JP4187625B2 - Method for producing solid catalyst component precursor for olefin polymerization, solid catalyst component and catalyst for olefin polymerization - Google Patents

Description

  INDUSTRIAL APPLICABILITY The present invention provides a novel method for producing a solid catalyst component precursor for polymerizing olefins, and can maintain a high degree of stereoregularity and yield of the polymer, and can obtain a polymer with less fine powder. The present invention relates to a solid catalyst component and a catalyst.

  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, any of these conventional methods is a preparation method in which a magnesium compound is dissolved with an alkoxytitanium compound and then a solid catalyst component is precipitated, so that the process of depositing a solid from a solution of the magnesium compound is complicated. In addition, since a large amount of the alkoxytitanium compound is used in the method for preparing the solid catalyst component, there is a problem in that the alkoxytitanium compound remains in the precipitated solid, and the performance such as activity is significantly reduced.
JP 63-3010 A (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)

  That is, the object of the present invention is to provide a novel method for producing a solid catalyst component precursor for polymerizing olefins, and the stereoregularity and yield of the polymer prepared using the precursor and subjected to olefin polymerization. An object of the present invention is to provide a solid catalyst component for olefin polymerization and a catalyst which are components of an olefin polymerization catalyst which can be maintained at a high level and can obtain a polymer having a small particle size and a uniform particle size distribution.

  In this situation, as a result of intensive investigations, the present inventors have found that the fine powder produced when forming the solid catalyst component, and the fine powder polymer obtained by polymerizing olefins using the fine powder are dialkoxymagnesium as a raw material. In addition, a dialkoxymagnesium powder is treated with a polyvalent carboxylic acid halide in the presence of an inert organic solvent to obtain a suspension containing a solid catalyst component precursor for olefin polymerization. A catalyst of a solid catalyst component prepared by obtaining a precursor of a solid catalyst component by using the precursor as a raw material, and maintaining a high level of polymer activity and stereoregularity, and having a finer powder than conventional products Has been found, and the present invention has been completed.

That is, in order to achieve the above object, the method for producing a solid catalyst component precursor for olefin polymerization according to the present invention comprises dialkoxymagnesium powder in polyvalent carboxylic acid at −10 to 40 ° C. in the presence of an inert organic solvent. The solid catalyst component precursor for olefin polymerization obtained by treatment with a halide is washed with an inert organic solvent to obtain a suspension containing the precursor in a washing liquid .

  Moreover, the solid catalyst component for olefin polymerization of the present invention is obtained by bringing the precursor (a) produced by the method for producing a solid catalyst component precursor for olefin polymerization into contact with a tetravalent titanium halogen compound (b). It is characterized by being prepared.

Furthermore, the catalyst for olefin polymerization of the present invention comprises (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). It is characterized by being.

Further, the olefin polymerization catalyst of the present invention comprises (A) a solid catalyst component for olefin polymerization, (B) an organoaluminum compound represented by the general formula (1), and (C) 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. Represents an alkyl group, a cycloalkyl group, a phenyl group, a vinyl group, an allyl group, or an aralkyl group, which may be the same or different, and q is an organic group represented by 0 ≦ q ≦ 3. It is formed from a silicon compound .

  The catalyst by the solid catalyst component for olefin polymerization prepared by using the solid catalyst component precursor for olefin polymerization obtained by the production method of the present invention is highly capable of maintaining a high degree of stereoregularity and yield of the polymer. A polymer with less fine powder can be obtained. Therefore, general-purpose polyolefin can be provided at low cost.

  In the method for producing a solid catalyst component precursor for olefin polymerization according to the present invention, dialkoxymagnesium powder is treated with a polyvalent carboxylic acid halide in the presence of an inert organic solvent. , Diethoxymagnesium, dipropoxymagnesium, dibutoxymagnesium, ethoxymethoxymagnesium, ethoxypropoxymagnesium, butoxyethoxymagnesium and the like, and diethoxymagnesium is particularly preferred. These dialkoxymagnesium powders can be used alone or in combination of two or more.

  The dialkoxymagnesium powder may be obtained by reacting magnesium metal 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 powder. The catalyst is preferably added at the beginning of the reaction step.

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

  The spherical dialkoxymagnesium 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 polyvalent carboxylic acid halide used in the present invention is an aliphatic polyvalent carboxylic acid halide or an aromatic polyvalent carboxylic acid halide. Specifically, maleic acid dichloride, maleic acid dibromide, malonic acid dichloride, malonic acid dichloride. Bromide, diisopropylmalonic dichloride, diisopropylmalonic dibromide, diisobutylmalonic dichloride, diisobutylmalonic dibromide, adipic dichloride, adipic dibromide, phthalic dichloride, phthalic dibromide, terephthalic dichloride, terephthalic dibromide 1,2-cyclohexanedicarboxylic acid dichloride, 1,2-cyclohexanedicarboxylic acid dibromide, sebacic acid dichloride, sebacic acid dibromide and the like. Among these, phthalic acid dichloride, phthalic acid dibromide, diisobutylmalonic acid dichloride, and diisobutylmalonic acid dibromide are preferable. These polyvalent carboxylic acid halides can be used alone or in combination.

  The inert organic solvent used for the preparation of the precursor of the present invention is one that dissolves the above polyvalent carboxylic acid halide and does not dissolve dialkoxymagnesium powder. Specifically, pentane, hexane, heptane, octane. , Saturated hydrocarbon compounds such as nonane, decane and cyclohexane, aromatic hydrocarbon compounds such as benzene, toluene, xylene and ethylbenzene, halogenated hydrocarbon compounds such as methylene chloride and 1,2-dichlorobenzene, methanol, ethanol, iso Examples thereof include alcohols such as octyl alcohol and ethers such as diethyl ether. Among these, aromatic hydrocarbon compounds which are liquid at room temperature such as toluene and xylene and saturated hydrocarbons which are liquid at room temperature such as hexane, heptane and cyclohexane are preferably used.

  The dialkoxymagnesium powder is contacted with a polyvalent carboxylic acid halide in the presence of the inert organic solvent. At this time, the dialkoxymagnesium is partially halogenated with the polyvalent carboxylic acid halide, and the dihalogenated magnesium and / or Or it becomes an alkoxy magnesium halide. On the other hand, the polyvalent carboxylic acid halide is converted into a polyvalent carboxylic acid ester by elimination of halogen and esterification. Accordingly, the solid catalyst component precursor for olefin polymerization of the present invention is a composition of dialkoxymagnesium, dihalogenated magnesium and / or halogenated alkoxymagnesium and a polyvalent carboxylic acid ester, or a mixture of these compounds. is there.

  As described above, the dialkoxymagnesium powder is partially halogenated by the polycarboxylic acid halide treatment, but preferably 5 to 60%, more preferably 20 to 50% of the dialkoxymagnesium is halogenated. When the halogenation rate is 5% or less, when the catalyst is formed and polymerized, the fine powder of the polymer cannot be reduced so much, and when it is halogenated by 60% or more, when the solid catalyst component is formed, the activity etc. The catalyst performance is reduced.

  The amount ratio of dialkoxymagnesium powder and polyvalent carboxylic acid halide is adjusted so that the halogenation rate is finally as described above. The carboxylic acid halide is 0.1 to 10 mol, preferably 0.5 to 5 mol.

  The temperature or time when the dialkoxymagnesium powder and the polyvalent carboxylic acid halide are brought into contact with each other may be appropriately adjusted so as to achieve the above-mentioned halogenation rate. As a result, catalyst performance and fine powder are not reduced. Therefore, the contact temperature is -20 to 50 ° C, preferably -15 to 50 ° C, particularly preferably -10 to 40 ° C.

The specific contact method of dialkoxymagnesium powder and polyvalent carboxylic acid halide is given below.
1) Suspend dialkoxymagnesium powder in an inert organic solvent such as toluene and stir. A solution of polyvalent carboxylic acid halide dissolved in an inert organic solvent is added to the suspension and brought into contact with the suspension.
2) Suspend dialkoxymagnesium powder in an inert organic solvent such as toluene and stir. This suspension is added to and brought into contact with a solution of a polyvalent carboxylic acid halide dissolved in an inert organic solvent.

  The solid catalyst component precursor (a) for olefin polymerization obtained as described above (hereinafter sometimes simply referred to as component (a)) is washed with the inert organic solvent as necessary.

  The solid catalyst component (A) is prepared by bringing the component (a) obtained as described above into contact with a tetravalent titanium halogen compound (b) (hereinafter sometimes simply referred to as component (b)). At this time, the component (a) remains as a suspension with the inert organic solvent used for its preparation or washing, or is separated or dried as necessary for use in the subsequent steps. Considering the simplification of the manufacturing process, it is desirable to use the suspension as it is without separation and drying. However, when an inert organic solvent such as an alcohol or ether that reacts with the component (b) is used, it is desirable to sufficiently remove dialkoxymagnesium by drying under vacuum or heating. Further, as the separation method performed as necessary, there is a method in which a suspension containing a solid catalyst component precursor for olefin polymerization is obtained, and then an inert organic solvent is removed from the suspension by decantation. Can be mentioned.

The component (b) used for the preparation of the solid catalyst component (A) in the present invention is represented by 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 tetrachloride such as titanium tetrachloride, titanium tetrabromide and titanium tetraiodide as titanium halide, methoxytitanium trichloride, ethoxytitanium trichloride, propoxytitanium trichloride, n-butoxytitanium trichloride as alkoxytitanium halide. Examples include chloride, dimethoxy titanium dichloride, diethoxy titanium dichloride, dipropoxy titanium dichloride, di-n-butoxy titanium dichloride, trimethoxy titanium chloride, triethoxy titanium chloride, tripropoxy titanium chloride, tri-n-butoxy titanium chloride. The Of these, titanium tetrahalide is preferable, and titanium tetrachloride is particularly preferable. These titanium compounds can be used alone or in combination of two or more.

  Further, in the preparation of the solid catalyst component (A) of the present invention, an electron donating compound (hereinafter sometimes simply referred to as component (c)) can also be used. The compound made of an electron donating compound is an organic compound containing an oxygen atom or a nitrogen atom. For example, alcohols, phenols, ethers, esters, ketones, acid halides, aldehydes, amines, amides , Nitriles, isocyanates, organosilicon compounds containing Si—O—C bonds, 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. Amides, nitriles such as acetonitrile, benzonitrile, tolunitrile, isocyanates such as methyl isocyanate, ethyl isocyanate, phenylalkoxysilane, alkylalkoxysilane, phenylalkylalkoxysilane, cycloalkylalkoxysilane, cycloalkylalkylalkoxysilane, etc. An organosilicon compound containing a Si—O—C bond can be given.

  Among the above electron donating compounds, esters such as monocarboxylic acid esters such as ethyl benzoate, methyl p-toluate, ethyl p-toluate, ethyl p-ethoxybenzoate and ethyl anisate, and phthalic acid diesters And aromatic dicarboxylic acid diesters such as phthalic acid diester derivatives are preferably used. 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 of R ⁵ being 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 Substitution with hydrogen atoms at positions 4 and 5 is preferred.

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, 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 (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.

  In the present invention, the components (a) and (b), and optionally (c), are contacted in the presence of an aromatic hydrocarbon (d) (hereinafter sometimes referred to simply as “component (d)”). The method of preparing the component (A) by making it is a preferred embodiment of the preparation method. Specific examples of the component (d) include aromatic hydrocarbons having a boiling point of 50 to 150 ° C. such as toluene, xylene, and ethylbenzene. Is preferably used. Moreover, these may be used independently or may be used in mixture of 2 or more types.

  Below, the preparation method of the component (A) of this invention is described. Specifically, a suspension formed by suspending component (a) in component (d), or obtained using component (d) as an inert organic solvent in the precursor production method of the present invention. A solid component is obtained by contacting the suspension containing the component (a) with the component (b) and, if necessary, the component (c). The contact of each component is performed with stirring in a container equipped with a stirrer in an inert gas atmosphere and in a state where moisture and the like are removed. The contact temperature is a temperature at the time of contact of each component, and may be the same temperature as the reaction temperature or a different temperature. The contact temperature may be a relatively low temperature range around room temperature when the mixture is simply brought into contact with stirring and mixed, or dispersed or suspended for modification, but the product is allowed to react after contact. When obtaining, the temperature range of -20-130 degreeC is preferable. If the temperature during the reaction is less than −20 ° C., the reaction does not proceed sufficiently, resulting in insufficient performance of the prepared solid component, and if it exceeds 130 ° C., the evaporation of the solvent used becomes remarkable. Therefore, it becomes difficult to control the reaction. The reaction time is 1 minute or longer, preferably 10 minutes or longer, more preferably 30 minutes or longer.

  A preferable method for preparing the solid catalyst component (A) of the present invention is a suspension formed by suspending the component (a) in the component (d), or an inert organic solvent in the method for producing the precursor of the present invention. The solid catalyst component (A) is obtained by bringing the component (b) into contact with the suspension containing the component (a) obtained using the component (d) as the component (b) and then bringing the component (c) into contact with the suspension. The method of preparing can be mentioned. Alternatively, the solid catalyst component (A) can be obtained by bringing the component (b) into contact with the suspension formed above or the suspension containing the component (a) and then reacting the component (b). The method of preparing can be mentioned.

Below, the preferable contact order at the time of preparing the solid catalyst component (A) of this invention is illustrated more concretely.
(1) (a) → (d) → (b) → (c) → << intermediate washing → (d) → (b) >> → final washing → solid catalyst component (A)
(2) (a) → (d) → (c) → (b) → << intermediate washing → (d) → (b) >> → final washing → solid catalyst component (A)
(3) (a) → (d) → (b) → (c) → << intermediate washing → (d) → (b) → (c) >> → final washing → solid catalyst component (A)
(4) (a) → (d) → (b) → (c) → << intermediate washing → (d) → (c) → (b) >> → final washing → solid catalyst component (A)
(5) (a) → (d) → (c) → (b) → << intermediate washing → (d) → (b) → (c) >> → final washing → solid catalyst component (A)
(6) (a) → (d) → (c) → (b) → << intermediate washing → (d) → (c) → (b) >> → final washing → solid catalyst component (A)
In each of the contact methods described above, the activity in the parentheses (<<) is further improved by repeating the process a plurality of times as necessary. In addition, the component (b) used in the steps in <<> may be newly added or may be the residue of the previous step. In addition to the washing steps shown in (1) to (6) above, the product obtained in each contact stage can be washed with a hydrocarbon compound that is liquid at room temperature.

  Based on the above, as a particularly preferred method for preparing the solid catalyst component (A) in the present application, in the suspension formed by suspending the component (a) in the component (d), or the method for producing the precursor of the present invention The component (b) is brought into contact with the suspension containing the component (a) obtained using the component (d) as an inert organic solvent, and then a reaction treatment is performed. At this time, before or after contacting the component (b) with the suspension, one or more of the components (c) are contacted at −20 to 130 ° C. to perform a reaction treatment, and a solid reaction The product (1) is obtained. At this time, it is desirable to carry out the aging reaction at a low temperature before or after contacting one or more of component (c). After washing this solid reaction product (1) with a liquid hydrocarbon compound at room temperature (intermediate washing), the component (b) is again contacted at −20 to 130 ° C. in the presence of the aromatic hydrocarbon compound. The reaction treatment is performed to obtain a solid reaction product (2). If necessary, intermediate cleaning and reaction treatment may be repeated a plurality of times. Next, the solid reaction product (2) is washed with a hydrocarbon compound that is liquid at room temperature (final washing) to obtain a solid catalyst component (A).

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

  The amount ratio of each component used in preparing the solid catalyst component (A) varies depending on the preparation method and cannot be specified unconditionally. For example, the component (b) is 0.5 to 100 per 1 mol of dialkoxymagnesium. Mol, preferably 0.5 to 50 mol, more preferably 1 to 10 mol, and when component (c) is used, component (c) is 0.01 to 10 mol, preferably 0.01 to 1 mol, More preferably, it is 0.02-0.6 mol, and a component (d) is 0.001-500 mol, Preferably it is 0.001-100 mol, More preferably, it is 0.005-10 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 2 0.0-8.0 wt%, more preferably 3.0-8.0 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 oxygen or nitrogen, for example, alcohols, phenols, ethers, esters, ketones, acid halides, aldehydes, amines, amides. , Nitriles, isocyanates, organosilicon compounds containing Si—O—C bonds, 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, 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, octylaldehyde 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 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) 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 precursor>
A round bottom flask equipped with a stirrer and sufficiently substituted with nitrogen gas was charged with 10 g of spherical diethoxymagnesium powder and 80 ml of toluene to form a suspension and cooled to 10 ° C. To this suspension, 5.3 ml of phthalic acid dichloride was added and stirred at 30 ° C. for 6 hours to obtain a toluene suspension containing the precursor, and further twice with 100 ml of 40 ° C. toluene, and then at 40 ° C. This was washed 5 times with 100 ml of heptane to obtain a heptane suspension containing the precursor. When this precursor was analyzed, 25% of diethoxymagnesium was chlorinated and diethyl phthalate contained 8.6% by weight.
<Preparation of solid catalyst component>
The heptane suspension containing the precursor obtained above was charged with 10 ml of toluene and 20 ml of titanium tetrachloride preliminarily charged in a 500 ml round bottom flask equipped with a stirrer and sufficiently substituted with nitrogen gas. Added in solution. Next, the suspension was reacted at −5 ° C. for 2 hours (low temperature aging treatment). Then, after heating up to 90 degreeC, the reaction process (1st process) was performed for 2 hours, 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 4.0% by weight.
<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, and polymerized at 70 ° C. for 1 hour. Table 1 shows the 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), and the melt flow rate value (MFR) of the produced polymer.

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.

<Preparation of solid catalyst component precursor>
A round bottom flask equipped with a stirrer and sufficiently substituted with nitrogen gas was charged with 10 g of spherical diethoxymagnesium powder and 80 ml of toluene to form a suspension and cooled to 10 ° C. To this suspension, 2.6 ml of phthalic acid dichloride was added and stirred at 30 ° C. for 6 hours to obtain a toluene suspension containing the precursor, and further twice with 100 ml of 40 ° C. toluene, and then at 40 ° C. This was washed 5 times with 100 ml of heptane to obtain a heptane suspension containing the precursor. Analysis of this precursor revealed that 14% of diethoxymagnesium was chlorinated and 4.4% by weight of diethyl phthalate.
<Preparation of solid catalyst component>
The heptane suspension containing the precursor obtained above was charged with 10 ml of toluene and 20 ml of titanium tetrachloride preliminarily charged in a 500 ml round bottom flask equipped with a stirrer and sufficiently substituted with nitrogen gas. Added in solution. Next, the suspension was reacted at −5 ° C. for 2 hours (low temperature aging treatment). Then, after heating up to 90 degreeC, 2.6 ml of dibutyl phthalates were added, and the reaction process (1st process) was performed for 2 hours, 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 3.8% 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.

The experiment was performed in the same manner as in Example 1 except that 8.7 ml of diisobutylmalonic acid dichloride was used instead of 5.3 ml of phthalic dichloride. 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 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.
<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.

表１の結果から、本発明の固体触媒成分および触媒を用いてプロピレンの重合を行うことにより、高活性および高立体規則性を維持し、微粉重合体の発生が極めて少ないことがわかる。

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

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

Claims (11)

The dialkoxymagnesium powder is treated with a polyvalent carboxylic acid halide at −10 to 40 ° C. in the presence of an inert organic solvent, and the resulting solid catalyst component precursor for olefin polymerization is washed with an inert organic solvent, A method for producing a solid catalyst component precursor for olefin polymerization, which comprises obtaining a suspension containing the precursor in a cleaning liquid . The method for producing a solid catalyst component precursor for olefin polymerization according to claim 1, wherein 5 to 60% of the dialkoxymagnesium is halogenated by treatment with the polyvalent carboxylic acid halide.   The method for producing a solid catalyst component precursor for olefin polymerization according to claim 1, wherein the dialkoxymagnesium is diethoxymagnesium.   The method for producing a solid catalyst component precursor for olefin polymerization according to claim 1, wherein the polyvalent carboxylic acid halide is an aromatic or aliphatic polyvalent carboxylic acid halide.   The method for producing a solid catalyst component precursor for olefin polymerization according to claim 1, wherein the polyvalent carboxylic acid halide is a phthalic acid halide or a malonic acid halide. The solid catalyst component precursor (a) for olefin polymerization produced by the production method according to any one of claims 1 to 5 and a tetravalent titanium halogen compound (b) are -10 to 60 ° C. A solid catalyst component for polymerization of olefins, which is prepared by contacting at a temperature of 5 ° C., subjecting to low temperature aging treatment, and subsequent reaction . A suspension containing the solid catalyst component precursor (a) for olefin polymerization obtained in the production method according to any one of claims 1 to 5 and a tetravalent titanium halogen compound (b) , A solid catalyst component for olefin polymerization, which is prepared by contacting at a temperature of −10 to 60 ° C., subjecting to low temperature aging treatment, and subsequent reaction . A suspension containing the solid catalyst component precursor (a) for olefin polymerization obtained in the production method according to any one of claims 1 to 5 , a tetravalent titanium halogen compound (b), and electron donation A solid catalyst component for polymerizing olefins, which is prepared by contacting the functional compound (c). 9. The solid catalyst component for olefin polymerization according to claim 8 , wherein the electron donating compound (c) is a monocarboxylic acid ester and / or a polyvalent carboxylic acid ester. (A) The solid catalyst component for olefin polymerization according to any one of claims 6 to 9 ,
(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). A catalyst for olefin polymerization. (A) The solid catalyst component for olefin polymerization according to any one of claims 6 to 9 ,
(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) and ( C) under 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. Represents an alkyl group, a cycloalkyl group, a phenyl group, a vinyl group, an allyl group, or an aralkyl group, which may be the same or different, and q is an organic group represented by 0 ≦ q ≦ 3. features and to Luo olefin such polymerization catalyst to be formed from a silicon compound.

Images