Solid catalyst component for olefin polymerization, method for producing solid catalyst component for olefin polymerization, catalyst for olefin polymerization, and method for producing olefin polymer

Abstract

To provide a solid catalyst component for olefin polymerization, a solid catalyst, and a method for producing an olefin polymer, which enable production of an olefin polymer having high rigidity and also enable higher polymerization activity.SOLUTION: A solid catalyst component for olefin polymerization, comprises magnesium, titanium, halogen, and at least one selected from succinic diester compounds represented by the general formula (1): R1-O-C(=O)-CHR2CHR3-C(=O)-O-R4 (1) (where R1 and R4 are linear or branched alkyl groups having 3 to 6 carbon atoms, which may be the same as or different from each other), the content of the succinic diester compound represented by the general formula (1) being 12.0 to 25.0 mass% based on the total content of all components when calculated as solid content, and the content of titanium atoms being 2.5 to 5.0 mass%.SELECTED DRAWING: None

Description

[Technical Field]

[0001] BACKGROUND ART In recent years, olefin polymers such as polypropylene (PP) have been used in a variety of applications, including molded products such as automobile parts and home appliances, as well as containers and films.

[0002] Polypropylene resin compositions are lightweight and have excellent moldability, and also have excellent chemical stability, such as heat resistance and chemical resistance, of molded articles, and are also very cost-effective, and therefore are used in many fields as one of the most important plastic materials. In fields such as automobile parts, polypropylenes with high rigidity are desired in order to achieve thin and lightweight walls.

[0003] Conventionally, for producing polymers of olefins such as propylene, which have high rigidity, olefins have been polymerized using a solid catalyst for olefin polymerization containing, as a solid catalyst component, a 2,3-diisopropyl succinic acid diester as an internal electron donor.

[0004] For example, Patent Document 1 describes in its working examples that propylene was polymerized using 2,3-diisopropyl succinic acid ethyl ester as an internal electron donor. [Prior art documents] [Patent documents]

[0005] [Patent Document 1] Japanese Patent Application Laid-Open No. 2013-533367 Summary of the Invention [Problem to be solved by the invention]

[0006] However, when olefins are polymerized using a solid catalyst for olefin polymerization containing, as a solid catalyst component, a solid catalyst component for olefin polymerization in which succinic acid diethyl ester is used as an internal electron donor, although an olefin polymer having high rigidity can be obtained, there is a problem that the polymerization activity tends to be low.

[0007] Therefore, an object of the present invention is to provide a solid catalyst component and solid catalyst for olefin polymerization, which are capable of producing an olefin polymer having high rigidity and high polymerization activity, and a method for producing an olefin polymer. [Means for solving the problem]

[0008] As a result of intensive investigations by the present inventors to solve the above technical problems, they have found that by using a dialkyl succinate ester having a carbon number of 3 to 6, preferably 4, as an internal electron donor in the solid catalyst component for olefin polymerization, a solid catalyst component and a solid catalyst for olefin polymerization that can produce an olefin polymer having high rigidity and can increase the polymerization activity during polymerization can be obtained, thereby solving the above technical problems, and have completed the present invention based on this finding.

[0009] That is, the present invention is (1) magnesium, titanium, a halogen, and the following general formula (1); R 1 -OC(=O)-CHR 2 CHR 3 -C(=O)-OR 4 (1) (In the formula, R 2 and R 3 are hydrogen atoms or alkyl groups having 1 to 4 carbon atoms, and may be the same or different; R 1 and R 4 are straight-chain or branched alkyl groups having 3 to 6 carbon atoms, and may be the same or different. The succinic acid diester compound may be one or more selected from the succinic acid diester compounds represented by the formula: the content of the succinic acid diester compound represented by the general formula (1) is 12.0 to 25.0 mass% and the content of titanium atoms is 2.5 to 5.0 mass% in the total amount of components when converted into solid content; A solid catalyst component for olefin polymerization, characterized by: (2) R in the general formula (1) 1 and R 4 are linear or branched alkyl groups having 4 carbon atoms, and may be the same or different from each other; (3) R in the general formula (1) 2 and R 3 are an isopropyl group, a methyl group, an ethyl group, or an isobutyl group, and may be the same or different from each other. (4) Dialkoxy magnesium, titanium halide compounds and compounds represented by the following general formula (1): R 1 -OC(=O)-CHR 2 CHR 3 -C(=O)-OR 4 (1) (In the formula, R 2 and R 3 are hydrogen atoms or alkyl groups having 1 to 4 carbon atoms, and may be the same or different; R 1 and R 4 are straight-chain or branched alkyl groups having 3 to 6 carbon atoms, and may be the same or different. contacting one or more succinic acid diester compounds selected from the succinic acid diester compounds represented by the total amount of the titanium halide compounds used is 2.0 to 12.0 mol relative to 1.0 mol of the dialkoxymagnesium, and the total amount of the succinic acid diester compounds represented by the general formula (1) used is 0.06 to 0.20 mol relative to 1.0 mol of the dialkoxymagnesium; A method for producing a solid catalyst component for olefin polymerization, (5) (I) A solid catalyst component for olefin polymerization according to any one of (1) to (3), and (II) the following general formula (2); R 5 p AlQ 3-p (2) (In the formula, R 5 is an alkyl group having 1 to 6 carbon atoms, Q is a hydrogen atom or a halogen atom, and p is 0. <p≦3であり、R 5 If there are multiple R 5 may be the same or different, and when there are multiple Qs, each Q may be the same or different. An organoaluminum compound represented by A catalyst for olefin polymerization, comprising: (6) (I) a solid catalyst component for olefin polymerization represented by any one of (1) to (3), (II) a catalyst represented by the following general formula (2): R 5 p AlQ 3-p (2) (In the formula, R 5 is an alkyl group having 1 to 6 carbon atoms, Q is a hydrogen atom or a halogen atom, and p is 0. <p≦3であり、R 5 If there are multiple R 5 may be the same or different, and when there are multiple Qs, each Q may be the same or different. and organoaluminum compounds represented by (III) External electron donor compounds (5) A catalyst for olefin polymerization, comprising: (7) A method for producing an olefin polymer, characterized by carrying out polymerization of olefins using the olefin polymerization catalyst according to (5) or (6). This provides: [Effects of the Invention]

[0010] According to the present invention, it is possible to provide a solid catalyst component and solid catalyst for olefin polymerization, which are capable of producing an olefin polymer having high rigidity and high polymerization activity, and a method for producing an olefin polymer. DETAILED DESCRIPTION OF THE INVENTION

[0011] First, the solid catalyst component for olefin polymerization according to the present invention will be described. The solid catalyst component for olefin polymerization according to the present invention comprises magnesium, titanium, a halogen, and a compound represented by the following general formula (1): R 1 -OC(=O)-CHR 2 CHR 3 -C(=O)-OR 4 (1) (In the formula, R 2 and R 3 are hydrogen atoms or alkyl groups having 1 to 4 carbon atoms, and may be the same or different; R 1 and R 4 are straight-chain or branched alkyl groups having 3 to 6 carbon atoms, and may be the same or different. The succinic acid diester compound may be one or more selected from the succinic acid diester compounds represented by the formula: the content of the succinic acid diester compound represented by the general formula (1) is 12.0 to 25.0 mass% and the content of titanium atoms is 2.5 to 5.0 mass% in the total amount of components when converted into solid content; It is characterized by the following.

[0012] The solid catalyst component for olefin polymerization according to the present invention may be a contact reaction product obtained by contacting and reacting a raw material component serving as a magnesium supply source, a raw material component serving as a titanium and halogen supply source, and an internal electron donor compound, i.e., a succinic acid diester compound represented by general formula (1), in an organic solvent. Specifically, the solid catalyst component may be a contact reaction product obtained by using a dialkoxymagnesium as the raw material component serving as a magnesium supply source and a tetravalent titanium halide compound as the raw material component serving as a titanium and halogen supply source, and by contacting these raw materials with an internal electron donor compound containing the succinic acid diester compound represented by general formula (1).

[0013] In the solid catalyst component for olefin polymerization according to the present invention, specific examples of dialkoxymagnesium, which is a raw material component serving as a magnesium supply source, include dimethoxymagnesium, diethoxymagnesium, dipropoxymagnesium, dibutoxymagnesium, ethoxymethoxymagnesium, ethoxypropoxymagnesium, and butoxyethoxymagnesium, with diethoxymagnesium being particularly preferred.

[0014] The dialkoxymagnesium may be one obtained by reacting metallic magnesium with an alcohol in the presence of a halogen or a halogen-containing metal compound.

[0015] The dialkoxymagnesium is preferably in the form of granules or powder, and the shape thereof may be irregular or spherical.

[0016] When a spherical dialkoxymagnesium is used, a polymer powder having a better particle shape (more spherical) and a narrow particle size distribution can be obtained, which improves the handleability of the polymer powder produced during the polymerization operation and makes it possible to suppress the occurrence of blockages and the like due to fine particles contained in the produced polymer powder.

[0017] The spherical dialkoxymagnesium does not necessarily have to be perfectly spherical, and ellipsoidal or potato-shaped ones can also be used.

[0018] The average particle size (average particle size D50) of the dialkoxymagnesium is preferably 1.0 to 200.0 μm, more preferably 5.0 to 150.0 μm, where the average particle size D50 refers to the particle size at 50% of the cumulative particle size in the volume cumulative particle size distribution measured using a laser light scattering diffraction particle size analyzer. When the dialkoxymagnesium is spherical, the average particle size D50 is preferably 1.0 to 100.0 μm, more preferably 5.0 to 80.0 μm, and even more preferably 10.0 to 70.0 μm.

[0019] Furthermore, the particle size distribution of the dialkoxy magnesium is preferably narrow, with few fine particles and few coarse particles. Specifically, when measured using a laser light scattering diffraction particle size analyzer, the dialkoxymagnesium preferably contains 20% or less, more preferably 10% or less, of particles with a particle size of 5.0 μm or less, while when measured using a laser light scattering diffraction particle size analyzer, the dialkoxymagnesium preferably contains 20% or less, more preferably 10% or less, of particles with a particle size of 100.0 μm or more. Furthermore, when the particle size distribution is expressed as ln(D90 / D10), it is preferably 3 or less, and more preferably 2 or less. Here, D90 means the particle size at 90% of the cumulative particle size in the volume cumulative particle size distribution when measured using a laser light scattering diffraction particle size analyzer. Also, D10 means the particle size at 10% of the cumulative particle size in the volume cumulative particle size distribution when measured using a laser light scattering diffraction particle size analyzer.

[0020] Methods for producing the above-mentioned spherical dialkoxymagnesium are exemplified in, for example, Japanese Patent Application Laid-Open Nos. 62-51633, 3-74341, 4-368391, and 8-73388.

[0021] In the solid catalyst component for olefin polymerization according to the present invention, the dialkoxy magnesium has a specific surface area of ​​5 m 2 / g or more is preferable, and 5 to 50m 2 / g is more preferable, and 10 to 40m 2 / g is more preferred. By using a dialkoxymagnesium having a specific surface area within the above range, a solid catalyst component for olefin polymerization having a desired specific surface area can be easily prepared.

[0022] In the present application, the specific surface area of ​​the dialkoxymagnesium refers to a value measured by the BET method. Specifically, the specific surface area of ​​the dialkoxymagnesium refers to a value measured by the BET method (automatic measurement) using an Automatic Surface Area Analyzer HM model-1230 manufactured by Mountech Co., Ltd., in the presence of a mixed gas of nitrogen and helium, after previously vacuum-drying the measurement sample at 50°C for 2 hours.

[0023] The dialkoxymagnesium is preferably in the form of a solution or suspension during the reaction, and being in the form of a solution or suspension allows the reaction to proceed favorably.

[0024] When the dialkoxymagnesium is solid, it can be dissolved in a solvent capable of solubilizing the dialkoxymagnesium to form a dialkoxymagnesium solution, or it can be suspended in a solvent not capable of solubilizing the dialkoxymagnesium to form a dialkoxymagnesium suspension. When the dialkoxymagnesium is liquid, it may be used as a solution of dialkoxymagnesium as it is, or may be further dissolved in a solvent capable of solubilizing the dialkoxymagnesium and used as a solution of dialkoxymagnesium.

[0025] The compound capable of solubilizing solid dialkoxymagnesium includes at least one compound selected from the group consisting of alcohols, ethers, and esters. Alcohols such as ethanol, propanol, butanol, and 2-ethylhexanol are preferred, with 2-ethylhexanol being particularly preferred. On the other hand, examples of the medium that does not have the ability to solubilize solid dialkoxymagnesium include one or more solvents selected from saturated hydrocarbon solvents and unsaturated hydrocarbon solvents that do not dissolve dialkoxymagnesium.

[0026] In the solid catalyst component for olefin polymerization according to the present invention, the tetravalent titanium halide compound, which is a raw material component serving as a supply source of titanium and halogen, is not particularly limited, but may be a compound represented by the following general formula (3): Ti(OR 6 ) r X 4-r (3) (In the formula, R 6 represents an alkyl group having 1 to 4 carbon atoms, X represents a halogen atom such as a chlorine atom, a bromine atom or an iodine atom, and r satisfies 0≦r≦3.

[0027] In the above general formula (3), r is 0≦r≦3, and specific examples of r include 0, 1, 2, and 3.

[0028] The titanium halide represented by the general formula (3) may be one or more titanium tetrahalides selected from titanium tetrachloride, titanium tetrabromide, titanium tetraiodide, and the like. In addition, examples of the alkoxytitanium halide represented by the general formula (3) include one or more selected from methoxytitanium trichloride, ethoxytitanium trichloride, propoxytitanium trichloride, n-butoxytitanium trichloride, dimethoxytitanium dichloride, diethoxytitanium dichloride, dipropoxytitanium dichloride, di-n-butoxytitanium dichloride, trimethoxytitanium chloride, triethoxytitanium chloride, tripropoxytitanium chloride, tri-n-butoxytitanium chloride, and the like. As the tetravalent titanium halide compound, titanium tetrahalide is preferred, and titanium tetrachloride is more preferred. These titanium compounds may be used alone or in combination of two or more.

[0029] In the solid catalyst component for olefin polymerization according to the present invention, the internal electron donor is represented by the following general formula (1): R 1-OC(=O)-CHR 2 CHR 3 -C(=O)-OR 4 (1) (In the formula, R 2 and R 3 are hydrogen atoms or alkyl groups having 1 to 4 carbon atoms, and may be the same or different; R 1 and R 4 are straight-chain or branched alkyl groups having 3 to 6 carbon atoms, and may be the same or different. The succinic acid diester compound is at least one selected from the succinic acid diester compounds represented by the following formula:

[0030] In the succinic acid diester compound represented by general formula (1), R 1 and R 4 are straight chain or branched alkyl groups having 3 to 6 carbon atoms, preferably straight chain or branched alkyl groups having 4 carbon atoms, and may be the same or different. R 1 and R 4 Examples of the alkyl group include an n-propyl group and an isopropyl group, which have three carbon atoms; an n-butyl group, a 1-methylpropyl group, a 2-methylpropyl group (isobutyl group), and a tert-butyl group, which have four carbon atoms; an n-pentyl group, a 1-methylbutyl group, a 2-methylbutyl group, and a 3-methylbutyl group (isopentyl group), which have five carbon atoms; and an n-hexyl group, a 1-methylpentyl group, a 2-methylpentyl group, a 3-methylpentyl group, and a 4-methylpentyl group (isohexyl group), which have six carbon atoms.

[0031] In the compound represented by general formula (1), R 2 and R 3 are hydrogen atoms or alkyl groups having 1 to 4 carbon atoms, and may be the same or different. R 2 and R 3 When is an alkyl group having 1 to 4 carbon atoms, specific examples include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, and an isobutyl group.

[0032] In the solid catalyst component for olefin polymerization according to the present invention, specific examples of the succinic acid diester compound represented by general formula (1) include succinic acid, propylsuccinic acid, isopropylsuccinic acid, n-butylsuccinic acid, isobutylsuccinic acid, sec-butylsuccinic acid, tert-butylsuccinic acid, 2,3-dimethylsuccinic acid, 2,3-diethylsuccinic acid, 2,3-dipropylsuccinic acid, 2,3-diisopropylsuccinic acid, 2,3-dibutylsuccinic acid, Examples of the di-n-propyl ester, diisopropyl ester, di-n-butyl ester, diisobutyl ester, di-tert-butyl ester, di-n-pentyl ester, bis(1-methylbutyl) ester, bis(2-methylbutyl) ester, diisopentyl ester, di-n-hexyl ester, bis(1-methylpentyl) ester, bis(2-methylpentyl) ester, bis(3-methylpentyl) ester, and diisohexyl ester of 2,3-diisobutylsuccinic acid, 2,3-di-sec-butylsuccinic acid, or 2,3-di-tert-butylsuccinic acid include di-n-propyl ester, diisopropyl ester, di-n-butyl ester, diisopropyl ester, di-tert-butyl ester, di-n-pentyl ...

[0033] The solid catalyst component for olefin polymerization according to the present invention contains, as an internal electron donor compound, a succinic acid diester compound represented by general formula (1) as an essential component, but may further contain other internal electron donor compounds (hereinafter, appropriately referred to as "other internal electron donor compounds") as internal electron donor compounds other than the succinic acid diester compound represented by general formula (1).

[0034] Such other internal electron donating compounds include at least one selected from carbonates, acid halides, acid amides, nitriles, acid anhydrides, diether compounds, and carboxylic acid esters.

[0035] Specific examples of such other internal electron donor compounds include one or more compounds selected from ether carbonate compounds, carboxylic acid diesters such as cycloalkane dicarboxylic acid diesters, cycloalkene dicarboxylic acid diesters, malonic acid diesters, alkyl-substituted malonic acid diesters, and maleic acid diesters, and diether compounds. More specifically, one or more selected from ether carbonate compounds such as (2-ethoxyethyl)methyl carbonate, (2-ethoxyethyl)ethyl carbonate, and (2-ethoxyethyl)phenyl carbonate; dialkylmalonic acid diesters such as dimethyl diisobutylmalonate and diethyl diisobutylmalonate; cycloalkanedicarboxylic acid diesters such as dimethyl cyclohexane-1,2-dicarboxylate; and 1,3-diethers such as (isopropyl)(isopentyl)-1,3-dimethoxypropane and 9,9-bis(methoxymethyl)fluorene are more preferred.

[0036] In the solid catalyst component for olefin polymerization according to the present invention, the content of the succinic acid diester compound represented by general formula (1) in the total amount of components, calculated as solid content, is 12.0 to 25.0 mass%, preferably 14.0 to 24.0 mass%, and more preferably 15.0 to 22.0 mass%. When the content of the succinic acid diester compound in the total amount of components, calculated as solid content, is within the above range, when the catalyst component is subjected to olefin polymerization, a highly rigid olefin polymer can be produced with high polymerization activity.

[0037] In the solid catalyst component for olefin polymerization according to the present invention, the content of titanium atoms in the total amount of components contained, calculated as solid content, is 2.5 to 5.0 mass%, preferably 3.0 to 5.0 mass%, more preferably 3.5 to 4.8 mass%. When the content of titanium atoms in the total amount of components contained, calculated as solid content, is within the above range, when the catalyst component is subjected to olefin polymerization, it is possible to produce an olefin polymer with high polymerization activity and high rigidity.

[0038] In the solid catalyst component for olefin polymerization according to the present invention, the molar ratio (S / T) of the molar amount (S) of the succinic acid diester compound represented by general formula (1) in the total amount of components to the molar amount (T) of titanium in the total amount of components is not particularly limited, but is preferably 0.50 to 2.00, more preferably 0.70 to 1.20. When the molar ratio (S / T) is within the above range, when the catalyst is subjected to olefin polymerization, an olefin polymer with high rigidity can be produced with high polymerization activity.

[0039] The solid catalyst component for olefin polymerization according to the present invention preferably contains 15.0 to 25.0 mass %, more preferably 16.0 to 25.0 mass %, and even more preferably 16.0 to 22.0 mass %, of magnesium in atomic weight terms.

[0040] The solid catalyst component for olefin polymerization according to the present invention preferably contains 50.0 to 70.0 mass %, more preferably 50.0 to 68.0 mass %, and even more preferably 55.0 to 68.0 mass %, of halogen, calculated as atomic weight.

[0041] In the present application, the titanium content in the solid catalyst component for olefin polymerization means the value measured in accordance with the method (oxidation-reduction titration) described in JIS 8311-1997 "Method for determining titanium in titanium ore."

[0042] In addition, in the present application, the content of magnesium in the solid catalyst component for olefin polymerization means a value measured by an EDTA titration method in which the solid catalyst component for olefin polymerization is dissolved in a hydrochloric acid solution and titrated with an EDTA solution.

[0043] In addition, in the present application, the content of halogen contained in the solid catalyst component for olefin polymerization means a value measured by silver nitrate titration in which the solid catalyst component is treated with a mixed solution of sulfuric acid and pure water to prepare an aqueous solution, a predetermined amount of which is then taken, and the halogen is titrated with a silver nitrate standard solution.

[0044] Furthermore, in the present application, the content of the succinic acid diester compound contained in the solid catalyst component for olefin polymerization and the content of other internal electron donor compounds added as needed refer to values ​​obtained by hydrolyzing the solid catalyst component for olefin polymerization, extracting the succinic acid diester compound and other internal electron donor compounds added as needed with an aromatic solvent, and measuring the solution by gas chromatography FID (Flame Ionization Detector).

[0045] The solid catalyst component for olefin polymerization in the present invention may contain a polysiloxane.

[0046] Since the solid catalyst component for olefin polymerization in the present invention contains a polysiloxane, when olefins are polymerized, the stereoregularity or crystallinity of the resulting polymer can be easily improved, and further, the amount of fine powder in the produced polymer can be easily reduced. Polysiloxane is a polymer with a siloxane bond (-Si-O- bond) in the main chain, and is also called silicone oil. Its viscosity at 25°C is 0.02 to 100.00 cm 2 / s (2 to 10,000 centistokes), more preferably 0.03 to 5.00 cm 2 / s (3 to 500 centistokes) and is a linear, partially hydrogenated, cyclic, or modified polysiloxane that is liquid or viscous at room temperature.

[0047] Examples of the chain polysiloxane include dimethylpolysiloxane and methylphenylpolysiloxane. Examples of the partially hydrogenated polysiloxane include methylhydrogenpolysiloxane having a hydrogenation rate of 10 to 80%. Examples of the cyclic polysiloxane include one or more selected from hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, 2,4,6-trimethylcyclotrisiloxane, and 2,4,6,8-tetramethylcyclotetrasiloxane.

[0048] The solid catalyst component for olefin polymerization according to the present invention is preferably prepared by contacting the dialkoxymagnesium, the titanium halide compound, and the succinic acid diester compound represented by general formula (1) in the presence of an inert organic solvent.

[0049] In the present invention, the inert organic solvent is preferably one that dissolves the titanium halide compound but does not dissolve the dialkoxymagnesium, and specific examples include one or more selected from saturated hydrocarbon compounds such as pentane, hexane, heptane, octane, nonane, decane, cyclohexane, methylcyclohexane, ethylcyclohexane, 1,2-diethylcyclohexane, methylcyclohexene, decalin, and mineral oil; aromatic hydrocarbon compounds such as benzene, toluene, xylene, and ethylbenzene; and halogenated hydrocarbon compounds such as ortho-dichlorobenzene, methylene chloride, 1,2-dichlorobenzene, carbon tetrachloride, and dichloroethane. As the inert organic solvent, a saturated hydrocarbon compound or an aromatic hydrocarbon compound that has a boiling point of about 50 to 200°C and is liquid at room temperature is preferably used. Among them, one or more selected from hexane, heptane, octane, ethylcyclohexane, mineral oil, toluene, xylene, and ethylbenzene are preferred, and one or more selected from hexane, heptane, ethylcyclohexane, and toluene are particularly preferred.

[0050] In the solid catalyst component for olefin polymerization according to the present invention, magnesium, titanium, a halogen, and the succinic acid diester compound represented by the general formula (1) can each be contained in a desired amount, so long as the titanium content and the succinic acid diester compound content represented by the general formula (1) satisfy the above-mentioned requirements.

[0051] The solid catalyst component for olefin polymerization according to the present invention contains a succinic acid diester compound represented by general formula (1) in a predetermined content as an internal electron donor, thereby making it possible to produce an olefin polymer having high rigidity and to increase polymerization activity.

[0052] The solid catalyst component for olefin polymerization according to the present invention can be suitably produced by the method for producing a solid catalyst component for olefin polymerization according to the present invention, which will be described below.

[0053] Next, the method for producing the solid catalyst component for olefin polymerization according to the present invention will be described. The method for producing a solid catalyst component for olefin polymerization according to the present invention comprises the steps of: (a) preparing a solid catalyst component for olefin polymerization by using a dialkoxymagnesium compound, a titanium halide compound, and a compound represented by the following general formula (1): R 1 -OC(=O)-CHR 2 CHR 3 -C(=O)-OR 4 (1) (In the formula, R 2 and R 3 are hydrogen atoms or alkyl groups having 1 to 4 carbon atoms, and may be the same or different; R 1 and R 4 are straight-chain or branched alkyl groups having 3 to 6 carbon atoms, and may be the same or different. contacting one or more succinic acid diester compounds selected from the succinic acid diester compounds represented by the total amount of titanium halide compounds used is 2.0 to 12.0 mol relative to 1.0 mol of the dialkoxymagnesium, and the total amount of succinic acid diester compounds represented by the general formula (1) used is 0.06 to 0.20 mol relative to 1.0 mol of the dialkoxymagnesium; It is characterized by the following.

[0054] In the method for producing a solid catalyst component for olefin polymerization according to the present invention, a titanium halide compound is contacted with a dialkoxymagnesium once or multiple times. The total amount of the titanium halide compound used is 2.0 to 12.0 mol, preferably 2.0 to 10.0 mol, and more preferably 4.0 to 8.0 mol per 1.0 mol of dialkoxymagnesium. By controlling the total amount of the titanium halide compound used per 1.0 mol of dialkoxymagnesium within the above range, a solid catalyst component for olefin polymerization capable of achieving high polymerization activity can be prepared.

[0055] In the method for producing a solid catalyst component for olefin polymerization according to the present invention, a succinic acid diester compound represented by general formula (1) is contacted with a dialkoxymagnesium once or multiple times. The total amount of the succinic acid diester compound represented by general formula (1) used is 0.06 to 0.20 mol, preferably 0.08 to 0.18 mol, and more preferably 0.12 to 0.18 mol per 1.0 mol of dialkoxymagnesium. By controlling the total amount of the succinic acid diester compound represented by general formula (1) used per 1.0 mol of dialkoxymagnesium within the above range, a solid catalyst component for olefin polymerization capable of producing an olefin polymer with high rigidity and high polymerization activity can be prepared.

[0056] In the method for producing a solid catalyst component for olefin polymerization according to the present invention, the amounts of the titanium halide compound and the succinic acid diester compound represented by general formula (1) used are adjusted so that the molar ratio (S / T) expressed as the molar amount (S) of the succinic acid diester compound to the molar amount (T) of titanium contained in the resulting solid catalyst component for olefin polymerization is preferably 0.50 to 2.00, more preferably 0.60 to 1.60, and even more preferably 0.70 to 1.20.

[0057] More specifically, the method for producing the solid catalyst component for olefin polymerization according to the present invention may include, for example, suspending dialkoxymagnesium, a titanium halide compound, and a succinic acid diester compound represented by general formula (1) in an inert hydrocarbon solvent and contacting them with each other while heating for a predetermined period of time, then adding a titanium halide compound to the suspension obtained and contacting them with each other while heating to obtain a solid product, and washing the solid product with a hydrocarbon solvent to obtain the desired solid catalyst component for olefin polymerization.

[0058] The inert organic solvent is preferably a liquid at room temperature (20°C) and has a boiling point of 50 to 150°C, and more preferably an aromatic hydrocarbon compound or a saturated hydrocarbon compound that is a liquid at room temperature and has a boiling point of 50 to 150°C.

[0059] Specific examples of the inert organic solvent include one or more selected from linear aliphatic hydrocarbon compounds such as hexane, heptane, and decane; branched aliphatic hydrocarbon compounds such as methylheptane; alicyclic hydrocarbon compounds such as cyclohexane, methylcyclohexane, and ethylcyclohexane; and aromatic hydrocarbon compounds such as toluene, xylene, and ethylbenzene. Among the above inert organic solvents, aromatic hydrocarbon compounds that are liquid at room temperature and have a boiling point of 50 to 150°C are preferred because they can improve the activity of the resulting solid catalyst component and the stereoregularity of the resulting polymer.

[0060] The heating temperature is preferably 70 to 150°C, more preferably 80 to 120°C, and even more preferably 90 to 115°C. The heating time is preferably 30 to 240 minutes, more preferably 60 to 180 minutes, and even more preferably 60 to 120 minutes.

[0061] The number of times the titanium halide compound may be added to the suspension is not particularly limited. When the titanium halide compound is added to the suspension a plurality of times, the heating temperature for each addition should be within the above range, and the heating time for each addition should be within the above range.

[0062] In the above preparation method, other internal electron donor compounds may be used in combination with the succinic acid diester compound represented by general formula (1). Furthermore, the contact may be carried out in the coexistence of other reaction agents such as silicon, phosphorus, and aluminum, or a surfactant.

[0063] In the production method of the present invention, suitable embodiments of the solid catalyst component for olefin polymerization obtained are as described in detail in the description of the solid catalyst component for olefin polymerization according to the present invention.

[0064] Next, the catalyst for olefin polymerization according to the present invention will be described. The catalyst for olefin polymerization according to the present invention comprises: (I) the solid catalyst component for olefin polymerization according to the present invention, and (II) the following general formula (2); R 5 p AlQ 3-p (2) (In the formula, R 5 is an alkyl group having 1 to 6 carbon atoms, Q is a hydrogen atom or a halogen atom, and p is 0. <p≦3であり、R 5 If there are multiple R 5 may be the same or different, and when there are a plurality of Qs, each Q may be the same or different. The olefin polymerization catalyst according to the present invention includes: (I) The solid catalyst component for olefin polymerization according to the present invention, (II) the following general formula (2); R 5 p AlQ 3-p (2) (In the formula, R 5is an alkyl group having 1 to 6 carbon atoms, Q is a hydrogen atom or a halogen atom, p is 0 < p ≤ 3, and R 5 When there are a plurality of them, each R 5 may be the same as or different from each other, and when there are a plurality of Qs, each Q may be the same as or different from each other. The organoaluminum compound represented by), and (III) an external electron donor compound is preferably one containing it.

[0065] The details of the solid catalyst component for olefin polymerization according to the present invention (I) constituting the catalyst for olefin polymerization according to the present invention are as described above.

[0066] In the catalyst for olefin polymerization according to the present invention, (II) the organoaluminum compound has the following general formula (2); R 5 p AlQ 3-p (2) (In the formula, R 5 is an alkyl group having 1 to 6 carbon atoms, Q is a hydrogen atom or a halogen atom, p is 0 < p ≤ 3, and R 5 When there are a plurality of them, each R 5 may be the same as or different from each other, and when there are a plurality of Qs, each Q may be the same as or different from each other.) is represented by.

[0067] In the compound represented by the general formula (2), p is 0 < p ≤ 3, and specifically, examples of p include 1, 2, or 3.

[0068] Specific examples of such (II) organoaluminum compounds include one or more selected from trialkylaluminums such as triethylaluminum, triisopropylaluminum, tri-n-butylaluminum, tri-n-hexylaluminum, and triisobutylaluminum; alkylaluminum halides such as diethylaluminum chloride and diethylaluminum bromide; and diethylaluminum hydride. Of these, one or more selected from alkylaluminum halides such as diethylaluminum chloride; trialkylaluminums such as triethylaluminum, tri-n-butylaluminum, and triisobutylaluminum are preferred, and one or more selected from triethylaluminum and triisobutylaluminum are more preferred.

[0069] The external electron donor compound (III) constituting the catalyst for olefin polymerization of the present invention includes: For example, the following general formula (4) R 7 r Si(NR 8 R 9 ) s (OR 10 ) 4-(r+s) (4) (In the formula, r is 0 or 1 to 2, s is 0 or 1 to 2, r+s is 0 or 1 to 4, R 7 , R 8 or R 9 R is a hydrogen atom or a group selected from a linear or branched alkyl group having 1 to 12 carbon atoms, a substituted or unsubstituted cycloalkyl group, a phenyl group, an allyl group, and an aralkyl group, and may contain a heteroatom, and may be the same or different from each other. 8 and R 9 may be bonded to form a ring, and R 7 , R 8 and R 9 may be the same or different. 10 is any group selected from an alkyl group, a cycloalkyl group, a phenyl group, a vinyl group, an allyl group and an aralkyl group having 1 to 4 carbon atoms, and may contain a hetero atom.

[0070] In the compound represented by the general formula (4), R 7 represents a hydrogen atom or a group selected from a linear or branched alkyl group having 1 to 12 carbon atoms, a substituted or unsubstituted cycloalkyl group, a phenyl group, an allyl group, and an aralkyl group, and may contain a heteroatom. R 7 As the alkyl group, a linear or branched alkyl group having 1 to 10 carbon atoms or a cycloalkyl group having 5 to 8 carbon atoms is preferred, and a linear or branched alkyl group having 1 to 8 carbon atoms or a cycloalkyl group having 5 to 8 carbon atoms is particularly preferred.

[0071] In the compound represented by the general formula (4), R 8 or R 9 represents a hydrogen atom or a group selected from a linear or branched alkyl group having 1 to 12 carbon atoms, a substituted or unsubstituted cycloalkyl group, a phenyl group, an allyl group, and an aralkyl group, and may contain a heteroatom. R 8 or R 9 As the alkyl group, a linear or branched alkyl group having 1 to 10 carbon atoms and a cycloalkyl group having 5 to 8 carbon atoms are preferred, and a linear or branched alkyl group having 1 to 8 carbon atoms and a cycloalkyl group having 5 to 8 carbon atoms are particularly preferred. Also, R 8 and R 9 may be bonded to form a ring, in which case the ring-forming (NR 8 R 9 ) is preferably a perhydroquinolino group or a perhydroisoquinolino group.

[0072] In the compound represented by the general formula (4), R 7 , R 8 and R 9 may be the same or different.

[0073] In the compound represented by the general formula (4), R 10is any group selected from an alkyl group, a cycloalkyl group, a phenyl group, an allyl group and an aralkyl group having 1 to 4 carbon atoms, and may contain a heteroatom. R 10 As the alkyl group, a linear or branched alkyl group having 1 to 4 carbon atoms is preferred.

[0074] In the compound represented by the above general formula (4), r is 0 or 1 to 2, and specifically, 0, 1 or 2 can be mentioned as r. In the compound represented by the above general formula (4), s is 0 or 1 to 2, and specifically, 0, 1 or 2 can be mentioned as s. In the compound represented by the above general formula (4), r+s is 0 or 1 to 4, and specifically, 0, 1, 2, 3, or 4 can be mentioned as r+s.

[0075] Specific examples of such compounds represented by the above general formula (4) include one or more organosilicon compounds selected from phenylalkoxysilanes, alkylalkoxysilanes, phenylalkylalkoxysilanes, cycloalkylalkoxysilanes, cycloalkylalkylalkoxysilanes, (alkylamino)alkoxysilanes, alkyl(alkylamino)alkoxysilanes, alkyl(alkylamino)silanes, alkylaminosilanes, and the like.

[0076] Particularly preferred compounds in which s is 0 in the above general formula (4) include di-n-propyldimethoxysilane, diisopropyldimethoxysilane, di-n-butyldimethoxysilane, diisobutyldimethoxysilane, di-t-butyldimethoxysilane, t-butylmethyldimethoxysilane, t-butylethyldimethoxysilane, di-n-butyldiethoxysilane, t-butyltrimethoxysilane, t-butyltriethoxysilane, dicyclohexyldimethoxysilane, dicyclohexyldiethoxysilane, cyclohexylmethyldimethoxysilane, cyclohexylmethyldiethoxysilane, and cyclohexylethyldimethoxysilane.

[0033] Examples of the organic silicon compound include one or more organic silicon compounds selected from the group consisting of cyclohexylsilane, cyclohexylethyldiethoxysilane, dicyclopentyldimethoxysilane, dicyclopentyldiethoxysilane, cyclopentylmethyldimethoxysilane, cyclopentylmethyldiethoxysilane, cyclopentylethyldiethoxysilane, cyclohexylcyclopentyldimethoxysilane, cyclohexylcyclopentyldiethoxysilane, 3-methylcyclohexylcyclopentyldimethoxysilane, 4-methylcyclohexylcyclopentyldimethoxysilane, and 3,5-dimethylcyclohexylcyclopentyldimethoxysilane.

[0077] Examples of the compound in which s is 1 or 2 in the above general formula (4) include one or more organosilicon compounds selected from di(alkylamino)dialkoxysilanes, (alkylamino)(cycloalkylamino)dialkoxysilanes, (alkylamino)(alkyl)dialkoxysilanes, di(cycloalkylamino)dialkoxysilanes, vinyl(alkylamino)dialkoxysilanes, allyl(alkylamino)dialkoxysilanes, (alkoxyamino)trialkoxysilanes, (alkylamino)trialkoxysilanes, and (cycloalkylamino)trialkoxysilanes, and particularly preferred are ethyl(t-butylamino)dialkoxysilanes. Examples of the organic silicon compounds include bis(perhydroisoquinolino)dimethoxysilane, cyclohexyl(cyclohexylamino)dimethoxysilane, ethyl(t-butylamino)dimethoxysilane, bis(cyclohexylamino)dimethoxysilane, bis(perhydroisoquinolino)dimethoxysilane, bis(perhydroquinolino)dimethoxysilane, ethyl(isoquinolino)dimethoxysilane, diethylaminotrimethoxysilane, and diethylaminotriethoxysilane. Among these, the organic silicon compounds include one or more selected from bis(perhydroisoquinolino)dimethoxysilane, diethylaminotrimethoxysilane, and diethylaminotriethoxysilane.

[0078] The compounds represented by the general formula (4) may be used in combination of two or more kinds.

[0079] The catalyst for olefin polymerization according to the present invention is a catalyst containing (I) the solid catalyst component for olefin polymerization according to the present invention and (II) an organoaluminum compound represented by general formula (2), or a catalyst containing (I) the solid catalyst component for olefin polymerization according to the present invention, (II) an organoaluminum compound represented by general formula (2), and (III) an external electron-donor compound, i.e., a contact product thereof. The catalyst for olefin polymerization according to the present invention may be prepared by contacting (I) the solid catalyst component for olefin polymerization according to the present invention with (II) an organoaluminum compound represented by general formula (2), or (III) an external electron donor compound, in the absence of olefins, or may be prepared by contacting them in the presence of olefins (in a polymerization system), as described below.

[0080] In the olefin polymerization catalyst according to the present invention, the content ratio of each component is not particularly limited and may be any as long as it does not affect the effects of the present invention, but typically, the (II) organoaluminum compound is preferably contained in an amount of 1 to 2,000 moles, more preferably 50 to 1,000 moles, per mole of titanium atom in the (I) solid catalyst component for olefin polymerization. Furthermore, the olefin polymerization catalyst according to the present invention preferably contains the (III) external electron donor compound in an amount of 0.002 to 10,000 moles, more preferably 0.010 to 2,000 moles, and even more preferably 0.010 to 0.500 moles, per mole of the (II) organoaluminum compound.

[0081] According to the present invention, it is possible to provide a catalyst for olefin polymerization that can produce a highly rigid olefin polymer with high polymerization activity.

[0082] Next, the method for producing an olefin polymer according to the present invention will be described. The process for producing an olefin polymer according to the present invention is characterized by carrying out polymerization of olefins in the presence of the olefin polymerization catalyst according to the present invention.

[0083] In the method for producing an olefin polymer according to the present invention, the polymerization of olefins may be homopolymerization or copolymerization. In the method for producing an olefin polymer according to the present invention, the olefin to be polymerized may be one or more selected from ethylene, propylene, 1-butene, 1-pentene, 4-methyl-1-pentene, vinylcyclohexane, etc., and among these, one or more selected from ethylene, propylene, and 1-butene are preferred, with propylene being more preferred. When the olefin is propylene, it may be a homopolymer of propylene, or it may be a copolymer with other α-olefins. The olefins to be copolymerized with propylene include one or more selected from ethylene, 1-butene, 1-pentene, 4-methyl-1-pentene, vinylcyclohexane, and the like.

[0084] When the olefin polymerization catalyst according to the present invention is prepared in the presence of olefins (within the polymerization system), the ratio of the amounts of the components used is not particularly limited and may be any ratio as long as it does not affect the effects of the present invention, but usually, the above-mentioned (II) organoaluminum compound is contacted in an amount of preferably 1 to 2,000 mol, more preferably 50 to 1,000 mol, per mol of titanium atom in the above-mentioned (I) solid catalyst component for olefin polymerization. Also, the above-mentioned (III) external electron donor compound is contacted in an amount of preferably 0.002 to 10,000 mol, more preferably 0.010 to 2,000 mol, even more preferably 0.010 to 0.500 mol, per mol of the above-mentioned (II) organoaluminum compound.

[0085] The order of contacting the components constituting the catalyst for olefin polymerization may be arbitrary. However, it is desirable to first charge the (II) organoaluminum compound into the polymerization system, and then, when the (III) external electron donor compound is used, charge the (III) external electron donor compound and bring them into contact, and then charge and bring into contact the (I) solid catalyst component for olefin polymerization.

[0086] The process for producing an olefin polymer according to the present invention may be carried out in the presence or absence of an organic solvent. Furthermore, olefin monomers such as propylene can be used in either a gaseous or liquid state. The polymerization temperature is preferably 200°C or lower, more preferably 100°C or lower, and the polymerization pressure is preferably 10 MPa or lower, more preferably 5 MPa or lower. The polymerization of olefins can be carried out by either a continuous polymerization method or a batch polymerization method. Furthermore, the polymerization reaction may be carried out in one stage or in two or more stages.

[0087] In addition, when polymerizing olefins using the olefin polymerization catalyst according to the present invention (also referred to as main polymerization), it is preferable to carry out prepolymerization prior to the main polymerization in order to further improve the catalytic activity, stereoregularity, particle properties of the polymer to be produced, etc., and in the prepolymerization, the same olefins as in the main polymerization or monomers such as styrene can be used.

[0088] In carrying out the prepolymerization, the components constituting the catalyst for olefin polymerization and the monomer (olefin) may be contacted in any order. Preferably, however, first (II) an organoaluminum compound is charged into a prepolymerization system set in an inert gas atmosphere or an olefin gas atmosphere, and then (I) the solid catalyst component for olefin polymerization according to the present invention is charged and contacted, and then an olefin such as propylene alone or a mixture of an olefin such as propylene and one or more other olefins is contacted. In the above prepolymerization, when (III) an external electron-donor compound is further charged into the prepolymerization system, it is preferred that (II) an organoaluminum compound is first charged into the prepolymerization system set in an inert gas atmosphere or an olefin gas atmosphere, and then (III) the external electron-donor compound is charged and contacted therewith, and then (I) the solid catalyst component for olefin polymerization according to the present invention is contacted therewith, and then an olefin such as propylene alone or a mixture of an olefin such as propylene and one or more other olefins is contacted therewith.

[0089] In the method for producing an olefin polymer according to the present invention, examples of the polymerization method include a slurry polymerization method using a solvent of an inert hydrocarbon compound such as cyclohexane or heptane, a bulk polymerization method using a solvent such as liquefied propylene, and a gas phase polymerization method which does not substantially use a solvent, and the bulk polymerization method or the gas phase polymerization method is preferred.

[0090] When copolymerizing propylene with other α-olefin monomers, typical methods include random copolymerization in which propylene and a small amount of ethylene are polymerized in one stage as comonomers, and so-called propylene-ethylene block copolymerization in which propylene is homopolymerized in the first stage (first polymerization tank) and then copolymerized with propylene and other α-olefins such as ethylene in the second stage (second polymerization tank) or in multiple stages (multistage polymerization tanks). Block copolymerization of propylene with other α-olefins is preferred.

[0091] A block copolymer obtained by block copolymerization is a polymer containing segments in which the composition of two or more monomers changes continuously, and is a polymer in which two or more types of polymer chains (segments) with different primary structures, such as monomer type, comonomer type, comonomer composition, comonomer content, comonomer sequence, and stereoregularity, are connected in a single molecular chain.

[0092] In the method for producing an olefin polymer according to the present invention, the block copolymerization reaction of propylene with other α-olefins can usually be carried out in the presence of the olefin polymerization catalyst according to the present invention by contacting propylene alone or propylene with a small amount of α-olefin (ethylene, etc.) in a first stage, and then contacting propylene with an α-olefin (ethylene, etc.) in a second stage. The first stage polymerization reaction may be repeated multiple times, or the second stage polymerization reaction may be repeated multiple times to carry out a multi-stage reaction.

[0093] Specifically, the block copolymerization reaction of propylene with other α-olefins is preferably carried out in a first step by adjusting the polymerization temperature and time so that the proportion of polypropylene parts (in the final copolymer) is 20 to 90% by mass, and then in a second step by introducing propylene and ethylene or other α-olefins and polymerizing them so that the proportion of rubber parts such as ethylene-propylene rubber (EPR) (in the final copolymer) is 10 to 80% by mass. The polymerization temperature in both the first and second stages is preferably 200°C or less, more preferably 100°C or less, even more preferably 65°C to 80°C, and still more preferably 75°C to 80°C, and the polymerization pressure is preferably 10 MPa or less, more preferably 6 MPa or less, and even more preferably 5 MPa or less. In the copolymerization reaction, either a continuous polymerization method or a batch polymerization method can be employed, and the polymerization reaction may be carried out in one stage or in two or more stages. The polymerization time (residence time in the reactor) is preferably 1 minute to 5 hours in each polymerization stage of the previous or subsequent polymerization stages, or in the case of continuous polymerization. Examples of the polymerization method include a slurry polymerization method using a solvent of an inert hydrocarbon compound such as cyclohexane or heptane, a bulk polymerization method using a solvent such as liquefied propylene, and a gas phase polymerization method which does not substantially use a solvent, and the bulk polymerization method or the gas phase polymerization method is preferred.

[0094] According to the present invention, it is possible to provide a method for producing an olefin polymer, which can produce an olefin polymer having high rigidity with high polymerization activity.

[0095] Next, an olefin polymer obtained by using a solid catalyst for olefin polymerization containing the solid catalyst component for olefin polymerization according to the present invention as the solid catalyst component for olefin polymerization will be described.

[0096] In the olefin polymer according to the present invention, the melt flow rate (MFR) indicating the melt flowability of the olefin polymer is 60 to 200 g / 10 min, preferably 100 to 200 g / 10 min.

[0097] When the melt flow rate (MFR) of the olefin polymer according to the present invention is within the above range, it can easily exhibit sufficient moldability for practical use.

[0098] In the present application, the melt flow rate (MFR) refers to a value measured in accordance with ASTM D 1238 and JIS K 7210.

[0099] The olefin polymer according to the present invention has a flexural modulus (FM) of 1700 to 2300 MPa, preferably 1800 to 2300 MPa, and more preferably 1900 to 2300 MPa.

[0100] When the olefin polymer according to the present invention has a flexural modulus (FM) within the above range, it can exhibit high rigidity.

[0101] In the present application, the flexural modulus (FM) of an olefin polymer refers to a value (unit: MPa) measured at an ambient temperature of 23°C in accordance with JIS K7171 using an injection-molded test piece having a thickness of 4.0 mm, a width of 10.0 mm and a length of 80.0 mm, which was prepared using NEX30III3EG manufactured by Nissei Plastic Industrial Co., Ltd. under conditions of a molding temperature of 200°C and a mold temperature of 40°C.

[0102] The olefin polymer according to the present invention has a bulk density (BD) of 0.38 to 0.46 g / cm 3 and is 0.39 to 0.45 g / cm 3 Preferably, the density is 0.40 to 0.45 g / cm 3 It is more preferable that:

[0103] In the olefin polymer according to the present invention, when the bulk density (BD) is within the above range, the storability of the polymer powder is improved, and a copolymer having excellent mechanical properties can be produced.

[0104] In the present application, the bulk density (BD) of a polymer refers to a value measured in accordance with JIS K-6721:1997 (unit: g / cm 3 ). [Example]

[0105] Next, the present invention will be explained in more detail by way of examples, but these are merely illustrative and do not limit the present invention.

[0106] Example 1 1. Synthesis of solid catalyst components As an internal electron donor compound, di-n-butyl diisopropylsuccinate, a succinic acid diester compound, was used, and a solid catalyst component for olefin polymerization was prepared by the following method. (i) A 500 mL flask equipped with a stirrer and purged with nitrogen gas was charged with 10 g (87.4 mmol) of diethoxymagnesium and 55.0 mL of toluene to form a suspension. (ii) Then, 20.0 mL (182 mmol) of titanium tetrachloride was added to obtain a liquid containing an initial contact product. (iii) The temperature of the initial contact product-containing liquid was raised, and 3.7 mL (11.1 mmol) of di-n-butyl diisopropylsuccinate was added at 90°C during the temperature increase, and the temperature was further raised to 100°C, and the reaction was carried out for 90 minutes while maintaining the temperature. After completion of the reaction, the supernatant was removed, and the reaction product, the first contact product, was washed four times with 53 mL of toluene at 90°C. (iv) Next, 30 mL (273 mmol) of titanium tetrachloride was added to the first contact product, and the mixture was heated to 115°C and reacted for 60 minutes. After completion of the reaction, the supernatant was removed, and the reaction product, that is, the second contact product, was washed twice with 53 mL of toluene at 90°C to obtain a final contact product. Next, the obtained final contact product was washed six times with 50 mL of n-heptane at 40° C., and solid-liquid separation was carried out to obtain a solid catalyst component (solid catalyst component for olefin polymerization). The obtained solid catalyst component was separated into solid and liquid, and the titanium content and the succinic acid diester compound content in the obtained solid were measured to be 4.7% by mass and 20.9% by mass, respectively. The molar ratio of the succinic acid diester compound content to the titanium content was 0.82. The properties of the obtained solid catalyst component are shown in Table 1.

[0107] The titanium content in the solid catalyst component, the content of the succinic acid diester compound as the internal electron donor compound, and other physical properties were measured by the following methods.

[0108] <Titanium content in solid catalyst component> The titanium content in the solid catalyst component was measured based on the method of JIS 8311-1997.

[0109] <Internal electron donating compound content> The content of the internal electron donor compound was determined by measurement using a gas chromatograph (GC-2014, manufactured by Shimadzu Corporation) under the following conditions: The number of moles of the internal electron donor compound was determined from the gas chromatographic measurement results using a calibration curve previously measured at known concentrations. <Measurement conditions> Column: Capillary column (φ0.32 mm, film thickness 1.0 μm, Rxi-1ms, GL Sciences Inc.) Detector: FID (Flame Ionization Detector) Carrier gas: Helium, flow rate 7.0 ml / min Measurement temperature: vaporizer 280℃, column 170℃, detector 280℃

[0110] 2. Formation of polymerization catalyst and polymerization reaction A polymerization catalyst was prepared by charging 1.32 mmol of triethylaluminum, 0.131 mmol of diisopropyldimethoxysilane (DIPDMSi), and 0.00132 mmol of the above solid catalyst component (calculated as titanium atoms) into a 2.0 L autoclave equipped with a stirrer and purged with nitrogen gas. 6.0 L of hydrogen gas and 1.4 L of liquefied propylene were then charged, and prepolymerization was carried out at 20°C for 5 minutes, followed by heating and polymerization at 70°C for 1 hour. The polymerization activity per 1 g of the solid catalyst component, the melt flow property (melt flow rate (MFR)), the flexural modulus (FM), and the bulk density (BD) of the polymer were measured by the following methods. The results are shown in Table 1.

[0111] <Polymerization activity per 1g of solid catalyst component> The polymerization activity per 1 g of the solid catalyst component was calculated by the following formula (6). Polymerization activity (g / g-cat) = polymer mass (g) / solid catalyst component mass (g) (6)

[0112] <Polymer melt flow (MFR)> The melt flow rate (MFR) (g / 10 min), which indicates the melt flowability of the polymer, was measured in accordance with ASTM D 1238 and JIS K 7210.

[0113] <Flexural modulus of polymer (FM)> Measurements were carried out in accordance with JIS K7171 using injection-molded test pieces measuring 4.0 mm thick, 10.0 mm wide, and 80 mm long, prepared using an NEX30III3EG manufactured by Nissei Plastic Industrial Co., Ltd. at a molding temperature of 200°C and a mold temperature of 40°C, at an ambient temperature of 23°C.

[0114] <Polymer bulk density (BD)> The bulk density (BD) of the polymer was measured in accordance with JIS K-6721:1997.

[0115] (Comparative Example 1) The same procedure as in Example 1 was carried out except that diethyl diisopropylsuccinate was used instead of di-n-butyl diisopropylsuccinate. The results are shown in Table 1.

[0116] [Table 1]

[0117] In Table 1, for the internal electron donor, "1" indicates di-n-butyl diisopropylsuccinate, and "2" indicates diethyl diisopropylsuccinate. [Industrial Applicability]

[0118] According to the present invention, an olefin polymer having high rigidity can be produced with high polymerization activity, and therefore, an olefin polymer having high rigidity can be produced efficiently.

Claims

1. Magnesium, titanium, a halogen, and a compound represented by the following general formula (1); R １ -O-C(=O)-CHR ２ CHR ３ -C(=O)-O-R ４ (1) (In the formula, R ２ and R ３ are hydrogen atoms or alkyl groups having 1 to 4 carbon atoms, and may be the same or different; R １ and R ４ are straight-chain or branched alkyl groups having 3 to 6 carbon atoms, and may be the same or different. The succinic acid diester compound may be one or more selected from the succinic acid diester compounds represented by the formula: the content of the succinic acid diester compound represented by the general formula (1) is 12.0 to 25.0 mass% and the content of titanium atoms is 2.5 to 5.0 mass% in the total amount of components when converted into solid content; A solid catalyst component for olefin polymerization, characterized by:

2. R in the general formula (1) １ and R ４ 2. The solid catalyst component for olefin polymerization according to claim 1, wherein each of the groups is a linear or branched alkyl group having 4 carbon atoms, and may be the same or different from each other.

3. R in the general formula (1) ２ and R ３ 3. The solid catalyst component for olefin polymerization according to claim 2, wherein each of the groups is an isopropyl group, a methyl group, an ethyl group, or an isobutyl group, and may be the same or different from each other.

4. Dialkoxy magnesium, titanium halide compound and the following general formula (1); R １ -O-C(=O)-CHR ２ CHR ３ -C(=O)-O-R ４ (1) (In the formula, R ２ and R ３ are hydrogen atoms or alkyl groups having 1 to 4 carbon atoms, and may be the same or different; R １ and R ４ are straight-chain or branched alkyl groups having 3 to 6 carbon atoms, and may be the same or different. contacting one or more succinic acid diester compounds selected from the succinic acid diester compounds represented by the total amount of the titanium halide compounds used is 2.0 to 12.0 mol per 1.0 mol of the dialkoxymagnesium, and the total amount of the succinic acid diester compounds represented by the general formula (1) used is 0.06 to 0.20 mol per 1.0 mol of the dialkoxymagnesium; A method for producing a solid catalyst component for olefin polymerization, characterized by:

5. (I) the solid catalyst component for olefin polymerization according to any one of claims 1 to 3, and (II) The following general formula (2): R ５ ｐ AlQ ３－ｐ (2) (In the formula, R ５ is an alkyl group having 1 to 6 carbon atoms, Q is a hydrogen atom or a halogen atom, p is 0<p≦3, and R ５ If there are multiple R ５ may be the same or different, and when there are multiple Qs, each Q may be the same or different. An organoaluminum compound represented by A catalyst for olefin polymerization, comprising:

6. (I) the solid catalyst component for olefin polymerization according to any one of claims 1 to 3, (II) a compound represented by the following general formula (2): R ５ ｐ AlQ ３－ｐ (2) (In the formula, R ５ is an alkyl group having 1 to 6 carbon atoms, Q is a hydrogen atom or a halogen atom, p is 0<p≦3, and R ５ If there are multiple R ５ may be the same or different, and when there are multiple Qs, each Q may be the same or different. and organoaluminum compounds represented by (III) External electron donor compound The catalyst for olefin polymerization according to claim 5, comprising:

7. A method for producing olefin polymers, comprising carrying out polymerization of olefins using the olefin polymerization catalyst according to claim 5 or 6.

Images