JP5254048B2 - Method for producing solid catalyst component for olefin polymerization - Google Patents

Description

  The present invention relates to a solid catalyst component for olefin polymerization, which can maintain a high degree of stereoregularity and yield of the polymer, and can obtain a polymer with a small amount of fine powder, a production method and a catalyst thereof, and an olefin polymer. It relates to the manufacturing method.

  Conventionally, in the polymerization of olefins, a large number of highly active olefin polymerization solid catalyst components containing magnesium, titanium, an electron donating compound and halogen as essential components have been proposed. When polymerization of olefins is carried out using a polymerization catalyst having a composition comprising this type of highly active solid catalyst component and an electron donating compound typified by an organoaluminum compound and a silicon compound, the solid catalyst component itself becomes fine powder. There was a tendency that a finely divided polymer was produced, or a finely divided polymer was produced due to particle breakage due to reaction heat at the time of polymerization, and that the produced polymer contained a lot of finely divided polymer, and the particle size distribution of the produced polymer tended to be broad. In particular, when the solid catalyst component was produced by a heterogeneous reaction, the fine powder of the solid catalyst component itself increased and the fine powder polymer in the produced polymer increased. If the amount of fine polymer increases, it may cause a process failure such as hindering the continuation of the uniform reaction and blockage of the piping during the transfer of the polymer. Therefore, a fine powder polymer is as little as possible, and a polymer having a uniform particle size and a narrow particle size distribution is desired.

  As a method for solving this problem, in Patent Document 1 (JP-A-6-287225), a suspension of spherical dialkoxymagnesium, an aromatic hydrocarbon compound and a phthalic acid diester is used as an aromatic hydrocarbon compound. It is added to the mixed solution of titanium tetrachloride and allowed to react. The resulting reaction product is washed with an aromatic hydrocarbon compound, and the solid component obtained by reacting with titanium tetrachloride again is dried to remove fine powder. A solid catalyst component for olefin polymerization obtained through a process has been proposed.

  In the above proposal, although the catalyst component obtained by removing the fine powder of the solid catalyst component itself is used, the effect of reducing the amount of fine powder in the region of 45 to 200 μm to some extent by the particle size in the produced polymer is recognized, In particular, the generation of ultrafine polymer that belongs to a region having a particle size of 45 μm or less, called microfine, has remained as an unsolved problem. These ultrafine polymers cause problems such as clogging of the filter in the polymer recovery process and gas recycling system in the continuous operation of the polymerization process, accumulation in the vessel and piping in the system, maintenance of plant equipment and temporary suspension of the plant It was recognized as a serious problem because it caused an increase in costs due to loss of production opportunities. From such an industrial point of view, a catalyst capable of obtaining a polymer in which the amount of ultrafine powder generated is greatly reduced is strongly desired.

  In Patent Document 2 (Japanese Patent Laid-Open No. 2006-274105), an alkoxy-containing magnesium compound is brought into contact with an alkoxy-containing magnesium compound in the presence of an electron-donating compound, and then at least completely alkoxylated. A catalyst manufacturing method has been proposed in which the halogenation of an alkoxy-containing magnesium compound is controlled by contacting an amount of a titanium halide compound that halogenates the magnesium-containing compound. However, since the reaction heat differs greatly between the initial stage and the latter stage of the addition of the titanium halide compound, the control of the halogenation reaction is insufficient, and a drastic improvement for suppressing the generation of ultrafine powder is necessary.

  Accordingly, an object of the present invention is to obtain a polymer in which fine powder polymers of 45 μm or less are sufficiently reduced while maintaining a high yield of highly stereoregular polymers when subjected to olefin polymerization. Another object of the present invention is to provide a solid catalyst component for olefin polymerization, a method for producing the same, a catalyst, and a method for producing an olefin polymer or copolymer using the same.

  Under such circumstances, the present inventors have conducted extensive studies, and as a result, (1) the fine powder produced when forming the solid catalyst component, and the fine powder polymer obtained by polymerizing olefins using this are the raw materials. If the reaction heat of the halogenation reaction generated when an alkoxy-containing magnesium compound (a) is brought into contact with the titanium halide compound (b) can be suppressed, (2) component (a) and component (b) In order to complete the present invention, it has been found that the catalyst component obtained by contacting under a specific condition) can maintain the polymer activity and stereoregularity at a high level and can obtain a polymer with a small amount of fine powder. It came.

That is , the present invention is a method for obtaining a solid catalyst component by intermittently contacting an alkoxy-containing magnesium compound (a) and a titanium halogen compound (b) a plurality of times, and contacting the component (b) with the component (a). The amount is 0.5 to 10 moles per minute with respect to 1 mole of component (a), and the amount of one contact is 13% by weight of the total amount used for contacting each of component (a) and component (b) The present invention provides a method for producing a solid catalyst component for olefin polymerization, which is characterized by the following.

  The present invention is also a method for obtaining a solid catalyst component by continuously contacting an alkoxy-containing magnesium compound (a) and a titanium halogen compound (b), wherein the contact amount of the component (b) with respect to the component (a) is The amount of component (a) added per minute per component (a) is 0.5 to 10 mol per minute and (0.3 to 1.0% by weight) × (contact The present invention provides a method for producing a solid catalyst component for olefin polymerization, characterized in that the total amount of component (a) used).

  When olefins are polymerized in the presence of a catalyst prepared using the solid catalyst component for olefin polymerization of the present invention, a finely divided polymer of 45 μm or less in particular while maintaining a high yield of highly stereoregular polymer. Can be obtained. Therefore, general-purpose polyolefin can be provided safely and at low cost.

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

  Examples of the alkoxy-containing magnesium compound used in the present invention (hereinafter sometimes simply referred to as “component (a)”) include alkoxyalkyl magnesium, alkoxy halogen magnesium, dialkoxy magnesium and the like. Of these, dialkoxymagnesium is preferred. Examples of dialkoxymagnesium include powdery materials such as diethoxymagnesium, dipropoxymagnesium, dibutoxymagnesium, ethoxymethoxymagnesium, ethoxypropoxymagnesium, and butoxyethoxymagnesium, with diethoxymagnesium being particularly preferred. These alkoxy-containing magnesium compounds can be used alone or in combination of two or more thereof, and can also be added to an inert organic solvent and used in a slurry state.

  The dialkoxymagnesium may be obtained by reacting metallic magnesium with an alcohol in the presence of a catalyst. Examples of the catalyst include alkyl halides such as methyl bromide, methyl chloride, ethyl bromide, and ethyl chloride, metal halides such as magnesium chloride and aluminum chloride, dialkoxymagnesium such as diethoxymagnesium, iodine, and acetate. Is used. Of these, iodine and diethoxymagnesium are particularly preferred. Metal magnesium and alcohol can be reacted by a known method, but as a preferred catalytic reaction method, the final addition ratio of metal magnesium and alcohol to the reaction system is metal magnesium / alcohol (weight ratio) = 1/9 to The final addition ratio of magnesium metal and alcohol was continuously or intermittently added to the reaction system under reflux of the alcohol and containing the catalyst, and allowed to react for 5 to 80 minutes. The mixture is kept under reflux for 1 to 30 hours and subjected to an aging reaction to obtain dialkoxymagnesium. The catalyst is preferably added at the beginning of the reaction step.

  Furthermore, dialkoxymagnesium suitable in the present invention is granular, 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 present invention is particularly effective in a method for producing a solid catalyst component by using spherical dialkoxymagnesium as a raw material and maintaining the shape of the raw material as it is.

  The spherical dialkoxymagnesium powder does not necessarily have a true spherical shape, and an elliptical shape or a potato shape 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 powder 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 powder, the average particle size is 1 to 100 μm, preferably 5 to 50 μm, more preferably 10 to 40 μm. As for the particle size distribution, it is desirable to use a fine particle and coarse powder with a small particle size distribution. 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 This is exemplified in, for example, Kaihei 8-73388.

The titanium halide compound used in the present invention (hereinafter sometimes simply referred to as “component b”) is a divalent, trivalent or tetravalent titanium halide compound, preferably a tetravalent titanium halide compound. It is. As a tetravalent titanium halide compound, the following general formula (2); Ti (OR ² ) _n Y _4-n (2)
(Wherein R ² represents an alkyl group having 1 to 4 carbon atoms, Y represents a halogen atom such as a chlorine atom, a bromine atom, or an iodine atom, and n is an integer of 0 or 1 to 3). One or two or more compounds selected from the group of titanium halides or alkoxytitanium halides. These titanium halide compounds can also be used after diluted with an inert organic solvent.

  Specifically, titanium tetrahalides such as titanium tetrachloride, titanium tetrabromide, and titanium tetraiodide as titanium halides, methoxy titanium trichloride, ethoxy titanium trichloride, propoxy titanium trichloride, and n-butoxy titanium as alkoxy titanium halides. Examples include trichloride, 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. Is done. 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.

  In the present invention, it is important to control the halogenation reaction between component (a) and component (b). However, when component (a) is dialkoxymagnesium, the generation of heat of reaction is particularly significant. The generated reaction heat is controlled so that fine powder is not generated in the obtained solid catalyst component. Specifically, the component (b) above the theoretical amount at which dialkoxymagnesium is completely halogenated is contacted continuously or intermittently and reacted to halogenate dialkoxymagnesium. In particular, the speed of the halogenation reaction is relatively fast, and in order to suppress the generation of excessive reaction heat, an extremely small amount of dialkoxymagnesium and an extremely small amount of titanium halogen compound are always brought into contact with each other at a constant ratio.

  That is, the solid catalyst component of the present invention is obtained by intermittently contacting the component (a) and the component (b) a plurality of times, and the contact amount of the component (b) with respect to the component (a) is (A) Contact that is 0.5 to 10 moles per minute with respect to 1 mole, and that the amount of contact at one time is 13% by weight or less of the total amount used for contact in each of component (a) and component (b) (Hereinafter also referred to as “specific intermittent contact conditions”) or obtained by continuously contacting the component (a) and the component (b). The contact amount of component (b) with respect to a) is 0.5 to 10 moles per minute per mole of component (a), and the amount of component (a) added per minute is (0.3). -1.0% by weight) × (total amount of component (a) used for contact) (hereinafter referred to as “specific Also referred to as connection contact condition ".) By is obtained.

  In the “specific intermittent contact conditions”, the contact amount of the component (b) with respect to the component (a) is 0.5 to 10 mol per minute per 1 mol of the component (a). In the halogenation reaction, when dialkoxymagnesium is used as the component (a) and titanium tetrachloride is used as the titanium halide compound, the contact amount is preferably 0.5 to 10 moles per mole of dialkoxymagnesium, preferably Is 0.6 to 2.5 mol, particularly preferably 1.2 to 1.8 mol.

  The amount of contact in the intermittent contact of the component (a) and the component (b) is 13% by weight or less of the total amount used for the contact of each of the component (a) and the component (b), that is, 1/8 or less, preferably Is 1/15 to 1/50, particularly preferably 1/15 to 1/40. In order to suppress the reaction heat of the halogenation reaction, this division amount can be carried out by arbitrarily changing the initial and late addition amounts. Further, it is not necessary that the component (a) and the component (b) have a constant addition ratio in each contact. Thus, it becomes easy to suppress the reaction heat which arises by a halogenation reaction by taking many contacts.

  In “specific continuous contact conditions”, the amount of component (a) added per minute is (0.3 to 1.0% by weight) × (total amount of component (a) used for contact (hereinafter “component”). (Total amount of (a) ")), preferably (0.35-0.8 wt%) x (total amount of component (a)), in particular (0.4-0.7 wt%) x (component (a) Total amount). If the amount of component (a) added per minute is too small, the production process may become long and this may lead to an increase in cost, and if too large, it is difficult to suppress reaction heat generated by the halogenation reaction. In addition, in the “specific continuous contact condition”, the amount of component (b) added per minute is 0.5 to 10 mol with respect to 1 mol of component (a). In the halogenation reaction, when dialkoxymagnesium is used as the component (a) and titanium tetrachloride is used as the titanium halide compound, the contact amount is preferably 0.5 to 10 moles per mole of dialkoxymagnesium, preferably Is 1.5 to 4.5 mol, particularly preferably 2 to 3.5 mol. If the amount of component (b) added per minute is too small, the reaction does not proceed and the production process is lengthened, which may lead to an increase in cost. If too much, the reaction heat generated by the halogenation reaction is suppressed. It becomes difficult to do.

  When a spherical dialkoxymagnesium powder is used as the component (a) in the halogenation reaction, it is particularly effective in terms of reducing fine powder. Such a powdered dialkoxymagnesium is used in a halogen such as titanium tetrachloride. When halogenated with a titanium halide compound, the halogenation reaction is intense and the dialkoxymagnesium particles are destroyed by the heat of reaction and fine powder is generated. On the other hand, the present invention pays attention to the halogenation reaction of dialkoxymagnesium by halogenating dialkoxymagnesium little by little, suppressing reaction heat, suppressing particle destruction, smoothing and strengthening the particle surface. Thus, it is possible to suppress the generation of fine powder in the first production stage and the generation of fine powder in the subsequent production stage of the solid catalyst component.

  The halogenation reaction may be a temperature at which a part of the alkoxy-containing magnesium compound is halogenated, preferably -30 to 30 ° C, more preferably -20 to 20 ° C, particularly preferably -10 to 10 ° C. . The reaction time is 1 minute or longer, preferably 10 minutes or longer, more preferably 30 minutes or longer. Halogenation of a part of the alkoxy-containing magnesium compound means that one alkoxy group of the alkoxy-containing magnesium compound is substituted with a halogen atom, and two alkoxy groups in a plurality of alkoxy-containing magnesium compound molecules are substituted with halogen atoms. It means both the presence and the non-halogenated side by side.

  In addition, the electron donating compound (c) (hereinafter, simply referred to as “component (c)”) before, during or after the continuous or intermittent contact of component (a) and component (b). Can be added). The electron donating compound is adsorbed on the halogenated particles, acts to smooth the particle surface and improve the particle strength, and can suppress generation of fine powder due to particle breakage.

  Examples of the electron donating compound include alcohols, phenols, ethers, esters, ketones, aldehydes, amines, amides, nitriles, iso-cyanates and the like.

  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-iso-propyl-2-iso-pentyl-1,3-dimethoxypropane, methyl formate, ethyl acetate, vinyl acetate, propyl acetate, octyl acetate, cyclohexyl acetate, propionic acid Ethyl, ethyl butyrate, methyl benzoate, ethyl benzoate, propyl benzoate, butyl benzoate, octyl benzoate, cyclohexyl benzoate, phenyl benzoate, methyl p-toluate, ethyl p-toluate, p-methoxybenzoate Monocarboxylic acid esters such as ethyl acetate, ethyl p-ethoxybenzoate, methyl anisate, ethyl anisate, diethyl maleate, dibutyl maleate, diethyl dimethylmalonate, diethyl diethylmalonate, di-n-propylmalonic acid Diethyl, diethyl diisopropylmalonate, diethyl di-n-butylmalonate, diethyl diisobutylmalonate, diethyl di-sec-butylmalonate, dimethyl adipate, diethyl adipate, dipropyl adipate, dibutyl adipate, diisodecyl adipate, Dicarboxylic acid esters such as dioctyl adipate, phthalic acid diester and phthalic acid diester derivatives, ketones such as acetone, methyl ethyl ketone, methyl butyl ketone, acetophenone and benzophenone, dichlore phthalate , Acid halides such as terephthalic acid dichloride, aldehydes such as acetaldehyde, propionaldehyde, octylaldehyde, benzaldehyde, amines such as methylamine, ethylamine, tributylamine, piperidine, aniline, pyridine, oleic acid amide, stearic acid amide Amides such as acetonitrile, nitriles such as acetonitrile, benzonitrile and tolunitrile, and isocyanates such as methyl isocyanate and ethyl isocyanate.

  Among the electron donating compounds, monocarboxylic acid esters such as ethyl benzoate, methyl p-toluate, ethyl p-toluate, ethyl p-ethoxybenzoate, ethyl anisate, phthalic acid diesters and phthalic acid diesters Esters such as aromatic dicarboxylic acid diesters such as derivatives are preferably used because they can further suppress fine powder generation due to particle breakage due to reaction heat during the halogenation reaction of alkoxymagnesium. 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 3) i C 6 H}} 4 - (COOR 4) (COOR 5) (3)
(In the formula, R ³ represents an alkyl group having 1 to 8 carbon atoms or a halogen atom, R ⁴ and R ⁵ represent an alkyl group having 1 to 12 carbon atoms, and R ⁴ and R ⁵ are the same or different. And the number i of the substituent R ³ is 1 or 2, and when i is 2, R ³ may be the same or different.

In the general formula (3), specific examples of R ³ being an alkyl group having 1 to 8 carbon atoms include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an 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 Specific examples of R ⁵ being a halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. R ³ is preferably a methyl group, a bromine atom or a fluorine atom, more preferably a methyl group or a bromine atom. The number i of the substituent R ³ is 1 or 2, and when i is 2, the R ³ may be the same or different. When i is 1, R ³ is substituted with a hydrogen atom at the 3-position, 4-position, 5-position or 6-position of the phthalate derivative of the general formula (3). When i is 2, R ³ is What substitutes the hydrogen atom of the 4th-position and the 5-position is preferable.

In the general formula (3), R ⁴ and R ⁵ 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, 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- A decyl group, an isodecyl group, and an 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.

  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. Di-n-butyl 4-bromophthalate, diisobutyl 4-bromophthalate, dineopentyl 4-methylphthalate, dineopentyl 4,5-dimethylphthalate, dineopentyl 4-methylphthalate, dineopentyl 4-ethylphthalate, 4-methylphthalate-t -Butyl neopentyl, 4-ethyl phthalate-t-butyl neopentyl, 4,5-dimethylphthalate dineopentyl, 4,5-diethyl phthalate dineopentyl, 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, 4-bromophthalic acid dineopentyl, and the like, alone or in combination of two or more of these can be used.

  The above esters are preferably used in combination of two or more, and the esters are used so that the total carbon number of the alkyl group of the ester used is 4 or more compared to that of other esters. It is desirable to combine.

  The contact between the component (a) and the component (b) is in the presence of an inert organic solvent (hereinafter sometimes simply referred to as “component (d)”) in terms of controlling the halogenation reaction. Preferably, the inert organic solvent dissolves the above-mentioned titanium halide compound and does not dissolve dialkoxymagnesium. Specifically, pentane, hexane, heptane, octane, nonane, decane, cyclohexane, etc. Saturated hydrocarbon compounds, aromatic hydrocarbon compounds such as benzene, toluene, xylene and ethylbenzene, halogenated hydrocarbon compounds such as methylene chloride and 1,2-dichlorobenzene, ethers such as diethyl ether, and the like. Among these, aromatic hydrocarbon compounds which are liquid at room temperature such as toluene and xylene and saturated hydrocarbon compounds which are liquid at room temperature such as hexane, heptane and cyclohexane are preferably used.

In the specific preparation method of the solid catalyst component (A) for olefin polymerization of the present invention, preferred contact methods of the components (a) to (d) are shown below.
(1) Component (a) and component (b) are added continuously or intermittently to component (d), and then component (c) is added to the suspension.
(2) Suspension in which component (a) is added to component (d) and component (b) are added to component (d) continuously or in portions, and then component (c) is added to the suspension. To do.
(3) A suspension obtained by adding the component (a) and the component (c) to the component (d) and the component (b) are added to the component (d) continuously or in portions.
(4) A suspension obtained by adding the component (a) and the component (c) to the component (d) and the component (b) are continuously or dividedly added to the component (d), and then the component (c) is added to the component (d). Add to suspension.
In these methods, the solid catalyst component (A) can be washed with an inert solvent such as an aromatic hydrocarbon compound, if necessary, and further contacted with the component (b).

  Based on the above, as a particularly preferred method for preparing the solid catalyst component (A) of the present invention, a suspension obtained by adding the component (a) to the component (d) and the component (b) are divided into the components (d). In addition, the halogenation reaction treatment is performed by contact at −20 to 20 ° C. under specific intermittent contact conditions. Subsequently, after adding a component (c) to this suspension, it heats up and makes it react in the range of 50-130 degreeC. After washing the obtained solid reaction product with a liquid hydrocarbon compound at room temperature (intermediate washing), component (b) is added again and contacted at −20 to 130 ° C. for reaction treatment, and then at room temperature. The solid catalyst component (A) is obtained by washing (final washing) with a liquid hydrocarbon compound.

  The amount ratio of the component (c) and the component (d) used for preparing the solid catalyst component (A) varies depending on the preparation method and cannot be defined unconditionally. For example, the component (c) ) Is 0.01 to 10 mol, preferably 0.01 to 1 mol, more preferably 0.02 to 0.6 mol, and component (d) is 0.001 to 500 mol, preferably 0.001 to 100 mol, more preferably 0.005 to 10 mol.

  Further, the content of titanium, magnesium, halogen atom and electron donating compound in the solid catalyst component (A) in the present invention is not particularly limited, but preferably titanium is 1.0 to 8.0% by weight, preferably 1 0.0-6.0 wt%, more preferably 1.0-4.0 wt%, magnesium 10-70 wt%, more preferably 10-50 wt%, particularly preferably 15-40 wt%, still more preferably Is 15 to 25% by weight, halogen atoms are 20 to 85% by weight, more preferably 30 to 85% by weight, particularly preferably 40 to 80% by weight, still more preferably 45 to 75% by weight, and the total amount of electron donating compounds is 0.5 to 30% by weight, more preferably 1 to 25% by weight in total, and particularly preferably 2 to 20% by weight in total.

  The solid catalyst component (A) of the present invention has a smooth particle surface and high particle strength. Moreover, the solid catalyst component (A) has few fine coarse powders, and its particle size distribution ((D90-D10) / D50) is as narrow as 0.3 to 0.8.

The organoaluminum compound (B) (hereinafter sometimes simply referred to as “component (B)”) used in forming the olefin polymerization catalyst of the present invention is a compound represented by the above general formula (1). if is not particularly limited, examples of R ^1, an ethyl group, isobutyl group are preferable, as the Q, hydrogen atom, a chlorine atom, preferably a bromine atom, p is preferably 2 or 3, most preferably 3. Specific examples of such an organoaluminum compound (B) include triethylaluminum, diethylaluminum chloride, triisobutylaluminum, diethylaluminum bromide, and diethylaluminum hydride, and one or more can be used. Triethylaluminum and triisobutylaluminum are preferable.

  In the catalyst of the present invention, an external electron donating compound (C) (hereinafter sometimes simply referred to as “component (C)”) is used in addition to the above components (A) and (B).

  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 used for the preparation of the solid catalyst component described above. The same electron donating compound (c) that can be used is used, and among them, ethers, esters, and organosilicon compounds are preferable. Among the ethers, 1,3 diether is preferable, and 9,9-bis (methoxymethyl) fluorene and 2-isopropyl-2-isopentyl-1,3-dimethoxypropane are particularly preferable. Of the esters, methyl benzoate and ethyl benzoate are preferred.

As said organosilicon compound, following General formula (3)
R ⁶ _q Si (NR ⁷ R ⁸ ) _r (OR ⁹ ) _{4- (q + r)} (3)
(In the formula, q is an integer of 0, 1 to 4, r is an integer of 0, 1 to 4, provided that q + r is an integer of 0 to 4, R ⁶ , R ⁷ or R ⁸ is a hydrogen atom, a carbon number of 1 to Any of 12 linear or branched alkyl groups, substituted or unsubstituted cycloalkyl groups, phenyl groups, vinyl groups, allyl groups, aralkyl groups, which may contain heteroatoms, and may be the same or different R ⁹ represents an alkyl group having 1 to 4 carbon atoms, a cycloalkyl group, a phenyl group, a vinyl group, an allyl group, or an aralkyl group, may contain a hetero atom, may be the same or different, and R ⁷ And R ⁸ may combine to form a ring.).

In general formula (3), R ⁶ is preferably a linear or branched alkyl group having 1 to 10 carbon atoms or a cycloalkyl group having 5 to 8 carbon atoms, and particularly a linear or branched group having 1 to 8 carbon atoms. An alkyl group and a cycloalkyl group having 5 to 8 carbon atoms are preferred. R ⁷ or R ⁸ is preferably a linear or branched alkyl group having 1 to 10 carbon atoms or a cycloalkyl group having 5 to 8 carbon atoms, particularly a linear or branched alkyl group having 1 to 8 carbon atoms. And a cycloalkyl group having 5 to 8 carbon atoms is preferred. In addition, R ⁷ and R ⁸ are combined to form a ring (NR ⁷ R ⁸ ), preferably a perhydroquinolino group or a perhydroisoquinolino group. R ⁹ is preferably a linear or branched alkyl group having 1 to 6 carbon atoms, and particularly preferably a linear or branched alkyl group having 1 to 4 carbon atoms.

  Examples of such organosilicon compounds include phenylalkoxysilane, alkylalkoxysilane, phenylalkylalkoxysilane, cycloalkylalkoxysilane, cycloalkylalkylalkoxysilane, (alkylamino) alkoxysilane, alkyl (alkylamino) alkoxysilane, alkyl ( Alkylamino) silane, alkylaminosilane and the like.

  In the formula, specific examples of the organosilicon compound in which r is 0 include trimethylmethoxysilane, trimethylethoxysilane, tri-n-propylmethoxysilane, tri-n-propylethoxysilane, tri-n-butylmethoxysilane, tri -Iso-butylmethoxysilane, tri-t-butylmethoxysilane, tri-n-butylethoxysilane, tricyclohexylmethoxysilane, tricyclohexylethoxysilane, cyclohexyldimethylmethoxysilane, cyclohexyldiethylmethoxysilane, cyclohexyldiethylethoxysilane, dimethyldimethoxy Silane, dimethyldiethoxysilane, di-n-propyldimethoxysilane, di-iso-propyldimethoxysilane, di-n-propyldiethoxysilane, di-iso-propyldi Toxisilane, di-n-butyldimethoxysilane, di-iso-butyldimethoxysilane, di-t-butyldimethoxysilane, t-butylmethylmethoxysilane, t-butylethylmethoxysilane, t-butyl (n-propyl) methoxysilane, t-butyl (isopropyl) methoxysilane, t-butyl (n-butyl) methoxysilane, t-butyl (isobutyl) methoxysilane, di-n-butyldiethoxysilane, n-butylmethyldimethoxysilane, bis (2-ethylhexyl) Dimethoxysilane, bis (2-ethylhexyl) diethoxysilane, dicyclopentyldimethoxysilane, dicyclopentyldiethoxysilane, dicyclohexyldimethoxysilane, dicyclohexyldiethoxysilane, bis (3-methylcyclohexyl) Methoxysilane, bis (4-methylcyclohexyl) dimethoxysilane, bis (3,5-dimethylcyclohexyl) dimethoxysilane, cyclohexylcyclopentyldimethoxysilane, cyclohexylcyclopentyldiethoxysilane, cyclohexylcyclopentyldipropoxysilane, 3-methylcyclohexylcyclopentyldimethoxysilane, 4-methylcyclohexylcyclopentyldimethoxysilane, 3,5-dimethylcyclohexylcyclopentyldimethoxysilane, 3-methylcyclohexylcyclohexyldimethoxysilane, 4-methylcyclohexylcyclohexyldimethoxysilane, 3,5-dimethylcyclohexylcyclohexyldimethoxysilane, cyclopentylmethyldimethoxysilane, cyclopentyl Methyldi Ethoxysilane, cyclopentylethyldiethoxysilane, cyclopentyl (iso-propyl) dimethoxysilane, cyclopentyl (iso-butyl) dimethoxysilane, cyclohexylmethyldimethoxysilane, cyclohexylmethyldiethoxysilane, cyclohexylethyldimethoxysilane, 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, diphenyldimethoxy Silane, diphenyldiethoxysilane, phenylmethyldimethoxysilane, phenylmethyldiethoxysilane, phenylethyldimethoxysilane, phenylethyldiethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, n -Propyltrimethoxysilane, iso-propyltrimethoxysilane, n-propyltriethoxysilane, iso-propyltriethoxysilane, n-butyltrimethoxysilane, iso-butyltrimethoxysilane, t-butyltrimethoxysilane, n- Butyltriethoxysilane, 2-ethylhexyltrimethoxysilane, 2-ethylhexyltriethoxysilane, cyclopentyltrimethoxysilane, cyclopentyltriethoxysilane , Cyclohexyltrimethoxysilane, cyclohexyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, tetrabutoxysilane .

  Among the above, di-n-propyldimethoxysilane, di-iso-propyldimethoxysilane, di-n-butyldimethoxysilane, di-iso-butyldimethoxysilane, di-t-butyldimethoxysilane, t-butylmethylmethoxysilane , T-butylethylmethoxysilane, di-n-butyldiethoxysilane, t-butyltrimethoxysilane, dicyclohexyldimethoxysilane, dicyclohexyldiethoxysilane, cyclohexylmethyldimethoxysilane, cyclohexylmethyldiethoxysilane, cyclohexylethyldimethoxysilane, cyclohexyl Ethyldiethoxysilane, dicyclopentyldimethoxysilane, dicyclopentyldiethoxysilane, cyclopentylmethyldimethoxysilane, cyclopentylmethyldiethoxy Silane, cyclopentylethyl diethoxysilane, cyclohexyl cyclopentyl dimethoxy silane, cyclohexyl cyclopentyl distearate triethoxysilane, 3-methyl-cyclohexyl cyclopentyl dimethoxy silane, 4-methylcyclohexyl cyclopentyl dimethoxysilane, 3,5-dimethyl-cyclohexyl cyclopentyl dimethoxysilane is preferable.

  In the formula, as the organosilicon compound in which r is 1 to 4, (alkylamino) trialkylsilane, (alkylamino) dialkylcycloalkylsilane, (alkylamino) alkyldicycloalkylsilane, (alkylamino) tricycloalkylsilane , (Alkylamino) (dialkylamino) dialkylsilane, (alkylamino) (dialkylamino) dicycloalkylsilane, bis (alkylamino) dialkylsilane, bis (alkylamino) alkylcycloalkylsilane, bis (alkylamino) dicyclo Alkylsilane, bis (alkylamino) (dialkylamino) alkylsilane, bis (alkylamino) (dialkylamino) cycloalkylsilane, di (alkylamino) dialkylsilane, di (alkylamino) al Dicycloalkylsilane, di (alkylamino) dicycloalkylsilane, di (cycloalkylamino) dialkylsilane, di (cycloalkylamino) alkylcycloalkylsilane, di (cycloalkylamino) dicycloalkylsilane, tris (alkylamino) ) Alkylsilane, Tris (alkylamino) cycloalkylsilane, Tri (alkylamino) alkylsilane, Tri (alkylamino) cycloalkylsilane, Tri (cycloalkylamino) alkylsilane, Tri (cycloalkylamino) cycloalkylsilane, Tetrakis (Alkylamino) silane, tris (alkylamino) dialkylaminosilane, tris (cycloalkylamino) dialkylaminosilane, bis (dialkylamino) bis (alkylamino) Lan, dialkylaminotris (alkylamino) silane, bis (per-hydroisoquinolino) bis (alkylamino) silane, bis (perhydroquinolino) bis (alkylamino) silane, bis (cycloalkylamino) bis (alkylamino) ) Silane, tetra (alkylamino) silane, tri (alkylamino) dialkylaminosilane, tri (cycloalkylamino) dialkylaminosilane, di (dialkylamino) di (alkylamino) silane, dialkylaminotri (alkylamino) silane, di ( Alkyl-substituted per-hydroisoquinolino) di (alkylamino) silane, di (alkyl-substituted perhydroquinolino) di (alkylamino) silane, di (cycloalkylamino) di (alkylamino) silane, alkyl (dialkylamino) ) (Alkylamino) alkoxysilane, cycloalkyl (dialkylamino) (alkylamino) alkoxysilane, vinyl (dialkylamino) (alkylamino) alkoxysilane, allyl (dialkylamino) (alkylamino) alkoxysilane, aralkyl (dialkylamino) (Alkylamino) alkoxysilane, dialkyl (alkylamino) alkoxysilane and the like can be mentioned.

  The organosilicon compound (C) can be used alone or in combination of two or more. These external electron donating compounds can be used alone or in combination of two or more.

  In the method for producing an olefin polymer of the present invention, olefins are polymerized or copolymerized in the presence of the olefin polymerization catalyst of the present invention. 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 use amount ratio of each component is arbitrary as long as it does not affect the effect of the present invention, and is not particularly limited. Usually, the component (B) is used per 1 mole of the titanium atom in the component (A). , 1 to 2000 mol, preferably 50 to 1000 mol. Component (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 mol of component (B).

  The order of contacting the components is arbitrary, but it is desirable to first charge the component (B) in the polymerization system, then contact the component (C), and then contact the component (A). Further or alternatively, the component (B) is first charged into the polymerization system, while the component (A) and the component (C) are contacted in advance, and the contacted components (A) and (C) are placed in the polymerization system. It is also a preferred embodiment to form a catalyst by charging and contacting. As described above, the component (A) and the component (C) are preliminarily brought into contact with each other for treatment, whereby the hydrogen-to-hydrogen activity of the catalyst and the crystallinity of the produced polymer can be further improved.

  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 polymerizing an olefin using the catalyst formed from the component (A), the component (B), and the component (C) in the present invention (also referred to as main polymerization), the catalytic activity, stereoregularity, and heavy weight to be generated. In order to further improve the particle properties and the like of the coalescence, 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. Specifically, component (A), component (B) or component (C) is contacted in the presence of olefins, 0.1 to 100 g of olefin per 1 g of component (A) is preliminarily polymerized, and Component (B) and component (C) are contacted to form a catalyst.

  In carrying out the prepolymerization, the order of contacting the components and the monomers is arbitrary, but preferably, the component (B) is first placed in a prepolymerization system set to an inert gas atmosphere or a gas atmosphere for carrying out polymerization such as propylene. Then, after contacting component (A), an olefin such as propylene and / or one or more other olefins are contacted.

  When olefins are polymerized in the presence of the catalyst for olefins polymerization of the present invention, the stereoregularity and yield of the polymer can be maintained at a high level and less fine powder is used than when a conventional catalyst is used. A polymer having a uniform particle size distribution can be obtained.

Example
EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples. However, this is merely an example and does not limit the present invention.

<Preparation of solid catalyst component>
A 500 ml round bottom flask equipped with a stirrer and sufficiently substituted with nitrogen gas was charged with 20 g (0.175 mol) of diethoxymagnesium and 140 ml of toluene to form a suspended state. On the other hand, a 500 ml round bottom flask equipped with a stirrer and sufficiently substituted with nitrogen gas was prepared. In this, a suspension of diethoxymagnesium and toluene, 60 ml of titanium tetrachloride (0.547 mol; specific gravity) 1.73) was added in 16 portions each. The condition of the divided addition at this time is that the contact amount of titanium tetrachloride with diethoxymagnesium is 3.1 mol per minute with respect to 1 mol of diethoxymagnesium, and the contact amount of one time is that diethoxymagnesium is The total amount of diethoxymagnesium was 6.3% by weight, and titanium tetrachloride was 6.3% by weight of the total amount of titanium tetrachloride. Further, the temperature was controlled in the range of 3.5 to 8.5 ° C. during the contact. The suspension was then reacted at 6 ° C. for 1 hour. Thereafter, 6 ml of di-n-butyl phthalate was added and the temperature was raised to 105 ° C., followed by reaction treatment for 2 hours with stirring. After completion of the reaction, the product was washed 4 times with 200 ml of toluene at 105 ° C., 100 ml of toluene and 20 ml of titanium tetrachloride were newly added, and the reaction treatment was carried out at 100 ° C. for 0.5 hours with stirring. The product was then washed 4 times with 150 ml of 40 ° C. heptane, filtered and dried to obtain a powdery solid component. The titanium content in the solid component was measured and found to be 3.3% by weight. The particle size distribution ((D90-D10) / D50) was 0.4.

<Formation and polymerization of polymerization catalyst>
Into an autoclave with a stirrer having an internal volume of 2.0 liters completely replaced with nitrogen gas, 1.32 mmol of triethylaluminum, 0.13 mmol of cyclohexylmethyldimethoxysilane and 0.0026 mmol of the solid catalyst component as titanium atoms were charged, A polymerization catalyst was formed. Thereafter, 1.5 liters of hydrogen gas and 1.4 liters of liquefied propylene were charged, preliminarily polymerized at 20 ° C. for 5 minutes, then heated up, and polymerized at 70 ° C. for 1 hour. Polymerization activity per gram of the solid catalyst component at this time, the ratio of boiling n-heptane insoluble matter in the produced polymer (HI), the melt flow rate value (MFR) of the produced polymer, 45 μm or less of the produced solid polymer, The amount of fine powder of 75 μm or less and 1700 μm or more, the average particle size and particle size distribution of the produced solid polymer are shown in Table 1.

The polymerization activity per solid catalyst component used here was calculated by the following equation.
Polymerization activity = produced polymer (g) / solid catalyst component (g)
Further, the ratio (HI) of boiling n-heptane insoluble matter in the produced polymer is the ratio (% by weight) of the polymer insoluble in n-heptane when this produced polymer is extracted with boiling n-heptane for 6 hours. ). Further, the melt flow rate value (MFR) of the produced polymer (a) was measured according to ASTM D 1238.

  In addition, the amount of fine powder of 45 μm or less or 75 μm or less of the produced solid polymer is measured by flowing ethanol through the produced polymer placed on a 330 mesh or 200 mesh sieve, and centrifuging the ethanol suspension containing the fine particles that have passed through the sieve. The solid content (fine particles) was recovered by separation and further measured by a method of drying under reduced pressure and measuring the weight. Next, the amount of coarse powder of 1700 μm or more of the produced solid polymer was measured by collecting the produced polymer on a 10 mesh sieve. The average particle size of the produced solid polymer was measured by measuring the particle size distribution according to JIS K0069 and determining the particle size corresponding to an integrated weight of 50%.

  A polymerization catalyst was formed and polymerized under the same conditions as in Example 1 except that continuous contact was used instead of split contact between the diethoxymagnesium suspension and titanium tetrachloride. The condition of continuous contact is that the contact amount of titanium tetrachloride with diethoxymagnesium is 3.1 mol per minute per 1 mol of diethoxymagnesium, and the addition amount of diethoxymagnesium per minute is diethoxymagnesium. The amount of titanium tetrachloride added per minute was 0.4% by weight of the total amount of titanium tetrachloride. The obtained results are shown in Table 2.

  A polymerization catalyst was formed and polymerized under the same conditions as in Example 1 except that diisobutyl phthalate was used instead of di-n-butyl phthalate to form and polymerize the polymerization catalyst. The obtained results are shown in Table 1.

Comparative Example 1
<Preparation of solid catalyst component>
A 500 ml round bottom flask equipped with a stirrer and sufficiently substituted with nitrogen gas was charged with 20 g of diethoxymagnesium and 100 ml of toluene to form a suspended state. The suspension was then added in 16 portions into a solution of 40 ml of toluene and 60 ml of titanium tetrachloride pre-charged in a 500 ml round bottom flask equipped with a stirrer and thoroughly substituted with nitrogen gas. . The suspension was then reacted at 6 ° C. for 1 hour. Then, after adding 6 ml of di-n-butyl phthalate, the temperature was further raised to 105 ° C., followed by a reaction treatment for 2 hours with stirring. After completion of the reaction, the product was washed 4 times with 200 ml of toluene at 100 ° C., 20 ml of titanium tetrachloride was newly added, and the reaction treatment was carried out at 100 ° C. for 0.5 hours with stirring. The product was then washed 4 times with 150 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 measured and found to be 3.8% by weight.

<Formation and polymerization of polymerization catalyst>
The experiment was performed in the same manner as in Example 1 except that the solid catalyst component obtained above was used. The obtained results are shown in Table 1.

Comparative Example 2
<Preparation of solid catalyst component>
A 500 ml round bottom flask equipped with a stirrer and sufficiently substituted with nitrogen gas was charged with 20 g of diethoxymagnesium and 140 ml of toluene to form a suspension and cooled to 6 ° C. To this suspension, 10 ml of titanium tetrachloride was added and stirred at 6 ° C. for 30 minutes. After 50 ml of titanium tetrachloride was added again at 5 ° C., the suspension was reacted at 6 ° C. for 1 hour. Then, after adding 6 ml of di-n-butyl phthalate, the temperature was further raised to 105 ° C., followed by a reaction treatment for 2 hours with stirring. After completion of the reaction, the product was washed 4 times with 200 ml of toluene at 100 ° C., 20 ml of titanium tetrachloride was newly added, and the reaction treatment was carried out at 100 ° C. for 0.5 hours with stirring. The product was then washed 4 times with 150 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 measured and found to be 3.3% by weight.

<Formation and polymerization of polymerization catalyst>
The experiment was performed in the same manner as in Example 1 except that the solid catalyst component obtained above was used. The obtained results are shown in Table 1.

  A polymerization catalyst was formed and polymerized under the same conditions as in Example 1 except that the addition was divided into 8 divisions instead of 16 divisional additions. The condition of the divided addition at this time is that the contact amount of titanium tetrachloride with diethoxymagnesium per minute is 3.1 moles per mole of diethoxymagnesium, and the contact amount at one time is diethoxymagnesium The total amount of diethoxymagnesium was 12.5% by weight, and titanium tetrachloride was 12.5% by weight of the total amount of titanium tetrachloride. The obtained results are shown in Table 1.

Comparative Example 3
A polymerization catalyst was formed and polymerized under the same conditions as in Example 1 except that the addition was divided into 8 divisions instead of 16 divisional additions. The condition of the divided addition at this time is that the contact amount of titanium tetrachloride with diethoxymagnesium per minute is 3.1 moles per mole of diethoxymagnesium, and the contact amount at one time is diethoxymagnesium The total amount of diethoxymagnesium was 17% by weight, and titanium tetrachloride was 17% by weight of the total amount of titanium tetrachloride. The obtained results are shown in Table 1.

  The addition amount of diethoxymagnesium per minute is 0.4% by weight of the total amount of diethoxymagnesium, and the addition amount of titanium tetrachloride per minute is changed to 0.4% by weight of the total amount of titanium tetrachloride. Except that the amount of diethoxymagnesium added per minute was 0.9% by weight of the total amount of diethoxymagnesium, and the amount of titanium tetrachloride added per minute was 0.9% by weight of the total amount of titanium tetrachloride. Under the same conditions as in Example 2, the polymerization catalyst was formed and polymerized.

Comparative Example 4
The addition amount of diethoxymagnesium per minute is 0.4% by weight of the total amount of diethoxymagnesium, and the addition amount of titanium tetrachloride per minute is changed to 0.4% by weight of the total amount of titanium tetrachloride. Except that the amount of diethoxymagnesium added per minute was 0.1% by weight of the total amount of diethoxymagnesium and the amount of titanium tetrachloride added per minute was 0.1% by weight of the total amount of titanium tetrachloride. Under the same conditions as in Example 2, the polymerization catalyst was formed and polymerized.

Comparative Example 5
The addition amount of diethoxymagnesium per minute is 0.4% by weight of the total amount of diethoxymagnesium, and the addition amount of titanium tetrachloride per minute is changed to 0.4% by weight of the total amount of titanium tetrachloride. Except that the amount of diethoxymagnesium added per minute was 1.1% by weight of the total amount of diethoxymagnesium, and the amount of titanium tetrachloride added per minute was 1.1% by weight of the total amount of titanium tetrachloride. Under the same conditions as in Example 2, the polymerization catalyst was formed and polymerized.

  A polymerization catalyst was formed and polymerized under the same conditions as in Example 2 except that the contact amount of titanium tetrachloride per mole of diethoxymagnesium was changed to 7.0 moles instead of 3.1 moles.

Comparative Example 6
A polymerization catalyst was formed and polymerized under the same conditions as in Example 2 except that the contact amount of titanium tetrachloride per 1 mol of diethoxymagnesium was changed to 0.4 mol instead of 0.4 mol.

Comparative Example 7
A polymerization catalyst was formed and polymerized under the same conditions as in Example 2 except that the amount of contact of titanium tetrachloride per 1 mol of diethoxymagnesium was 11 mol instead of 3.1 mol.

Comparative Example 8
<Preparation of solid catalyst component>
A 500 ml round bottom flask equipped with a stirrer and thoroughly substituted with nitrogen gas was charged with 10 g of diethoxymagnesium, 4 ml of di-n-butyl phthalate and 80 ml of toluene to form a suspension. Cooled to 0 ° C. To this suspension, 2 ml of titanium tetrachloride was added and stirred at 0 ° C. for 30 minutes to carry out the first stage halogenation reaction. Next, 18 ml of titanium tetrachloride was added at 0 ° C., then the temperature was raised to 90 ° C. and the mixture was stirred for 2 hours to perform a second stage halogenation reaction. After completion of the reaction, the product was washed 4 times with 100 ml of toluene at 90 ° C. (intermediate washing), 15 ml of titanium tetrachloride was newly added, and the reaction treatment (second treatment) was performed at 100 ° C. for 1 hour with stirring. It was. Subsequently, the product was washed 7 times with 100 ml of heptane at 40 ° C., filtered and dried to obtain a powdery solid catalyst component (A). The titanium content in the solid catalyst component was measured and found to be 2.8% by weight. The contact amount of titanium tetrachloride in the first stage is 0.2 mole per 1 mole of diethoxymagnesium, and the contact amount of titanium tetrachloride in the second stage is 1 mole of diethoxymagnesium. 1.9 moles.

<Formation and polymerization of polymerization catalyst>
The experiment was performed in the same manner as in Example 1 except that the solid catalyst component obtained above was used. The obtained results are shown in Table 1.

  From the results in Table 1, it can be seen that by polymerizing propylene using the solid catalyst component and catalyst obtained by the present invention, high activity and high stereoregularity are maintained, and the generation of a fine powder polymer is extremely small. .

JP-A-6-287225 (Claims) JP 2006-274105 A (Claims)

Claims (2)

  A method for obtaining a solid catalyst component by intermittently contacting an alkoxy-containing magnesium compound (a) and a titanium halogen compound (b) a plurality of times, wherein the contact amount of the component (b) with respect to the component (a) ) 0.5 to 10 moles per minute per mole, and the amount of one contact is 13% by weight or less of the total amount used for contact in each of component (a) and component (b) A method for producing a solid catalyst component for olefin polymerization.   A method of obtaining a solid catalyst component by continuously contacting an alkoxy-containing magnesium compound (a) and a titanium halogen compound (b), wherein the contact amount of the component (b) with respect to the component (a) is the component (a) 1 The amount of component (a) added per minute is 0.5 to 10 mol per minute, and the amount of component (a) added per minute is (0.3 to 1.0% by weight) × (component (a) used for contact) The total amount of the solid catalyst component for olefin polymerization.