemical Corporation). Mn and Z average molecular weight (Mz / Mw) were evaluated.
Solvent: o-dichlorobenzene (ODCB)
Temperature: 140 ° C (SEC)
Column: Shodex GPC UT-806M
Sample concentration: 4g / liter-ODCB (200mg / 50ml-ODCB)
Injection volume: 0.5ml
Flow rate: 1.0ml / min
Measuring range: 0 ℃ ~ 140 ℃

[Preparation of solid catalyst component (A)]
(1) Preparation of solid component (a) A 500 ml round bottom flask equipped with a stirrer and sufficiently substituted with nitrogen gas was charged with 20 g of diethoxymagnesium and 160 ml of toluene to form a suspended state. . Next, 40 ml of titanium tetrachloride was added to the suspension. Next, the suspension was heated to 110 ° C. and reacted for 2.0 hours with stirring. After completion of the reaction, washing was performed 3 times with 200 ml of toluene at 90 ° C. Thereafter, 160 ml of toluene and 40 ml of titanium tetrachloride were newly added, and a reaction treatment was performed at 110 ° C. for 2 hours while stirring. The product was then washed 8 times with 200 ml of 40 ° C. heptane, filtered and dried to obtain a powdered solid catalyst component (A). The titanium content in the solid catalyst component was 19.2% by weight, and no electron-donating compound was detected.

(2) Preparation of solid component (b) A 500 ml round bottom flask equipped with a stirrer and sufficiently substituted with nitrogen gas was charged with 20 g of diethoxymagnesium and 160 ml of toluene to form a suspended state. . Next, 40 ml of titanium tetrachloride was added to the suspension. Next, the suspension was heated to 90 ° C., 5.4 ml of di-n-butyl phthalate was added, the temperature was further raised to 110 ° C., and the reaction treatment was performed for 1.5 hours with stirring. After completion of the reaction, washing was performed 3 times with 180 ml of 90 ° C. toluene. Thereafter, 140 ml of toluene and 40 ml of titanium tetrachloride were newly added, and a reaction treatment was performed at 100 ° C. for 2 hours while stirring. The product was then washed 8 times with 200 ml of 40 ° C. heptane, filtered and dried to obtain a powdered solid catalyst component (A). The titanium content in the solid catalyst component was 2.9% by weight, and the electron donating compound was 10.9% by weight.

(3) Contact mixing of solid component (a) and solid component (b) To a 100 ml round bottom flask fully substituted with nitrogen gas and equipped with a stirrer, 10 g of the solid component (a) obtained above 90 g (weight ratio 10:90) of the solid component (b) was charged and stirred at room temperature for 5 minutes to obtain a solid catalyst component (A). The Ti content in the solid component was 4.5% by weight.

[Preparation and polymerization of polymerization catalyst]
Into an autoclave with a stirrer having an internal volume of 2.0 liters completely substituted with nitrogen gas, 1.32 mmol of triethylaluminum, 0.13 mmol of cyclohexylmethyldimethoxysilane and 0.0026 mmol of the above solid catalyst component as titanium atoms were charged. A polymerization catalyst was formed. Thereafter, 0.8 to 2.2 liters of hydrogen gas and 1.4 liters of liquefied propylene were charged, preliminarily polymerized at 20 ° C. for 5 minutes, and then heated to 70 ° C. for 1 hour. The polymerization activity per gram of the solid catalyst component was calculated by the following formula.
Polymerization activity = produced polymer (F) (g) / solid catalyst component (g)
Further, when this polymer was extracted with boiling n-heptane for 6 hours, the polymer (G) insoluble in n-heptane was measured, and the ratio of boiling n-heptane insoluble matter (HI) in the polymer was expressed by Calculated by
HI = (G) (g) / (F) (g)
Table 1 shows the polymerization activity, heptane-insoluble content (HI), melt index (MI) and xylene-soluble component (XS), Mw / Mn and Mz / Mw.

(1) Preparation of solid component (a) A 500 ml round bottom flask equipped with a stirrer and sufficiently substituted with nitrogen gas was charged with 20 g of diethoxymagnesium and 160 ml of toluene to form a suspended state. . Next, 40 ml of titanium tetrachloride was added to the suspension. Next, the suspension was heated to 80 ° C., 1.35 ml of di-n-butyl phthalate was added, the temperature was further raised to 110 ° C., and the reaction treatment was performed for 2.0 hours with stirring. After completion of the reaction, washing was performed 3 times with 200 ml of toluene at 90 ° C. Thereafter, 160 ml of toluene and 40 ml of titanium tetrachloride were newly added, and a reaction treatment was performed at 100 ° C. for 2 hours while stirring. The product was then washed 8 times with 200 ml of 40 ° C. heptane, filtered and dried to obtain a powdered solid catalyst component (A). The titanium content in the solid catalyst component was 14.8% by weight, and the electron donating compound was 2.1% by weight.

  A solid catalyst component was prepared in the same manner as in Example 1 except that the solid component (a) was used, and a polymerization catalyst was prepared and polymerized. The obtained results are shown in Table 1.

(1) Preparation of solid component (a) A 500 ml round bottom flask equipped with a stirrer and sufficiently substituted with nitrogen gas was charged with 20 g of diethoxymagnesium and 160 ml of toluene to form a suspended state. . Next, 40 ml of titanium tetrachloride was added to the suspension. Next, the temperature of the suspension was raised to 90 ° C., and then diethyl diisobutylmalonate (5.8 ml) was added. The temperature was further raised to 110 ° C., and the reaction treatment was performed for 2.0 hours with stirring. After completion of the reaction, washing was performed 3 times with 200 ml of toluene at 90 ° C. Thereafter, 160 ml of toluene and 40 ml of titanium tetrachloride were newly added, and a reaction treatment was performed at 100 ° C. for 2 hours while stirring. The product was then washed 8 times with 200 ml of 40 ° C. heptane, filtered and dried to obtain a powdered solid catalyst component (A). The titanium content in the solid catalyst component was 15.9% by weight, and the electron donating compound was 1.7% by weight.

  A solid catalyst component was prepared in the same manner as in Example 1 except that the solid component (a) was used, and a polymerization catalyst was prepared and polymerized. The obtained results are shown in Table 1.

Comparative Example 1
A polymerization catalyst was prepared and polymerized under the same conditions as in Example 1 except that the solid component (a) prepared in Example 1 was used as it was as a solid catalyst component. The results are shown in Table 1.

Comparative Example 2
A polymerization catalyst was prepared and polymerized under the same conditions as in Example 1 except that the solid component (b) prepared in Example 1 was used as it was as a solid catalyst component. The results are shown in Table 1.

Comparative Example 3
A polymerization catalyst was prepared and polymerized under the same conditions as in Example 1 except that the solid component (a) prepared in Example 2 was used as it was as a solid catalyst component. The results are shown in Table 1.

Comparative Example 4
A polymerization catalyst was prepared and polymerized under the same conditions as in Example 1 except that the solid component (a) prepared in Example 3 was used as it was as a solid catalyst component. The results are shown in Table 1.

  From the above results, it can be seen that the catalyst of the present invention has a significantly higher polymerization activity and a polymer with a broader molecular weight distribution while maintaining a high degree of polymer stereoregularity as compared with conventional catalysts. In particular, the value of Mz / Mw is high, and it can be seen that the polymer in the polymer region that has a large effect on processability increases and the molecular weight distribution is broadened. Furthermore, the polymerization activity is improved, HI and XS are not lowered, and the stereoregularity of the polymer is maintained at a high level.

It is a flowchart figure which shows the process of preparing the catalyst component and polymerization catalyst of this invention.

Claims (8)

  It is characterized in that it is obtained by mixing two or more solid components containing magnesium, titanium and halogen or an electron-donating compound and having two or more solid components having different electron-donating compound weight contents. Solid catalyst component for olefin polymerization.   2. The solid component obtained by mixing two solid components containing magnesium, titanium and halogen or an electron donating compound and having different weight contents of the electron donating compound. The solid catalyst component for olefin polymerization as described.   Of the two kinds of solid components, the weight content Da of the electron donating compound having a small weight content of the electron donating compound and the electron donating compound of the solid component having a large weight content of the electron donating compound The solid catalyst component for olefin polymerization according to claim 2, wherein the ratio Da / Db to the weight content Db satisfies 0 ≦ Da / Db <1.   3. The solid catalyst component for olefin polymerization according to claim 2, wherein the ratio Da / Db satisfies 0 ≦ Da / Db <0.5.   The solid catalyst component for olefin polymerization according to claim 2, wherein the ratio Da / Db satisfies Da / Db = 0.   3. The solid catalyst component for olefin polymerization according to claim 1, wherein the electron donating compound is a dicarboxylic acid diester. An olefin polymerization catalyst formed from the following components (A), (B) and (C):
(A) The solid catalyst component for olefin polymerization according to claims 1 to 6,
(B) the following general formula (1);
R ¹ _q AlY _3-q (1)
(Wherein R ¹ represents an alkyl group having 1 to 4 carbon atoms, Y represents a hydrogen atom or a halogen atom, and q represents a real number of 0 <q <3), and (C) External electron donating compound. The (C) external electron donating compound is represented by the following general formula (2):
R ² _r Si (OR ³ ) _4-r (2)
(Wherein, R ² is an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group, a phenyl group, a vinyl group, an allyl group, in any of the aralkyl group may .R ³ be the same or different 1 to carbon atoms 4 is an alkyl group, a cycloalkyl group, a phenyl group, a vinyl group, an allyl group, or an aralkyl group, which may be the same or different (r is an integer of 0 or 1 to 3). The catalyst for olefin polymerization according to claim 7, which is a compound.

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