JP4521821B2 - Method for producing solid catalyst component for olefin polymerization - Google Patents

Description

  The present invention relates to a solid catalyst component and a catalyst for olefin polymerization, which can maintain a high degree of stereoregularity and yield of the polymer, and can obtain a polymer with less fine powder, and an olefin polymer using the same. Alternatively, the present invention relates to a method for producing a copolymer.

  Conventionally, in the polymerization of olefins, many solid catalyst components for olefin polymerization containing magnesium, titanium, an electron donating compound and halogen as essential components have been proposed. In particular, diethoxymagnesium is representative as a magnesium raw material. Solid catalyst components prepared using alkoxymagnesium compounds have high performance and are widely used industrially.

  For example, in Patent Document 1 (Japanese Patent Laid-Open No. 63-3010), a product obtained by contacting dialkoxymagnesium, an aromatic dicarboxylic acid diester, an aromatic hydrocarbon compound and a titanium halide is in a powder state. A method for polymerizing olefins and a solid catalyst component prepared by heat treatment with olefin, an olefin polymerization catalyst comprising an organoaluminum compound and an organosilicon compound have been proposed.

  Moreover, in patent document 2 (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 next. A solid catalyst component prepared by catalytically reacting the solid product with titanium tetrachloride in the presence of alkylbenzene, a catalyst for olefin polymerization comprising an organoaluminum compound and an organosilicon compound, and A process for the polymerization of olefins in the presence of a catalyst has been proposed.

  Each of the above prior arts has a high activity capable of omitting a so-called deashing step for removing catalyst residues such as chlorine and titanium remaining in the produced polymer, and also has a high degree of stereoregularity. These efforts are focused on improving the yield of coalescence and increasing the sustainability of the catalytic activity during polymerization, and each has achieved excellent results. This type of highly active catalyst component, organoaluminum compound and silicon Polymerization of olefins using a polymerization catalyst composed of an electron donating compound typified by a compound causes a fine polymer of the solid catalyst component itself and particle breakage due to heat of reaction when polymerized, resulting in a polymer produced There was a tendency to broaden the particle size distribution with a lot of fine powder contained therein. Increasing the amount of finely divided polymer prevents process continuation, causing blockage of piping during polymer transfer, etc., and widening the particle size distribution results in favorable polymer processing. As a result, the amount of fine powder polymer is as small as possible, and a polymer having a uniform particle size and a narrow particle size distribution has been sought.

  As a method for solving this problem, in Patent Document 3 (Japanese Patent Laid-Open No. 6-157659), a spherical dialkoxymagnesium, an aromatic hydrocarbon compound, and phthalate are added to a mixed solution of an aromatic hydrocarbon compound and titanium tetrachloride. A catalyst for olefin polymerization using a solid catalyst component obtained by adding a suspension of an acid diester, reacting it, and further reacting with titanium tetrachloride has been proposed.

  In Patent Document 4 (JP-A-6-287225), a suspension of spherical dialkoxymagnesium, an aromatic hydrocarbon compound and a phthalic acid diester is mixed with an aromatic hydrocarbon compound and titanium tetrachloride. Olefin compounds obtained by adding to the solution and reacting, washing the resulting reaction product with an aromatic hydrocarbon compound, drying the solid component obtained by reacting again with titanium tetrachloride, and subjecting to a fine powder removal process Solid catalyst components for polymerization have been proposed.

  Further, in Patent Document 5 (Japanese Patent Laid-Open No. 6-287217), a suspension of spherical dialkoxymagnesium, aromatic hydrocarbon compound and phthalic acid diester is mixed with an aromatic hydrocarbon compound and titanium tetrachloride. In addition to the above, the reaction product obtained is washed with an aromatic hydrocarbon compound, the solid component obtained by reacting again with titanium tetrachloride is dried, subjected to fine powder removal treatment, and then powdered. A solid catalyst component for polymerizing olefins obtained through a treatment process of adding a nonionic surfactant has been proposed.

  Although the above-mentioned proposal has the effect of removing the fine powder of the solid catalyst component itself and reducing the amount of fine powder of the resulting polymer to some extent, the generation of ultrafine polymer called microfine is still in particular. The development of a catalyst with little generation of a fine polymer has been desired, but the above-described prior art is not sufficient to solve the problem.

  On the other hand, as a prior art, there is known a method of preparing a solid catalyst component by dissolving a magnesium compound such as magnesium chloride or diethoxymagnesium with an alkoxytitanium compound to form a uniform solution and then depositing it.

  For example, in Patent Document 6 (Japanese Patent Laid-Open No. 62-18405), a titanium alkoxy compound, dialkoxy magnesium, a diester of an aromatic dicarboxylic acid, a halogenated hydrocarbon compound, and a titanium halide represented by a specific formula are contacted. A catalyst component for polymerization of olefins, which is obtained by the above process and used in combination with a silicon compound and an organoaluminum compound represented by a specific formula, has been proposed.

  In Patent Document 7 (Japanese Patent Laid-Open No. 3-72503), a magnesium compound represented by a specific formula, a tetraalkyltitanium compound, and a silicon compound represented by a specific formula are subjected to a heat reaction, and then the reaction product. A solid catalyst component for polymerizing olefins obtained by treating with a halogen-containing titanium compound represented by the specific formula and an electron donating compound represented by the specific formula is disclosed.

However, although these conventional catalysts are catalysts with little generation of fine polymer, they are still not sufficient, and development of a catalyst with less generation of fine polymer is desired.
Japanese Patent Laid-Open No. 63-3010 (Claims) JP-A-1-315406 (Claims) JP-A-6-157659 (Claims) JP-A-6-287225 (Claims) JP-A-6-287217 (Claims) JP-A-62-18405 (Claims) Japanese Patent Laid-Open No. 3-72503 (Claims)

  Accordingly, an object of the present invention is to provide an olefin which is a component of an olefin polymerization catalyst that can maintain a high degree of polymer stereoregularity and yield when obtained for olefin polymerization, and can obtain a polymer with less fine powder. It is to provide a solid catalyst component for polymerization and a catalyst.

  Under such circumstances, the present inventors have made 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 raw materials. It can be reduced by preparing a solid catalyst component by controlling the halogenation reaction that occurs when dialkoxymagnesium is brought into contact with the titanium halide compound, and (2) the catalyst based on the solid catalyst component thus prepared is active in the polymer. The inventors have found that a polymer having a high degree of stereoregularity and a small amount of fine powder can be obtained, and the present invention has been completed.

  That is, the present invention suspends an alkoxy-containing magnesium compound in an inert organic solvent that is liquid at room temperature in the presence of an ester compound, and the titanium halide compound has a molar ratio of less than 0.3 with respect to the alkoxy-containing magnesium. A method for producing a solid catalyst component for olefin polymerization, comprising preparing a suspension, and then contacting the suspension with an amount of a halogenated titanium compound that at least completely halogenates the alkoxy-containing magnesium compound. It is to provide.

The present invention also provides: (A) the solid catalyst component for olefin polymerization, (B) the following general formula (1); R ¹ _p AlQ _3-p (1)
(Wherein R ¹ represents an alkyl group having 1 to 4 carbon atoms, Q represents a hydrogen atom or a halogen atom, and p is a real number of 0 <p ≦ 3). The olefin polymerization catalyst is provided.

  Moreover, this invention provides the manufacturing method of the olefin polymer or copolymer performed in presence of said catalyst for olefin polymerization.

  The catalyst prepared by using the solid catalyst component for olefin polymerization of the present invention can obtain a polymer with very little fine powder while maintaining a high degree of stereoregularity and yield of the polymer. Therefore, general-purpose polyolefin can be provided at low cost.

  The solid catalyst component for olefin polymerization of the present invention (hereinafter sometimes simply referred to as “component A”) is firstly used as an electron donating compound as a first stage (hereinafter also referred to as “first stage”). In the presence of, a halogenated titanium compound that partially halogenates is brought into contact with the alkoxy-containing magnesium compound. As the alkoxy-containing magnesium compound (hereinafter sometimes simply referred to as “component a”), dialkoxymagnesium is preferable. Examples of dialkoxymagnesium include powdery materials such as diethoxymagnesium, dipropoxymagnesium, dibutoxymagnesium, ethoxymethoxymagnesium, ethoxypropoxymagnesium, and butoxyethoxymagnesium, with diethoxymagnesium being particularly preferred. These dialkoxymagnesiums can be used alone or in combination of two or more.

  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, the particle size distribution is expressed as ln (D ₉₀ / D ₁₀ ) (where D ₉₀ is the cumulative particle size and the particle size at 90%, and D ₁₀ is the cumulative particle size and the particle size at 10%). Yes, 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. A compound. As a tetravalent titanium halide compound, the following general formula (3); Ti (OR ⁴ ) _n Y _4-n (3)
(Wherein R ⁴ 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.

  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, when component (a) is dialkoxymagnesium, in the presence of an electron-donating compound, first, a titanium halide compound in an amount for halogenating a part of dialkoxymagnesium of component (a) is contacted ( First stage). That is, it is important that the dialkoxymagnesium is not completely halogenated as the first stage reaction. Specifically, the halogenated titanium halide compound is brought into contact with and reacted with less than the theoretical amount at which dialkoxymagnesium is completely halogenated. Alternatively, a theoretical amount or a larger amount of a titanium halide compound that is completely halogenated may be brought into contact with dialkoxymagnesium, but the temperature may be set in a region where the rate of the halogenation reaction is extremely slow. However, since the rate of the halogenation reaction of dialkoxymagnesium is relatively fast and it is difficult to control the reaction rate by temperature, it is preferable to control the halogenation reaction by the amount of the titanium halide compound brought into contact with the former.

  In the first stage reaction, the partial halogenation means that one alkoxy group of dialkoxymagnesium is substituted with a halogen atom, and two alkoxy groups among a plurality of dialkoxymagnesium molecules are substituted with halogen atoms. It means both the presence and the non-halogenated side by side.

  In the first stage, when a spherical dialkoxymagnesium powder is used as the component (a), it is particularly effective in terms of reducing fine powders. Such powdery 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 this halogenation reaction of dialkoxymagnesium, and the first stage halogenation halogenates one part of dialkoxymagnesium, suppresses heat of reaction and suppresses particle destruction, By first halogenating the vicinity of the surface of the ethoxymagnesium particles first, the particle surface is smoothed and strengthened, thereby generating fines in this initial production stage and subsequent fine powders in the production stage of the solid catalyst component. It became possible to suppress the occurrence of. The halogenation reaction in the first stage can be carried out by bringing the titanium halide compound into contact with dialkoxymagnesium all at once. However, the halogenation reaction is carried out by intermittently or continuously dividing the titanium halide compound. You can also.

  In the first stage halogenation reaction, when dialkoxymagnesium is used as the component (a) and titanium tetrachloride is used as the titanium halide compound, the contact amount is 0.5 moles per mole of dialkoxymagnesium. Less than, preferably less than 0.4 mol, particularly preferably less than 0.3 mol. The reaction temperature may be a temperature at which a part of component (a) is halogenated, but is preferably -30 to 30 ° C, preferably -20 to 20 ° C, particularly preferably -10 to 10 ° C. . The reaction time is 1 minute or longer, preferably 5 minutes or longer, more preferably 10 minutes or longer.

  The contact between the component (a) and the component (b) is preferably carried out in the presence of an inert organic solvent from the viewpoint of controlling the halogenation reaction, and the inert organic solvent (hereinafter simply referred to as “component d”). Is a compound in which the above-mentioned titanium halide compound is dissolved and dialkoxymagnesium is not dissolved. Specifically, it is saturated with pentane, hexane, heptane, octane, nonane, decane, cyclohexane and the like. Examples include 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.

  The first stage halogenation reaction is carried out in the presence of an electron donating compound (hereinafter sometimes simply referred to as “component (c)”). By making the electron donating compound coexist in the halogenation reaction in the first stage, it is possible to suppress the generation of fine powder due to the destruction of particles due to the heat of reaction during the halogenation reaction of alkoxymagnesium.

  Examples of the electron donating compound include alcohols, phenols, ethers, esters, ketones, aldehydes, amines, amides, nitriles, isocyanates 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-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, ethyl p-methoxybenzoate Monocarboxylic acid esters such as ethyl p-ethoxybenzoate, methyl anisate, ethyl anisate, diethyl maleate, dibutyl maleate, diethyl dimethylmalonate, diethyl diethylmalonate, diethyl di-n-propylmalonate, Diethyl diisopropylmalonate, diethyl di-n-butylmalonate, diethyl diisobutylmalonate, diethyl di-sec-butylmalonate, dimethyl adipate, diethyl adipate, dipropyl adipate, dibutyl adipate, diisodecyl adipate, adipic acid Dicarboxylic acid esters such as dioctyl, phthalic acid diester and phthalic acid diester derivatives, ketones such as acetone, methyl ethyl ketone, methyl butyl ketone, acetophenone and benzophenone, phthalic acid dichloride, Acid halides such as phthalic acid dichloride, aldehydes such as acetaldehyde, propionaldehyde, octylaldehyde, benzaldehyde, amines such as methylamine, ethylamine, tributylamine, piperidine, aniline, pyridine, oleic acid amide, stearic acid amide, etc. Examples thereof include amides, 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 (4);
R ⁵ _i C ₆ H _4-i (COOR ⁶ ) (COOR ⁷ ) (4)
(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 are the same or different. And the number i of the substituent R ⁵ is 1 or 2, and when i is 2, R ⁵ may be the same or different.

In the above general formula (4), specific examples when R ⁵ is an alkyl group having 1 to 8 carbon atoms include 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 Specific examples when R ⁵ is a halogen atom include a fluorine atom, a chlorine atom, a bromine atom and 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. The number i of the substituent R ⁵ is 1 or 2, and when i is 2, R ⁵ may be the same or different. When i is 1, R ⁵ 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), and when i is 2, R ⁵ is What substitutes the hydrogen atom of the 4th-position and the 5-position is preferable.

In the general formula (4), 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, 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, n-butyl group, isobutyl group, t-butyl group, neopentyl group, isohexyl group, and isooctyl group are preferable, and an ethyl group, n-butyl group, and neopentyl group are particularly preferable.

  Examples of the phthalic acid diester derivative represented by the general formula (4) 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.

  Next, as described above, a part of the alkoxy-containing magnesium compound is brought into contact with an amount of a halogenated titanium compound to be halogenated, and then a part of the halogenated titanium compound is brought into contact with at least a completely halogenated titanium halide compound ( Second stage). In the second stage, when component (a) is dialkoxymagnesium, dialkoxymagnesium that has not been halogenated in the halogenation reaction in the first stage and monoalkoxymagnesium halide in which only one alkoxy group is halogenated are completely removed. An amount of a halogenated titanium compound equal to or greater than the amount to be halogenated is brought into contact with the dialkoxymagnesium to be completely halogenated, and a titanium component (active point) effective as a catalyst is supported on the produced magnesium halide. This second stage reaction is preferably carried out in the presence of an inert organic solvent from the viewpoint of controlling the halogenation reaction. The halogenation reaction in the second stage can be carried out by bringing the titanium halide compound into contact with dialkoxymagnesium all at once, but it is carried out by contacting the titanium halide compound intermittently or continuously. You can also.

  In the second stage halogenation reaction, when dialkoxymagnesium is used as the alkoxy-containing magnesium compound and titanium tetrachloride is used as the titanium halide compound, the contact amount is 0.5 to 1 mol per dialkoxymagnesium. The amount is 3.0 mol, preferably 1.0 to 2.5 mol, particularly preferably 1.5 to 2.5 mol. The reaction temperature may be a temperature at which a part of the alkoxy-containing magnesium compound is halogenated, but is preferably -30 to 30 ° C, 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.

  The first-stage halogenation and second-stage halogenation reaction are carried out by contacting the titanium halide compound stepwise as described above. After the first-stage halogenation reaction, the resulting solid product is obtained. May be washed with the above-mentioned inert organic solvent as necessary, or the second stage halogenation reaction may be carried out by continuously contacting the titanium halide compound with a solid material without washing.

  As a specific method for preparing the solid catalyst component (A) for olefin polymerization of the present invention, the component (a) is suspended in the component (d), the component (c) is added to the suspension, The component (b) is added to the suspension for reaction (first stage), and then the component (b) is newly added to the suspension for reaction to obtain the solid catalyst component (A) (first step). 2 steps) suspend the method, component (a) and component (c) in component (d), add this suspension into component (b) and react (first step), then component (B) is added and reacted to obtain a solid catalyst component (A) (second stage). Method and component (a) are suspended in component (d), and component (c) is suspended in this suspension. And then component (b) is added to the suspension and allowed to react (first stage), after which component (b) and component (c) are freshly added to the suspension Added to obtain solid catalyst component (A) is reacted with (second step) methods. In these methods, the solid catalyst component (A) can be washed with an inert solvent such as an aromatic hydrocarbon, 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) in the present application, the component (b) is added to a suspension formed by suspending the component (a) and the component (c) in the component (d). Is contacted at −20 to 20 ° C., and then the first stage halogenation reaction treatment is performed. Subsequently, a component (b) is added to this suspension at -10-20 degreeC, and it heats up after that, and makes it react in the range of 50-130 degreeC. After washing the obtained solid reaction product with a hydrocarbon compound that is liquid at room temperature (intermediate washing), the component (b) is contacted again at -20 to 130 ° C. in the presence of the component (b) to react. The treatment is performed, followed by washing with a hydrocarbon compound that is liquid at room temperature (final washing) to obtain the solid catalyst component (A).

  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 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). Is not particularly limited, but R ¹ is preferably an ethyl group or an isobutyl group, Q is preferably a hydrogen atom, a chlorine atom or a bromine atom, and p is preferably 2 or 3, particularly 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)”) can be used in addition to the components (A) and (B). In particular, when stereoregular polymerization of propylene is performed, the activity of the catalyst and the stereoregularity of the polymer can be improved by using the component (C).

  The external electron donating compound (C) is an organic compound containing an oxygen atom or a nitrogen atom. For example, alcohols, phenols, ethers, esters, ketones, acid halides, aldehydes, amines, Examples thereof include 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, ethyl p-methoxybenzoate, ethyl p-ethoxybenzoate, p-toluyl Monocarboxylic acid esters such as methyl, ethyl p-toluate, methyl anisate, ethyl anisate, diethyl maleate, dibutyl maleate, dimethyl adipate, diethyl adipate, dipropyl adipate, dibutyl adipate, diisodecyl adipate Dicarboxylic acid esters such as dioctyl adipate, dimethyl phthalate, diethyl phthalate, dipropyl phthalate, dibutyl phthalate, dipentyl phthalate, dihexyl phthalate, diheptyl phthalate, dioctyl phthalate, dinonyl phthalate, and didecyl phthalate , Ketones such as acetone, methyl ethyl ketone, methyl butyl ketone, acetophenone, benzophenone, acid halides such as phthalic dichloride, terephthalic dichloride, acetaldehyde, propional Aldehydes such as hydride, octyl aldehyde and benzaldehyde, amines such as methylamine, ethylamine, tributylamine, piperidine, aniline and pyridine, amides such as oleic acid amide and stearic acid amide, nitriles such as acetonitrile, benzonitrile and tolunitrile And isocyanates such as methyl isocyanate and ethyl isocyanate.

  Among these, monocarboxylic acid esters such as ethyl benzoate, ethyl p-methoxybenzoate, ethyl p-ethoxybenzoate, methyl p-toluate, ethyl p-toluate, methyl anisate, ethyl anisate, etc. preferable.

An organosilicon compound is also preferably used as component (C), and is represented by the following general formula (2);
R ² _q Si (OR ³ ) _4-q (2)
(In the formula, R ² is an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group, a phenyl group, a vinyl group, an allyl group, or an aralkyl group, and may be the same or different. R ³ has 1 carbon atom. And an alkyl group, a cycloalkyl group, a phenyl group, a vinyl group, an allyl group, or an aralkyl group of -4, which may be the same or different, and q is an integer of 0 ≦ q ≦ 3. Is 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, triisobutylmethoxysilane, tri -T-butylmethoxysilane, tri-n-butylethoxysilane, tricyclohexylmethoxysilane, tricyclohexylethoxysilane, cyclohexyldimethylmethoxysilane, cyclohexyldiethylmethoxysilane, cyclohexyldiethylethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, di -N-propyldimethoxysilane, diisopropyldimethoxysilane, di-n-propyldiethoxysilane, diisopropyldiethoxysilane, di-n-butyl Rudimethoxysilane, diisobutyldimethoxysilane, 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, cyclohexylcyclopentyldipropoxysila , 3-methylcyclohexylcyclopentyldimethoxysilane, 4-methylcyclohexylcyclopentyldimethoxysilane, 3,5-dimethylcyclohexylcyclopentyldimethoxysilane, 3-methylcyclohexylcyclohexyldimethoxysilane, 4-methylcyclohexylcyclohexyldimethoxysilane, 3,5-dimethylcyclohexylcyclohexyl Dimethoxysilane, cyclopentylmethyldimethoxysilane, cyclopentylmethyldiethoxysilane, cyclopentylethyldiethoxysilane, cyclopentyl (isopropyl) dimethoxysilane, cyclopentyl (isobutyl) dimethoxysilane, cyclohexylmethyldimethoxysilane, cyclohexylmethyldiethoxysilane, cyclohexylethyldimethoxysilane Lan, cyclohexylethyldiethoxysilane, cyclohexyl (n-propyl) dimethoxysilane, cyclohexyl (isopropyl) dimethoxysilane, cyclohexyl (n-propyl) diethoxysilane, cyclohexyl (isobutyl) dimethoxysilane, cyclohexyl (n-butyl) diethoxysilane , Cyclohexyl (n-pentyl) dimethoxysilane, cyclohexyl (n-pentyl) diethoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, phenylmethyldimethoxysilane, phenylmethyldiethoxysilane, phenylethyldimethoxysilane, phenylethyldiethoxysilane , Methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, n Propyltrimethoxysilane, isopropyltrimethoxysilane, n-propyltriethoxysilane, isopropyltriethoxysilane, n-butyltrimethoxysilane, isobutyltrimethoxysilane, t-butyltrimethoxysilane, n-butyltriethoxysilane, 2- Ethylhexyltrimethoxysilane, 2-ethylhexyltriethoxysilane, cyclopentyltrimethoxysilane, cyclopentyltriethoxysilane, cyclohexyltrimethoxysilane, cyclohexyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxy Examples include silane, tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, tetrabutoxysilane, etc. Can.

  Among the above, di-n-propyldimethoxysilane, diisopropyldimethoxysilane, di-n-butyldimethoxysilane, diisobutyldimethoxysilane, di-t-butyldimethoxysilane, di-n-butyldiethoxysilane, t-butyltrimethoxy Silane, dicyclohexyldimethoxysilane, dicyclohexyldiethoxysilane, cyclohexylmethyldimethoxysilane, cyclohexylmethyldiethoxysilane, cyclohexylethyldimethoxysilane, cyclohexylethyldiethoxysilane, dicyclopentyldimethoxysilane, dicyclopentyldiethoxysilane, cyclopentylmethyldimethoxysilane, cyclopentyl Methyldiethoxysilane, cyclopentylethyldiethoxysilane, cyclohexylcyclopentyl Methoxysilane, cyclohexylcyclopentyldiethoxysilane, 3-methylcyclohexylcyclopentyldimethoxysilane, 4-methylcyclohexylcyclopentyldimethoxysilane, and 3,5-dimethylcyclohexylcyclopentyldimethoxysilane are preferably used, and the organosilicon compound (C) may be one kind or Two or more types can be used in combination.

  Polymerization or copolymerization of olefins is carried out 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).

  Although the order of contacting the components is arbitrary, it is desirable to first charge the component (B) in the polymerization system and contact the component (A). When component (C) is used, it is desirable to first charge component (B), then contact component (C), and then contact 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 it is possible to further improve the hydrogen activity of the catalyst and the crystallinity of the produced polymer.

  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) and the component (B) or the component (C) in the present invention (also referred to as main polymerization), catalytic activity, stereoregularity, and formation are generated. In order to further improve the particle properties and the like of the polymer, it is desirable to perform preliminary polymerization 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) or component (C) is 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.

  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 thoroughly substituted with nitrogen gas was charged with 10 g of spherical diethoxymagnesium powder having an average particle size of 35 μm, 4 ml of di-n-butyl phthalate and 80 ml of toluene. A suspension was formed and 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 2.9% by weight. In Example 1, the contact amount of titanium tetrachloride in the first stage is 0.2 mole with respect to 1 mole of diethoxymagnesium, and the contact amount of titanium tetrachloride in the second stage is diethoxymagnesium. It is 1.9 mol with respect to 1 mol.

<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 1 g of the solid catalyst component at this time, ratio of boiling n-heptane insoluble matter in the produced polymer (HI), value of melt flow rate of the produced polymer (MFR), 44 μm or less of the produced solid polymer or The amount of fine powder of 105 μm or less, the average particle size of the produced solid polymer, and the particle size distribution 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 106 μm or less of the produced solid polymer is obtained by flowing ethanol through the produced polymer placed on a 330 mesh or 140 mesh sieve, and centrifuging the ethanol suspension containing fine particles that have passed through the sieve. The solid content (fine particles) is recovered by separation, and further dried under reduced pressure to measure the weight. The average particle size of the resulting solid polymer is measured according to JISK0069, the particle size distribution is measured, and particles corresponding to an integrated weight of 50% It measured by the method of calculating | requiring a diameter.

  A polymerization catalyst was formed and polymerized under the same conditions as in Example 1 except that a spherical diethoxymagnesium powder having an average particle diameter of 52 μm was used instead of the spherical diethoxymagnesium powder having an average particle diameter of 35 μm. 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 polymerization catalyst was formed and polymerized using isobutyl phthalate instead of 4 ml of phthalic acid-n-butyl. The obtained results are shown in Table 1.

<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 spherical diethoxymagnesium powder having an average particle size of 35 μm, 2 ml of phthalic dichloride and 80 ml of toluene, and suspended. And 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 and 2 ml of n-butyl phthalate were added at 0 ° C., and then the temperature was raised to 90 ° C. and stirred for 2 hours to carry out the 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 2.5% by weight. In Example 4, the contact amount of titanium tetrachloride in the first stage and the contact amount of titanium tetrachloride in the second stage are the same as in Example 1.

<Formation and polymerization of polymerization catalyst>
A polymerization catalyst was formed and polymerized in the same manner as in Example 1 except that the solid catalyst component obtained above was used. The 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 thoroughly substituted with nitrogen gas was charged with 10 g of diethoxymagnesium, 80 ml of toluene, 20 ml of titanium tetrachloride and 2.4 ml of dibutyl phthalate, and suspended. It was. Next, the suspension was reacted at −5 ° C. for 2 hours (low temperature aging treatment). Thereafter, the temperature was further raised to 90 ° C., and then a reaction treatment (first treatment) was performed for 2 hours with stirring. After completion of the reaction, the product was washed four times with 100 ml of 90 ° C. toluene (intermediate washing), 20 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 3.7% by weight. In Comparative Example 1, the contact amount of titanium tetrachloride in the first treatment is 2 moles per mole of diethoxymagnesium, and the contact amount of titanium tetrachloride in the second stage is 1 mole of diethoxymagnesium. Is 2.1 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 of Table 1, high activity and high stereoregularity are maintained by the polymerization of propylene using the solid catalyst component and catalyst obtained by the method of the present invention, and the generation of a fine powder polymer is extremely small. I understand.

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

Claims (1)

  In the presence of an ester compound, the alkoxy-containing magnesium compound is suspended in an inert organic solvent that is liquid at room temperature, and the alkoxy-containing magnesium is suspended by contacting a titanium halide compound having a molar ratio of less than 0.3. A method for producing a solid catalyst component for olefin polymerization, comprising preparing a liquid, and then contacting the suspension with a titanium halide compound in an amount that at least completely halogenates the alkoxy-containing magnesium compound.

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