Catalyst for olefin polymerization and method for producing olefin polymer

Abstract

This catalyst for olefin polymerization is characterized by comprising: (I) a solid catalyst component for olefin polymerization containing at least magnesium, titanium, a halogen and at least one compound selected from succinic diester compounds and at least one compound selected from phthalic diester compounds as internal electron donors; (II) an organoaluminum compound; and (III) at least one compound selected from alkoxysilane compounds and at least one compound selected from (alkylamino)alkylsilane compounds as external electron donars. According to the present invention, it is possible to provide: a catalyst for olefin polymerization capable of producing an olefin polymer that has high rigidity and high impact resistance; and a method for producing an olefin polymer by using the catalyst.

Description

Catalyst for olefin polymerization and method for producing olefin polymers

[0001] This invention relates to a catalyst for olefin polymerization and a method for producing olefin polymers using the same.

[0002] In recent years, olefin polymers such as polypropylene (PP) have been used in a variety of applications, including molded products such as automotive parts and home appliances, as well as containers and films.

[0003] Polypropylene resin has become an extremely important material in many fields due to its excellent properties. These include its lightweight nature, excellent moldability, and high chemical stability such as heat resistance and chemical resistance during molding. Furthermore, it offers excellent cost performance.

[0004] Conventionally, in the production of polymers of olefins such as polypropylene, which have high rigidity, the polymerization of olefins has been carried out using a catalyst for olefin polymerization that uses 2,3-diisopropyl succinate diester as an internal electron donor.

[0005] For example, the example in Patent Document 1 describes the polymerization of propylene using ethyl 2,3-diisopropyl succinate as an internal electron donor.

[0006] Japanese Patent Publication No. 2013-533367

[0007] However, when performing homopolymerization of olefins or copolymerization of ethylene and propylene using a solid catalyst component containing diethyl succinate as an internal electron-donating compound, in homopolymerization of olefins or copolymerization of ethylene and propylene, where high impact resistance is required, using a diethyl succinate compound increases rigidity but reduces melt flowability. Therefore, in order to obtain a homopolymer or copolymer with practical melt flowability using a diethyl succinate compound as the internal electron-donating compound, a large amount of hydrogen must be used during polymerization. This, in turn, leads to the problem of reduced impact resistance.

[0008] In other words, in the polymerization of olefins using catalysts for olefin polymerization, there is a strong tendency for the rigidity and impact resistance of the resulting olefin copolymer to be in a trade-off relationship, making it difficult to obtain olefin polymers that possess both rigidity and impact resistance.

[0009] Therefore, the present invention aims to provide an olefin polymerization catalyst that can produce olefin polymers with higher rigidity and impact resistance than those obtained using conventional olefin polymerization catalysts when compared under similar polymerization conditions, and a method for producing olefin polymers using the same.

[0010] In order to solve the above technical problems, the inventors conducted extensive research and found that by using succinic acid diester compounds and phthalic acid diester compounds as internal electron-donating compounds for the solid catalyst component of the olefin polymerization catalyst, and by using alkoxysilane compounds and (alkylamino)alkylsilane compounds as external electron-donating compounds to be combined with the solid catalyst component of the olefin polymerization catalyst, sufficient melt flowability can be obtained even with a small amount of hydrogen used during polymerization. As a result, it is possible to increase the production of high molecular weight polymers and suppress the production of low molecular weight polymers. Consequently, when compared under similar polymerization conditions, olefin polymers with higher rigidity and impact resistance can be obtained compared to conventional olefin polymerization catalysts. Based on this finding, the present invention was completed.

[0011] In other words, the present invention comprises (1) (I) at least magnesium, titanium, halogen and an internal electron-donating compound, comprising at least the following general formula (1):

[0012]

[0013] (In the formula, R １ and R ２ Each of these is independently a linear alkyl group having 1 to 12 carbon atoms, a branched alkyl group having 3 to 12 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms, a cycloalkenyl group having 3 to 12 carbon atoms, or an aromatic hydrocarbon group having 6 to 20 carbon atoms, and they may be the same or different from each other.３ , R ４ , R ５ and R ６ are each independently a hydrogen atom, a halogen atom, a linear alkyl group having 1 to 12 carbon atoms, a branched alkyl group having 3 to 12 carbon atoms, a vinyl group, a linear alkenyl group or a branched alkenyl group having 3 to 12 carbon atoms, a linear or branched halogen-substituted alkyl group having 2 to 12 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms, a cycloalkenyl group having 3 to 12 carbon atoms, an aromatic hydrocarbon group having 6 to 20 carbon atoms, a nitrogen-containing group, a phosphorus-containing group, and a silicon-containing group, and may be the same or different from each other. ) at least one compound selected from the group consisting of diester compounds, and the following general formula (2):

[0014]

[0015] (wherein, R ７ represents an alkyl group having 1 to 8 carbon atoms or a halogen atom, R ８ and R ９ are alkyl groups having 1 to 12 carbon atoms, which may be the same or different, and the number n of the substituent R ７ is 0, 1 or 2, and when n is 2, R ７ may be the same or different from each other. ) a solid catalyst component for olefin polymerization containing at least one compound selected from the group consisting of diester compounds, (II) an organoaluminum compound, and (III) as an external electron donor compound, at least the following general formula (3): Si(OR １０ )(OR １１ )(OR １２ )(OR １３ )(3) (wherein, R １０ , R １１ , R １２ and R １３ are linear alkyl groups having 1 to 8 carbon atoms or branched alkyl groups having 3 to 8 carbon atoms, which may be the same or different from each other. ) at least one selected from the group consisting of alkoxysilane compounds represented by the following general formula (4): R １４ R １５ Si(NHR １６ )(NHR １７) (4) (wherein, R １４ and R １５ R is a linear alkyl group having 1 to 8 carbon atoms, a branched alkyl group having 3 to 12 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms, a cycloalkenyl group having 3 to 12 carbon atoms, or an aromatic hydrocarbon group having 6 to 20 carbon atoms, and they may be the same or different from each other. １６ and R １７A catalyst for olefin polymerization, characterized by containing one or more (alkylamino)alkylsilane compounds represented by (wherein are alkyl groups having 1 to 8 carbon atoms, which may be the same or different from each other), and(2) The succinate diester compound represented by the general formula (1) is diethyl succinate, diethyl 2,3-dimethyl succinate, diethyl 2,3-diethyl succinate, diethyl 2,3-di-n-propyl succinate, diethyl 2,3-di-n-butyl succinate, diethyl 2,3-diisopropyl succinate, diethyl 2,3-di-n-butyl succinate, diethyl 2,3-diisobutyl succinate, diisobutyl 2,3-diisopropyl succinate, di-n-butyl 2,3-diisopropyl succinate, dicyclohexyl Diethyl 2-methylsuccinate, diisobutyl 2,3-dicyclohexyl-2-methylsuccinate, diethyl 2,3-diisopropyl-2-cyanosuccinate, di-n-butyl 2,3-diisopropyl-2-cyanosuccinate, di-n-butyl 2,3-diisopropyl-2-cyanosuccinate, diisobutyl 2,3-dicyclopentyl-2-cyanosuccinate, diethyl 2,3-dicyclopentyl-2-cyanosuccinate, di-n-butyl 2,3-dicyclopentyl-2-cyanosuccinate Diisobutyl citrate, 2,3-dicyclohexyl-2-cyanosuccinate diethyl, 2,3-dicyclohexyl-2-cyanosuccinate di-n-butyl, 2,3-dicyclohexyl-2-cyanosuccinate diisobutyl, 2-cyclopentyl-3-cyclohexyl-2-cyanosuccinate diethyl, 2,3-diisopropyl-2-cyanosuccinate 1-isobutyl 4-ethyl, 2,3-diisopropyl-2-cyanosuccinate 1-n-butyl 4-ethyl, 2-isopropyl-3-methyl-2-cyanosuccinate diethyl, 2-isopropyl The catalyst for polymerization of olefins according to (1), characterized by being at least one selected from the group consisting of diethyl 3-ethyl-2-cyanosuccinate, diethyl 2-isopropyl-3-n-propyl-2-cyanosuccinate, diethyl 2-isopropyl-3-butyl-2-cyanosuccinate, diethyl 2-isopropyl-3-phenyl-2-cyanosuccinate, diethyl 2-cyclohexyl-3-isopropyl-2-cyanosuccinate, and 1-ethyl-4-isobutyl 2-isopropyl-3-phenyl-2-cyanosuccinate.(3) The phthalate diester compound represented by the general formula (2) is dimethyl phthalate, diethyl phthalate, di-n-propyl phthalate, diisopropyl phthalate, di-n-butyl phthalate, diisobutyl phthalate, ethylmethyl phthalate, methyl(isopropyl) phthalate, ethyl(n-propyl) phthalate, ethyl(n-butyl) phthalate, ethyl(isobutyl) phthalate, di-n-pentyl phthalate, diisopentyl phthalate, dineopentyl phthalate, dihexyl phthalate, di-n-heptyl phthalate, di-n-octyl phthalate, bis(2,2-dimethylhexyl) phthalate, bis(2-ethylhexyl) phthalate, di-n-nonyl phthalate, diisodecyl phthalate, bis(2,2-dimethylheptyl) phthalate, n-butyl(isohexyl) phthalate, n-butyl(2-ethyl) phthalate The catalyst for polymerization of olefins according to (1), characterized by being at least one selected from the group consisting of n-pentylhexyl phthalate, n-pentyl(isohexyl) phthalate, isopentyl(heptyl) phthalate, n-pentyl(2-ethylhexyl) phthalate, n-pentyl(isononyl) phthalate, isopentyl(n-decyl) phthalate, n-pentylundecyl phthalate, isopentyl(isohexyl) phthalate, n-hexyl(2,2-dimethylhexyl) phthalate, n-hexyl(2-ethylhexyl) phthalate, n-hexyl(isononyl) phthalate, n-hexyl(n-decyl) phthalate, n-heptyl(2-ethylhexyl) phthalate, n-heptyl(isononyl) phthalate, n-heptyl(neodecyl) phthalate, and 2-ethylhexyl(isononyl) phthalate. (4) The catalyst for polymerization of olefins according to (1), characterized in that the alkoxysilane compound represented by the general formula (3) is at least one selected from the group consisting of tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, tetraisopropoxysilane, tetrabutoxysilane, and tetrakis(2-ethylhexyloxy)silane.(5) The catalyst for polymerization of olefins according to (1), characterized in that the (alkylamino)alkylsilane compound represented by general formula (4) is at least one selected from the group consisting of diisopropylbis(ethylamino)silane, dicyclopentylbis(ethylamino)silane, dicyclohexylbis(ethylamino)silane, cyclohexylmethylbis(ethylamino)silane, and cyclohexylcyclopentylbis(ethylamino)silane. (6) The catalyst for polymerization of olefins according to (1), characterized in that the molar ratio (Y / X) of the content (Y) of the (alkylamino)alkylsilane compound represented by general formula (4) to the content (X) of the alkoxysilane compound represented by general formula (3) is 1 / 99 to 50 / 50. (7) A method for producing an olefin polymer, characterized by polymerizing olefins using the catalyst for polymerization of olefins according to (1).

[0016] According to the present invention, it is possible to provide an olefin polymerization catalyst that can produce olefin polymers with higher rigidity and impact resistance than those obtained using conventional olefin polymerization catalysts when compared under similar polymerization conditions, and a method for producing olefin polymers using the same.

[0017] The olefin polymerization catalyst of the present invention comprises (I) at least magnesium, titanium, a halogen, and an internal electron-donating compound, comprising at least the following general formula (1):

[0018]

[0019] (In the formula, R １ and R ２ Each of these is independently a linear alkyl group having 1 to 12 carbon atoms, a branched alkyl group having 3 to 12 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms, a cycloalkenyl group having 3 to 12 carbon atoms, or an aromatic hydrocarbon group having 6 to 20 carbon atoms, and they may be the same or different from each other. ３ , R ４ , R ５ and R ６Each of these atoms or groups is independently selected from a hydrogen atom, a halogen atom, a linear alkyl group having 1 to 12 carbon atoms, a branched alkyl group having 3 to 12 carbon atoms, a vinyl group, a linear alkenyl group or branched alkenyl group having 3 to 12 carbon atoms, a linear or branched halogen-substituted alkyl group having 2 to 12 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms, a cycloalkenyl group having 3 to 12 carbon atoms, an aromatic hydrocarbon group having 6 to 20 carbon atoms, a nitrogen-containing group, a phosphorus-containing group, and a silicon-containing group, and they may be the same or different from each other.) One or more compounds selected from succinate diester compounds represented by the following general formula (2):

[0020]

[0021] (In the formula, R ７ R represents an alkyl group or halogen atom having 1 to 8 carbon atoms. ８ and R ９ R is an alkyl group having 1 to 12 carbon atoms, and may be the same or different, and the substituent R ７ The number n is 0, 1, or 2, and when n is 2, R ７ (1) a solid catalyst component for olefin polymerization comprising one or more compounds selected from phthalate diester compounds represented by (2) (which may be the same or different from each other), (2) an organoaluminum compound, and (3) an external electron-donating compound comprising at least the following general formula (3): Si(OR １０ ) ( OR １１ ) ( OR １２ ) ( OR １３ ) (3) (wherein, R １０ , R １１ , R １２ and R １３ (wherein C1 to C8 is a linear alkyl group or a branched alkyl group having C3 to C8, and they may be the same or different from each other.) One or more compounds selected from alkoxysilane compounds represented by the following general formula (4): R １４ R １５ Si (NHR １６ ) (NHR １７ ) (4) (wherein, R １４ and R １５R is a linear alkyl group having 1 to 8 carbon atoms, a branched alkyl group having 3 to 12 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms, a cycloalkenyl group having 3 to 12 carbon atoms, or an aromatic hydrocarbon group having 6 to 20 carbon atoms, and they may be the same or different from each other. １６ and R １７ The catalyst for olefin polymerization is characterized by containing one or more compounds selected from (alkylamino)alkylsilane compounds represented by ) (where is an alkyl group having 1 to 8 carbon atoms, which may be the same or different from each other), and .

[0022] In other words, the olefin polymerization catalyst of the present invention is an olefin polymerization catalyst that contains: (I) a solid catalyst component for olefin polymerization containing at least magnesium, titanium, halogen and an internal electron-donating compound, which includes at least a succinate diester compound and a phthalate diester compound; (II) an organoaluminum compound; and (III) an external electron-donating compound, which includes at least one selected from alkoxysilane compounds represented by general formula (3) and one selected from (alkylamino)alkylsilane compounds represented by general formula (4).

[0023] The olefin polymerization catalyst of the present invention contains (I) a solid catalyst component for olefin polymerization containing at least a succinate diester compound and a phthalate diester compound.

[0024] The solid catalyst component for olefin polymerization containing a succinate diester compound and a phthalate diester compound according to the present invention is a solid catalyst component for olefin polymerization that contains at least magnesium, titanium, halogen, and an internal electron-donating compound, specifically a succinate diester compound represented by general formula (1) and a phthalate diester compound represented by general formula (2). The solid catalyst component for olefin polymerization containing a succinate diester compound and a phthalate diester compound is a solid catalyst component in which both the succinate diester compound and the phthalate diester compound are supported within the solid catalyst component.

[0025] Examples of solid catalyst components for the polymerization of olefins containing succinate diester compounds and phthalate diester compounds include a catalytic reaction product obtained by contacting and reacting a raw material component that serves as a source of magnesium, a raw material component that serves as a source of titanium and halogens, and an internally electron-donating compound, such as a succinate diester compound and a phthalate diester compound, in an organic solvent. Specifically, examples include a catalytic reaction product obtained by using dialkoxymagnesium as the raw material component that serves as the source of magnesium, and a tetravalent titanium-halogen compound as the raw material component that serves as the source of titanium and halogens, and contacting these raw materials with an internally electron-donating compound containing a succinate diester compound and an internally electron-donating compound containing a phthalate diester compound.

[0026] In solid catalyst components for olefin polymerization containing succinate diester compounds and phthalate diester compounds, dialkoxymagnesium, which is a raw material component that serves as a source of magnesium, can be one or more selected from magnesium dihalides, dialkylmagnesium, alkylmagnesium halides, dialkoxymagnesium, diaryloxymagnesium, alkoxymagnesium halides, or fatty acid magnesium. Among these magnesium compounds, magnesium dihalides, mixtures of magnesium dihalides and dialkoxymagnesium, and dialkoxymagnesium are preferred, with dialkoxymagnesium being particularly preferred.

[0027] Specific examples of dialkoxymagnesium include dimethoxymagnesium, diethoxymagnesium, dipropoxymagnesium, dibutoxymagnesium, ethoxymethoxymagnesium, ethoxypropoxymagnesium, and butoxyethoxymagnesium. These dialkoxymagnesiums may also be obtained by reacting metallic magnesium with an alcohol in the presence of a halogen or a halogen-containing metal compound. Furthermore, one or more of the above-mentioned dialkoxymagnesiums can be used in combination.

[0028] The above-mentioned dialkoxymagnesium is preferably in granular or powder form, and may be of an irregular shape or spherical.

[0029] When spherical dialkoxymagnesium is used, a polymer powder with a better particle shape (more spherical) and a narrower particle size distribution can be obtained, improving the handling of the polymer powder generated during the polymerization operation and suppressing the occurrence of blockages and other problems caused by fine particles contained in the generated polymer powder.

[0030] The spherical dialkoxymagnesium particles described above do not necessarily have to be perfectly spherical; elliptical or potato-shaped particles can also be used. Specifically, the particle shape is such that the ratio of the major axis diameter l to the minor axis diameter w (l / w) is 3 or less, preferably 1 to 2, and more preferably 1 to 1.5.

[0031] Furthermore, the average particle size (average particle size D50) of the dialkoxymagnesium is preferably 1.0 to 200.0 μm, and more preferably 5.0 to 150.0 μm. Here, the average particle size D50 refers to the particle size that accounts for 50% of the cumulative particle size distribution in the volume cumulative particle size distribution when 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.

[0032] Furthermore, regarding the particle size distribution of dialkoxymagnesium, it is preferable to have a narrow particle size distribution with few fine and coarse particles. Specifically, when measured using a laser scattering diffraction particle size analyzer, it is preferable that 20% or less of the particles have a particle size of 5.0 μm or less, and more preferably 10% or less. On the other hand, when measured using a laser scattering diffraction particle size analyzer, it is preferable that 20% or less of the particles have a particle size of 100.0 μm or more, and more preferably 10% or less. Furthermore, when the particle size distribution is expressed as ln(D90 / D10), it is preferable that it is 3 or less, and more preferably 2 or less. Here, D90 represents the particle size that accounts for 90% of the integrated particle size in the volume integrated particle size distribution when measured using a laser scattering diffraction particle size analyzer. Also, D10 represents the particle size that accounts for 10% of the integrated particle size in the volume integrated particle size distribution when measured using a laser scattering diffraction particle size analyzer.

[0033] Methods for producing the above-mentioned spherical dialkoxymagnesium are exemplified in, for example, Japanese Patent Publication No. 62-51633, Japanese Patent Publication No. 3-74341, Japanese Patent Publication No. 4-368391, Japanese Patent Publication No. 8-73388, and the like.

[0034] Dialkoxymagnesium has a specific surface area of ​​5 m². ２ Preferably, it is 5 to 50 m ２ It is more preferable that the amount is / g, and 10 to 40m ２ A value of / g is even more preferable. By using a dialkoxymagnesium with 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.

[0035] In this application, the specific surface area of ​​dialkoxymagnesium refers to the value measured by the BET method. Specifically, the specific surface area of ​​dialkoxymagnesium refers to the value measured by the BET method (automatic measurement) using a Mounttech Automatic Surface Area Analyzer HM model-1230 in the presence of a mixed gas of nitrogen and helium, after the sample has been vacuum-dried at 50°C for 2 hours.

[0036] The above-mentioned dialkoxymagnesium is preferably in solution or suspension form during the reaction, as this allows the reaction to proceed smoothly.

[0037] If the above-mentioned dialkoxymagnesium is a solid, it can be dissolved in a solvent that has the ability to solubilize dialkoxymagnesium to obtain a solution of dialkoxymagnesium, or suspended in a solvent that does not have the ability to solubilize dialkoxymagnesium to obtain a suspension of dialkoxymagnesium. If the dialkoxymagnesium is a liquid, it may be used as is as a solution of dialkoxymagnesium, or it may be further dissolved in a solvent that has the ability to solubilize dialkoxymagnesium to obtain a solution of dialkoxymagnesium.

[0038] Compounds that can solubilize solid dialkoxymagnesium include at least one compound selected from the group consisting of alcohols, ethers, and esters. Among these, alcohols such as ethanol, propanol, butanol, and 2-ethylhexanol are preferred, and 2-ethylhexanol is particularly preferred. On the other hand, media that do not have the ability to solubilize solid dialkoxymagnesium include one or more solvents selected from saturated hydrocarbon solvents or unsaturated hydrocarbon solvents that do not dissolve dialkoxymagnesium.

[0039] In solid catalyst components for olefin polymerization containing succinate diester compounds and phthalate diester compounds, the tetravalent titanium halogen compound, which is a raw material component that supplies titanium and halogen, is not particularly limited, but the following general formula (5): Ti(OR １８ ) ｐ X ４－ｐ (5) (wherein, R １８ It is preferable that the compound is one or more compounds selected from the titanium halide or alkoxy titanium halide group represented by (where 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 p is 0 ≤ p ≤ 3).

[0040] In the general formula (5) above, p is 0 ≤ p ≤ 3, and specifically, p can be 0, 1, 2, or 3.

[0041] Examples of titanium halides represented by the above general formula (5) include one or more titanium tetrahalides selected from titanium tetrachloride, titanium tetrabromide, titanium tetraiodide, etc. Examples of alkoxy titanium halides represented by the above general formula (5) 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, trippropoxytitanium chloride, tri-n-butoxytitanium chloride, etc. As the tetravalent titanium halogen compound, titanium tetrahalide is preferred, and titanium tetrachloride is more preferred. These titanium compounds may be used individually or in combination of two or more.

[0042] The solid catalyst component for olefin polymerization containing succinate diester compounds and phthalate diester compounds is an internally electron-donating compound, with the following general formula (1):

[0043]

[0044] (In the formula, R １ and R ２ Each of these is independently a linear alkyl group having 1 to 12 carbon atoms, a branched alkyl group having 3 to 12 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms, a cycloalkenyl group having 3 to 12 carbon atoms, or an aromatic hydrocarbon group having 6 to 20 carbon atoms, and they may be the same or different from each other. ３ , R ４ , R ５ and R ６ Each of these atoms or groups is independently selected from a hydrogen atom, a halogen atom, a linear alkyl group having 1 to 12 carbon atoms, a branched alkyl group having 3 to 12 carbon atoms, a vinyl group, a linear or branched alkenyl group having 3 to 12 carbon atoms, a linear or branched halogen-substituted alkyl group having 2 to 12 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms, a cycloalkenyl group having 3 to 12 carbon atoms, an aromatic hydrocarbon group having 6 to 20 carbon atoms, a nitrogen-containing group, a phosphorus-containing group, and a silicon-containing group, and they may be the same or different from each other. The catalyst contains one or more compounds selected from succinate diester compounds represented by general formula (1) as an internal electron-donating compound. The presence of a succinate diester compound represented by general formula (1) in the olefin polymerization catalyst is preferable because it allows for the generation of a large amount of high molecular weight polymer during polymerization, thereby increasing rigidity.

[0045] In a succinate diester compound represented by general formula (1), R １ and R ２ Each of these is independently a linear alkyl group having 1 to 12 carbon atoms, a branched alkyl group having 3 to 12 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms, a cycloalkenyl group having 3 to 12 carbon atoms, or an aromatic hydrocarbon group having 6 to 20 carbon atoms, and they may be the same or different from each other. １ and R ２ When R is an alkyl group having 1 to 4 carbon atoms, specifically, examples include a methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, or isobutyl group. In a succinic acid diester compound represented by general formula (1), R ３ , R ４ , R ５ and R ６Each of these atoms or groups is independently selected from hydrogen atoms, halogen atoms, linear alkyl groups having 1 to 12 carbon atoms, branched alkyl groups having 3 to 12 carbon atoms, vinyl groups, linear or branched alkenyl groups having 3 to 12 carbon atoms, linear or branched halogen-substituted alkyl groups having 2 to 12 carbon atoms, cycloalkyl groups having 3 to 12 carbon atoms, cycloalkenyl groups having 3 to 12 carbon atoms, aromatic hydrocarbon groups having 6 to 20 carbon atoms, nitrogen-containing groups, phosphorus-containing groups, and silicon-containing groups, and may be the same as or different from each other. ３ , R ４ , R ５ and R ６ When is a linear alkyl group having 1 to 12 carbon atoms or a branched alkyl group having 3 to 12 carbon atoms, specific examples include an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, or an isobutyl group. ３ , R ４ , R ５ and R ６ When the group is a nitrogen-containing group, specific examples include amino groups and cyano groups.

[0046] In solid catalyst components for olefin polymerization containing succinate diester compounds and phthalate diester compounds, the succinate diester compound represented by general formula (1) is not particularly limited, and examples include: diethyl succinate, 2,3-dimethyl succinate diethyl, 2,3-diethyl succinate diethyl, 2,3-di-n-propyl succinate diethyl, 2,3-diisopropyl succinate diethyl, 2,3-di-n-butyl succinate diethyl, and 2,3-diisobutyl succinate diethyl; Di-n-propyl succinate, di-n-propyl 2,3-dimethyl succinate, di-n-propyl 2,3-diethyl succinate, di-n-propyl succinate, di-n-propyl 2,3-diisopropyl succinate, di-n-propyl 2,3-diisobutyl succinate, di-n-propyl 2,3-diisobutyl succinate; diisopropyl succinate, diisopropyl 2,3-dimethyl succinate, diisopropyl 2,3-diethyl succinate, diisopropyl 2,3-di-n-propyl succinate, diisopropyl 2,3-diisopropyl succinate, diisopropyl 2,3-diisobutyl succinate; Di-n-butyl succinate, 2,3-dimethylsuccinate, 2,3-diethylsuccinate, 2,3-di-n-propylsuccinate, 2,3-diisopropylsuccinate, 2,3-diisobutylsuccinate, 2,3-diisobutylsuccinate; Diisobutyl succinate, 2,3-dimethylsuccinate, 2,3-diethylsuccinate, 2,3-di-n-propylsuccinate, 2,3-diisopropylsuccinate, 2,3-diisobutylsuccinate, 2,3-diisobutylsuccinate; 2,3-Diisopropyl-2-cyanosuccinate diethyl, 2,3-Diisopropyl-2-cyanosuccinate di-n-butyl, 2,3-Diisopropyl-2-cyanosuccinate di-n-butyl, 2,3-Diisopropyl-2-cyanosuccinate diisobutyl, 2,3-Dicyclopentyl-2-cyanosuccinate diethyl, 2,3-Dicyclopentyl-2-cyanosuccinate di-n-butyl, 2,3-Dicyclopentyl-2-cyanosuccinate diisobutyl, 2,3-Dicyclohexyl-2-cyanosuccinate diethyl, 2,3-Dicyclohexyl-2-cyanosuccinate di-n-butyl, 2,3-Dicyclohexyl-2-cyanosuccinate diisobutyl, 2-Cyclopentyl-3-cyclohexyl-2-cyanosuccinate diethyl, 2,3-Diisopropyl-2-cyanosuccinate 1-isobutyl 4-ethyl, 2,3-Diisopropyl-2-cyanosuccinate 1-n-butyl 4-ethyl, 2-Isopropyl-3-methyl-2-cyanosuccinate diethyl, 2 Examples include one or more compounds selected from diethyl-isopropyl-3-ethyl-2-cyanosuccinate, diethyl-2-isopropyl-3-n-propyl-2-cyanosuccinate, diethyl-2-isopropyl-3-butyl-2-cyanosuccinate, diethyl-2-isopropyl-3-phenyl-2-cyanosuccinate, diethyl-2-cyclohexyl-3-isopropyl-2-cyanosuccinate, and 1-ethyl-4-isobutyl-2-isopropyl-3-phenyl-2-cyanosuccinate. Among these succinate diesters, diethyl succinate, di-n-propyl succinate, di-n-butyl succinate, diisobutyl succinate, 2,3-di-n-propyl succinate diethyl, 2,3-diisopropyl succinate diethyl, 2,3-di-n-propyl succinate di-n-propyl, 2,3-diisopropyl succinate di-n-propyl, 2,3-diisopropyl succinate diisopropyl, 2,3-di-n-propyl succinate di-n-butyl succinate, 2,3-diisopropyl succinate di -n-butyl, diisobutyl 2,3-di-n-propylsuccinate, diisobutyl 2,3-diisopropylsuccinate, diethyl 2,3-diisopropyl-2-cyanosuccinate, 1-isobutyl 4-ethyl 2,3-diisopropyl-2-cyanosuccinate, diethyl 2-isopropyl-3-methyl-2-cyanosuccinate, diethyl 2-isopropyl-3-ethyl-2-cyanosuccinate, diethyl 2-cyclopentyl-3-isopropyl-2-cyanosuccinate, and di-n-butyl 2,3-diisopropyl-2-cyanosuccinate are preferably used.

[0047] Furthermore, the succinate diester compounds represented by the above general formula (1) may be used alone or in combination of two or more types.

[0048] The solid catalyst component for olefin polymerization containing a succinic diester compound and a phthalic diester compound contains, as an internal electron donor compound, the following general formula (2):

[0049]

[0050] (In the formula, R ７ represents an alkyl group having 1 to 8 carbon atoms or a halogen atom, R ８ and R ９ are alkyl groups having 1 to 12 carbon atoms, which may be the same or different, and the number n of the substituent R ７ is 0, 1 or 2. When n is 2, R ７ may be the same or different.) It contains one or more compounds selected from phthalic diester compounds represented by the formula. In the catalyst for olefin polymerization, since a phthalic diester compound represented by the general formula (2) exists as an internal electron donor compound, a high MFR can be obtained during polymerization, and it is preferable in that a polymer with high fluidity can be produced.

[0051] In the phthalic diester compound represented by the general formula (2), R ７ represents an alkyl group having 1 to 8 carbon atoms or a halogen atom. When R ７ is a halogen atom, examples of the halogen atom include one or more atoms selected from a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. When R ７ is an alkyl group having 1 to 8 carbon atoms, examples of the alkyl group having from 1 to 8 carbon atoms include one or more selected from a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a t-butyl group, an n-pentyl group, an isopentyl group, a neopentyl group, an n-hexyl group, an isohexyl group, a 2,2-dimethylbutyl group, a 2,2-dimethylpentyl group, an isooctyl group, and a 2,2-dimethylhexyl group. As R ７ , a methyl group, a bromine atom, and a fluorine atom are preferable, and a methyl group and a bromine atom are more preferable. In the phthalic diester compound represented by the general formula (2), R ８ and R ９is an alkyl group having 1 to 12 carbon atoms, which may be the same or different from each other. R ８ and R ９ Examples thereof include an ethyl group, an n-butyl group, an isobutyl group, a t-butyl group, a neopentyl group, an isohexyl group, and an isooctyl group, and it is preferably an ethyl group, an n-propyl group, an n-butyl group, an isobutyl group, or a neopentyl group. In the phthalic acid diester compound represented by the general formula (2), n is the number of the substituent R ７ and is 1 or 2. When n is 1, R ７ is an alkyl group, and when n is 2, R ７ may be the same or different, but at least one of them is an alkyl group.

[0052] In solid catalyst components for olefin polymerization containing succinate diester compounds and phthalate diester compounds, the phthalate diester compound represented by general formula (2) is not particularly limited, and examples include dimethyl phthalate, diethyl phthalate, di-n-propyl phthalate, diisopropyl phthalate, di-n-butyl phthalate, diisobutyl phthalate, di-n-pentyl phthalate, diisopentyl phthalate, dineopentyl phthalate, di-n-hexyl phthalate, ditexyl phthalate, methyl ethyl phthalate, ethyl (ethyl) n-propyl phthalate, ethyl isopropyl phthalate, ethyl (ethyl) n-butyl phthalate, ethyl isobutyl phthalate, ethyl (ethyl) n-pentyl phthalate, ethyl isopentyl phthalate, and ethyl phthalate. Examples include phthalate diesters such as opentyl and ethyl (ethyl) n-hexyl phthalate, halogen-substituted phthalate diesters such as diethyl 4-chlorophthalate, di-n-propyl 4-chlorophthalate, diisopropyl 4-chlorophthalate, di-n-butyl 4-chlorophthalate, diisobutyl 4-chlorophthalate, diethyl 4-bromophthalate, di-n-propyl 4-bromophthalate, diisopropyl 4-bromophthalate, di-n-butyl 4-bromophthalate, and diisobutyl 4-bromophthalate, as well as alkyl-substituted phthalate diesters such as diethyl 4-methylphthalate, di-n-propyl 4-methylphthalate, diisopropyl 4-methylphthalate, di-n-butyl 4-methylphthalate, or diisobutyl 4-methylphthalate.

[0053] Furthermore, the phthalate diester compounds represented by the above general formula (2) may be used alone or in combination of two or more types.

[0054] Furthermore, the succinate diester compounds represented by general formula (1) and the phthalate diester compounds represented by general formula (2) may be used individually or in combination of two or more.

[0055] Solid catalyst components for olefin polymerization containing succinate diester compounds and phthalate diester compounds contain succinate diester compounds represented by general formula (1) and phthalate diester compounds represented by general formula (2) as essential internal electron-donating compounds, but may also contain other internal electron-donating compounds (hereinafter referred to as "other internal electron-donating compounds" as appropriate).

[0056] Other internally electron-donating compounds include one or more compounds selected from carbonates, acid halides, acid amides, nitriles, acid anhydrides, and carboxylic acid esters.

[0057] Examples of other internally electron-donating compounds include one or more selected from ether carbonate compounds, cycloalkane dicarboxylic acid diesters, cycloalkene dicarboxylic acid diesters, alkyl-substituted malonic acid diesters, maleic acid diesters, and other carboxylic acid diesters. More specifically, ether carbonate compounds such as (2-ethoxyethyl)methyl carbonate, (2-ethoxyethyl)ethyl carbonate, and (2-ethoxyethyl)phenyl carbonate, and cycloalkane dicarboxylic acid diesters such as 1,2-dicarboxylic acid dimethyl, and one or more compounds selected from these are preferred.

[0058] In solid catalyst components for olefin polymerization containing succinate diester compounds and phthalate diester compounds, the content of the succinate diester compound represented by general formula (1) in the total amount of components, when calculated on a solid content basis, is 8.0 to 24.0% by mass, preferably 12.0 to 22.0% by mass, and more preferably 14.0 to 20.0% by mass. When the content of the succinate diester compound represented by general formula (1) in the total amount of components, when calculated on a solid content basis, is within the above range, the molecular weight distribution of the olefin polymer can be broadened and the rigidity can be increased during olefin polymerization. On the other hand, if the content of the succinate diester compound represented by general formula (1) in the total amount of components, when calculated on a solid content basis, is less than the above range, the molecular weight distribution will not be sufficiently broad, and if it exceeds the above range, the polymerization activity will be low.

[0059] In solid catalyst components for olefin polymerization containing succinate diester compounds and phthalate diester compounds, the content of the phthalate diester compound represented by general formula (2) in the total amount of components, when calculated on a solid content basis, is 8.0 to 24.0% by mass, preferably 12.0 to 22.0% by mass, and more preferably 14.0 to 20.0% by mass. When the content of the phthalate diester compound represented by general formula (2) in the total amount of components, when calculated on a solid content basis, is within the above range, the molecular weight distribution of the olefin polymer can be broadened and the rigidity can be increased during olefin polymerization. On the other hand, if the content of the phthalate diester compound represented by general formula (2) in the total amount of components, when calculated on a solid content basis, is less than the above range, the molecular weight distribution will not be sufficiently broad, and if it exceeds the above range, the polymerization activity will be low.

[0060] In solid catalyst components for olefin polymerization containing succinate diester compounds and phthalate diester compounds, the titanium atom content in the total amount of components, when calculated on a solid content basis, is 2.0 to 6.0% by mass, preferably 2.5 to 5.0% by mass, and more preferably 3.0 to 4.5% by mass.

[0061] In solid catalyst components for olefin polymerization containing succinate diester compounds and phthalate diester compounds, the halogen atom content in the total amount of components, when calculated on a solid content basis, is 50.0 to 70.0% by mass, preferably 55.0 to 68.0% by mass, and more preferably 58.0 to 67.0% by mass.

[0062] In solid catalyst components for olefin polymerization containing succinate diester compounds and phthalate diester compounds, the magnesium atom content in the total amount of components, when calculated on a solid content basis, is 15.0 to 25.0% by mass, preferably 16.0 to 23.0% by mass, and more preferably 16.0 to 22.0% by mass.

[0063] The solid catalyst component for olefin polymerization containing succinate diester compounds and phthalate diester compounds is preferably prepared by contacting the above-mentioned dialkoxymagnesium, titanium halogen compound, succinate diester compound represented by general formula (1), and phthalate diester compound represented by general formula (2) in the presence of an inert organic solvent.

[0064] In the present invention, the above inert organic solvent is preferably one that dissolves titanium halogen compounds but does not dissolve dialkoxymagnesium. Specifically, one or more solvents can be 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 orthodichlorobenzene, methylene chloride, 1,2-dichlorobenzene, carbon tetrachloride, and dichloroethane. The above inert organic solvent is preferably a saturated hydrocarbon compound or aromatic hydrocarbon compound that is liquid at room temperature and has a boiling point of about 50 to 200°C. Among these, one or more solvents selected from hexane, heptane, octane, ethylcyclohexane, mineral oil, toluene, xylene, and ethylbenzene are preferred, and one or more solvents selected from hexane, heptane, ethylcyclohexane, and toluene are particularly preferred.

[0065] In this application, the titanium content in the solid catalyst component for olefin polymerization refers to the value measured according to the method (redox titration) described in JIS 8311-1997 "Method for determining titanium in titanium ore".

[0066] Furthermore, in this application, the magnesium content in the solid catalyst component for olefin polymerization refers to the value measured by the 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.

[0067] Furthermore, in this application, the halogen content in the solid catalyst component for olefin polymerization refers to the value measured by a silver nitrate titration method, in which the solid catalyst component is treated with a mixed solution of sulfuric acid and pure water to make an aqueous solution, a predetermined amount is taken, and the halogen is titrated with a silver nitrate standard solution.

[0068] Furthermore, in this application, the content of succinate diester compounds and phthalate diester compounds contained in the solid catalyst component for olefin polymerization, as well as the content of other internally electron-donating compounds added as needed, refers to the values ​​obtained by hydrolyzing the solid catalyst component for olefin polymerization, extracting the succinate diester compounds, phthalate diester compounds, and other internally electron-donating compounds added as needed using an aromatic solvent, and measuring this solution by gas chromatography-FID (Flame Ionization Detector).

[0069] Solid catalyst components for olefin polymerization containing succinate diester compounds and phthalate diester compounds can be suitably produced by the method for producing solid catalyst components for olefin polymerization containing succinate diester compounds and phthalate diester compounds described below.

[0070] Next, a method for producing solid catalyst components for olefin polymerization containing succinate diester compounds and phthalate diester compounds will be described.

[0071] A method for producing solid catalyst components for olefin polymerization containing succinate diester compounds and phthalate diester compounds involves contacting and reacting a raw material component that serves as a source of magnesium, a raw material component that serves as a source of titanium and halogen with an internally electron-donating compound, such as a succinate diester compound and a phthalate diester compound, in an organic solvent to obtain solid catalyst components for olefin polymerization containing succinate diester compounds and phthalate diester compounds. Specifically, a method involves using dialkoxymagnesium as the raw material component that serves as the source of magnesium, and a tetravalent titanium halogen compound as the raw material component that serves as the source of titanium and halogen, and contacting these raw materials with an internally electron-donating compound containing a succinate diester compound represented by general formula (1) and an internally electron-donating compound containing a phthalate diester compound represented by general formula (2), respectively, to obtain solid catalyst components for olefin polymerization containing succinate diester compounds and phthalate diester compounds.

[0072] The contact of the above components is preferably carried out in an inert gas atmosphere, with moisture removed, in a container equipped with a stirrer, while stirring. The temperature at which the above components are brought into contact is preferably around room temperature when simply bringing the components into contact and stirring to mix them, or when dispersing or suspending them for modification treatment, but it is preferably in a relatively low temperature range, preferably in the range of -20 to 30°C. Furthermore, when a solid product is obtained by reacting the components at a high temperature while they are in contact, it is preferably a relatively high temperature range, preferably in the range of 40 to 130°C. If the reaction temperature is below 40°C, the reaction will not proceed sufficiently, and as a result the performance of the prepared solid catalyst component will be insufficient, and if it exceeds 130°C, evaporation of the solvent used will become significant, making it difficult to control the reaction. The reaction time after contact is preferably 1 minute or more, more preferably 10 minutes or more, and even more preferably 30 minutes or more.

[0073] The following provides a more specific example of the order in which each component is brought into contact when producing a solid catalyst component for the polymerization of olefins containing succinate diester compounds and phthalate diester compounds. (1) Magnesium compound → internally electron-donating compound → inert organic solvent → tetravalent titanium halogen compound → (intermediate cleaning → inert organic solvent → tetravalent halogen compound) → final cleaning (2) Magnesium compound → inert organic solvent → internally electron-donating compound → tetravalent halogen compound → (intermediate cleaning → inert organic solvent → tetravalent titanium halogen compound) → final cleaning (3) Magnesium compound → tetravalent halogen compound → inert organic solvent → internally electron-donating compound → (intermediate cleaning → inert organic solvent → internally electron-donating compound → tetravalent titanium halogen compound) → final cleaning (4) Magnesium compound → tetravalent titanium halogen compound → inert organic solvent → internally electron-donating compound → (intermediate cleaning → inert organic solvent → tetravalent titanium halogen compound → internally electron-donating compound) → final cleaning (5) Magnesium compound → tetravalent halogen compound → inert organic solvent → internally electron-donating compound → (intermediate cleaning → inert organic solvent → internally electron-donating compound → tetravalent titanium halogen compound) → final cleaning (6) Magnesium compound → inert organic solvent → tetravalent titanium halogen compound → internal electron-donating compound → (intermediate washing → inert organic solvent → tetravalent titanium halogen compound → internal electron-donating compound) → final washing (7) Magnesium compound → inert organic solvent → internal electron-donating compound → tetravalent titanium halogen compound → (intermediate washing → internal electron-donating compound → inert organic solvent → tetravalent titanium halogen compound) → final washing(8) Magnesium compound → inert organic solvent → internally electron-donating compound → tetravalent titanium halogen compound → [intermediate washing → internally electron-donating compound → inert organic solvent → tetravalent titanium halogen compound] → final washing In the method for producing solid catalyst components for polymerization of olefins containing succinate diester compounds and phthalate diester compounds, the order of contact between the succinate diester compound represented by general formula (1) and the phthalate diester compound represented by general formula (2), which are internally electron-donating compounds, is not particularly limited. The succinate diester compound represented by general formula (1) may be contacted first, the phthalate diester compound represented by general formula (2) may be contacted first, or they may be contacted simultaneously. However, as the conversion of dialkoxymagnesium to magnesium chloride by the titanium halogen compound progresses, it becomes more difficult for the succinate diester compound represented by general formula (1) to be supported on the solid catalyst component. Therefore, it is preferable to contact the succinate diester compound represented by general formula (1) first, followed by the phthalate diester compound represented by general formula (2).

[0074] In the above contact examples (1) to (8), "→" indicates the order of contact. For example, "magnesium compound → internal electron-donating compound" means that the magnesium compound and the internal electron-donating compound are brought into contact in this order. In addition, in the above contact examples (1) to (8), the steps enclosed in double brackets (《 》) indicate steps that can be repeated multiple times as needed, and the activity is further improved by repeating the steps enclosed in double brackets. The tetravalent halogen compound and inert organic solvent used in the steps enclosed in double brackets may be newly added or may be residues from the previous step. When adding a tetravalent titanium halogen compound, the tetravalent titanium halogen compound used in the step enclosed in double brackets may be newly added or may be residues of the tetravalent halogen compound from the previous step. In the above contact examples (1) to (8), it is preferable to perform the intermediate and final washing using a hydrocarbon compound that is liquid at room temperature, and it is preferable to wash the products obtained at each contact stage in steps other than the intermediate and final washing steps shown in the above contact examples (1) to (8).

[0075] A particularly preferred preparation method for producing solid catalyst components for olefin polymerization containing succinate diester compounds and phthalate diester compounds is the method described in (2), (4), and (6) above, namely, a method in which dialkoxymagnesium, a magnesium compound, is suspended in an inert organic solvent such as toluene, heptane, or cyclohexane, and then titanium tetrachloride, a tetravalent titanium halogen compound, is added to the resulting suspension and brought into contact with it, and before or after contact with the suspension of the tetravalent titanium halogen compound, one or more succinate diester compounds and phthalate diester compounds, which are internal electron-donating compounds, are brought into contact with the suspension at -20 to 130°C and reacted. In this case, it is desirable to carry out the aging reaction at a low temperature before or after contact with the suspension of the internal electron-donating compound.

[0076] The solid obtained in this way may, if necessary, be washed with a liquid hydrocarbon compound at room temperature (pre-washing), then contacted with a tetravalent titanium halogen compound in the presence of the hydrocarbon compound, and the reaction treatment may be carried out at 40 to 130°C. The resulting reactant may then be washed with a liquid hydrocarbon compound at room temperature (post-washing) to obtain the desired solid catalyst component for olefin polymerization. The above pre-washing and reaction between the pre-washed product and the tetravalent titanium halogen compound may be repeated multiple times.

[0077] The preferred conditions for the above processing or washing are as follows: <Conditions for low-temperature aging reaction before or after contact with internally electronegative compounds> The low-temperature aging temperature is preferably -20 to 70°C, more preferably -10 to 50°C, and even more preferably -5 to 30°C. The low-temperature aging time is preferably 1 minute to 6 hours, more preferably 5 minutes to 4 hours, and even more preferably 10 minutes to 3 hours.

[0078] <Reaction conditions in the step before intermediate washing> In the step before intermediate washing, the reaction temperature of the magnesium compound, internal electron-donating compound, and tetravalent titanium halogen compound in the inert organic solvent is preferably 0 to 130°C, more preferably 40 to 120°C, and even more preferably 50 to 115°C. The reaction time is preferably 0.5 to 6 hours, more preferably 0.5 to 5 hours, and even more preferably 1 to 4 hours.

[0079] <Cleaning conditions during intermediate and final cleaning> The cleaning temperature is preferably 0 to 110°C, more preferably 30 to 100°C, and even more preferably 30 to 90°C. The number of cleaning cycles is preferably 1 to 20, more preferably 1 to 15, and even more preferably 1 to 10. The hydrocarbon compounds used in the intermediate and final cleaning cycles that are liquid at room temperature are preferably aromatic hydrocarbon compounds or saturated hydrocarbon compounds that are liquid at room temperature (20°C). Specifically, aromatic hydrocarbon compounds include toluene, xylene, and ethylbenzene, and saturated hydrocarbon compounds include hexane, heptane, cyclohexane, and methylcyclohexane. Preferably, aromatic hydrocarbon compounds are used in the intermediate cleaning cycle, and saturated hydrocarbon compounds are used in the final cleaning cycle.

[0080] The ratio of each component used in the production of solid catalyst components for olefin polymerization containing succinate diester compounds and phthalate diester compounds varies depending on the preparation method and cannot be specified in general terms. For example, per mole of magnesium compound, the total number of moles of succinate diester compound represented by general formula (1) and phthalate diester compound represented by general formula (2) is preferably 0.01 to 1 mole, more preferably 0.01 to 1 mole, and even more preferably 0.02 to 0.6 moles; the tetravalent titanium halogen compound is preferably 0.5 to 100 moles, more preferably 0.5 to 50 moles, and even more preferably 1 to 10 moles; and the inert organic solvent is preferably 0.001 to 500 moles, more preferably 0.001 to 100 moles, and particularly preferably 0.005 to 10 moles.

[0081] In addition, in the above preparation method, other internally electron-donating compounds may be used in combination with the succinic acid diester compound represented by general formula (1) and the phthalic acid diester compound represented by general formula (2). Furthermore, the above contact may be carried out in the presence of other reaction reagents or surfactants, such as silicon, phosphorus, or aluminum.

[0082] In the method for producing solid catalyst components for olefin polymerization containing succinate diester compounds and phthalate diester compounds, preferred embodiments of the obtained solid catalyst components for olefin polymerization containing succinate diester compounds and phthalate diester compounds are as described in detail in the description of solid catalyst components for olefin polymerization containing succinate diester compounds and phthalate diester compounds.

[0083] In the olefin polymerization catalyst of the present invention, the mass ratio (S / P) of the content of the succinate diester compound represented by general formula (1) to the content (P) of the phthalate diester compound represented by general formula (2) in the solid catalyst component for olefin polymerization containing the succinate diester compound and the phthalate diester compound is preferably 1 / 99 to 50 / 50, and more preferably 5 / 95 to 40 / 60. By having the mass ratio (S / P) within the above range, polymers with high rigidity can be polymerized.

[0084] The olefin polymerization catalyst of the present invention contains (II) an organoaluminum compound.

[0085] In the olefin polymerization catalyst of the present invention, (II) the organoaluminum compound is general formula (6): R １９ ｑ AlQ ３－ｑ (6) (wherein, R １９ is an alkyl group having 1 to 6 carbon atoms, Q is a hydrogen atom or a halogen atom, q is 0 < q ≤ 3, and R １９ If there are multiple R １９ The elements Q may be the same or different from each other, and if there are multiple Qs, each Q may be the same or different from each other. ) This is an organoaluminum compound represented by .

[0086] In the organoaluminum compound represented by general formula (6), q is 0 < q ≤ 3, and specifically, q can be 1, 2, or 3.

[0087] Specific examples of such (II) organoaluminum compounds include one or more compounds selected from trialkylaluminum such as triethylaluminum, triisopropylaluminum, tri-n-butylaluminum, tri-n-hexylaluminum, and triisobutylaluminum; alkylaluminum halides such as diethylaluminum chloride and diethylaluminum bromide; and diethylaluminum hydrides. Preferably, one or more compounds selected from alkylaluminum halides such as diethylaluminum chloride, trialkylaluminum such as triethylaluminum, tri-n-butylaluminum, and triisobutylaluminum are used, and more preferably, one or more compounds selected from triethylaluminum and triisobutylaluminum are used.

[0088] The olefin polymerization catalyst of the present invention contains, as (III) external electron-donating compounds, at least an alkoxysilane compound represented by general formula (3) and an (alkylamino)alkylsilane compound represented by general formula (4).

[0089] The catalyst for olefin polymerization of the present invention is an external electron-donating compound, and is defined by the following general formula (3): Si(OR １０ ) ( OR １１ ) ( OR １２ ) ( OR １３ ) (3) (wherein, R １０ , R １１ , R １２ and R １３ It contains one or more compounds selected from alkoxysilane compounds represented by (where (1 to 8) is a linear alkyl group or a branched alkyl group having 3 to 8 carbon atoms, and they may be the same or different from each other).

[0090] In an alkoxysilane compound represented by general formula (3), R １０ , R １１ , R １２ and R １３ R is a linear alkyl group or branched alkyl group having 1 to 8 carbon atoms, preferably 1 to 4 carbon atoms, and may be the same or different from each other. １０ , R１１ , R １２ and R １３ When the group is a linear alkyl group having 1 to 4 carbon atoms or a branched alkyl group, specific examples include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, or an isobutyl group.

[0091] The alkoxysilane compound represented by general formula (3) is not particularly limited, and examples include tetramethoxysilane, tetraethoxysilane, tetra-n-propoxysilane, and tetraisopropoxysilane, among which tetraethoxysilane and tetra-n-propoxysilane are preferred.

[0092] The catalyst for olefin polymerization of the present invention is an external electron-donating compound, and is defined by the following general formula (4): R １４ R １５ Si (NHR １６ ) (NHR １７ ) (4) (wherein, R １４ and R １５ R is a linear alkyl group having 1 to 8 carbon atoms, a branched alkyl group having 3 to 12 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms, a cycloalkenyl group having 3 to 12 carbon atoms, or an aromatic hydrocarbon group having 6 to 20 carbon atoms, and they may be the same or different from each other. １６ and R １７ It contains one or more compounds selected from (alkylamino)alkylsilane compounds represented by (wherein C1 is a straight-chain alkyl group having 1 to 8 carbon atoms, and they may be the same or different from each other).

[0093] In an (alkylamino)alkylsilane compound represented by general formula (4), R １４ and R １５ R is a linear alkyl group having 1 to 8 carbon atoms, a branched alkyl group having 3 to 12 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms, a cycloalkenyl group having 3 to 12 carbon atoms, or an aromatic hydrocarbon group having 6 to 20 carbon atoms, preferably a linear alkyl group having 1 to 6 carbon atoms, a branched alkyl group having 3 to 8 carbon atoms, or a cycloalkyl group having 3 to 8 carbon atoms, and may be the same as or different from each other. １４ and R １５Examples include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, neopentyl group, cyclopentyl group, n-hexyl group, cyclohexyl group, and 2-ethylhexyl group. In the (alkylamino)alkylsilane compound represented by general formula (4), R １６ and R １７ R is an alkyl group having 1 to 8 carbon atoms, preferably a linear alkyl group having 1 to 6 carbon atoms or a branched alkyl group having 3 to 6 carbon atoms, and may be the same or different from each other. １６ and R １７ Examples include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, n-pentyl group, neopentyl group, n-hexyl group, and cyclohexyl group.

[0094] Examples of (alkylamino)alkylsilane compounds represented by general formula (4) include diisopropylbis(ethylamino)silane, dicyclopentylbis(ethylamino)silane, dicyclohexylbis(ethylamino)silane, cyclohexylmethylbis(ethylamino)silane, and cyclohexylcyclopentylbis(ethylamino)silane.

[0095] In the olefin polymerization catalyst of the present invention, the molar ratio (Y / X) of the content (Y) of the (alkylamino)alkylsilane compound represented by general formula (4) to the content (X) of the alkoxysilane compound represented by general formula (3) is preferably 1 / 99 to 50 / 50, more preferably 10 / 90 to 30 / 70.

[0096] The olefin polymerization catalyst of the present invention comprises (I) a solid catalyst component for olefin polymerization containing a succinic acid diester compound and a phthalic acid diester compound, (II) an organoaluminum compound, and (III) an external electron-donating compound, at least an alkoxysilane compound represented by general formula (3) and an (alkylamino)alkylsilane compound represented by general formula (4), i.e., a contact thereof. The olefin polymerization catalyst of the present invention may be prepared by contacting (I) a solid catalyst component for olefin polymerization containing a succinic acid diester compound and a phthalic acid diester compound, (II) an organoaluminum compound, and (III) an external electron-donating compound, an alkoxysilane compound represented by general formula (3) and an (alkylamino)alkylsilane compound represented by general formula (4), in the absence of olefins, or, as described later, by contacting them in the presence of olefins (within the polymerization system).

[0097] In the olefin polymerization catalyst of the present invention, the content ratio of each component is arbitrary as long as it does not affect the effects of the present invention, and is not particularly limited. However, it is generally preferable that the (II) organoaluminum compound is contained in an amount of 1 to 2,000 moles, and more preferably 50 to 1,000 moles, per total mole of titanium atoms in the (I) succinic acid diester compound and phthalic acid diester compound-containing solid catalyst component for olefin polymerization. Furthermore, the olefin polymerization catalyst of the present invention is preferably contained 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, in a total of moles, of the (III) external electron-donating compounds, which are alkoxysilane compounds represented by general formula (3) and (alkylamino)alkylsilane compounds represented by general formula (4).

[0098] The inventors of the present invention have found that a solid catalyst component for olefin polymerization that uses a succinate diester compound alone as an internal electron-donating compound yields polymers with high rigidity (FM), but requires a large amount of hydrogen to achieve high melt flow rate (MFR). This increased hydrogen usage generates low molecular weight polymer components, which worsen the dispersibility of the ethylene propylene rubber component, resulting in low impact resistance (IZOD).

[0099] The inventors have further discovered that when polymerizing olefins, by using a solid catalyst component for olefin polymerization that uses a succinate diester compound alone as an internal electron-donating compound, in combination with a solid catalyst component for olefin polymerization that uses a phthalate diester compound alone as an internal electron-donating compound, and by using an alkoxysilane compound represented by general formula (3) as an external electron-donating compound, polymers with high melt flow rate (MFR) can be obtained even with a small amount of hydrogen used. Based on this finding, the inventors have now discovered that by using a succinate diester compound and a phthalate diester compound in combination as internal electron-donating compounds in the solid catalyst component for olefin polymerization that constitutes the catalyst for olefin polymerization, it is possible to moderately increase the melt flow rate (MFR) of the resulting olefin polymer, broaden the molecular weight distribution of the olefin polymer, and generate polymer components with very large molecular weights, thereby enabling the acquisition of polymers with high melt flow rate (MFR) while increasing the rigidity (FM) of the olefin polymer. Furthermore, in the olefin polymerization catalyst of the present invention, in addition to using such solid catalyst components for olefin polymerization, a (alkylamino)alkylsilane compound represented by general formula (4), which is characterized by reducing xylene-soluble components (XS) in the polymer while maintaining high levels of polymerization activity and hydrogen responsiveness during olefin polymerization, and an alkoxysilane compound represented by general formula (3) are combined as external electron-donating compounds constituting the olefin polymerization catalyst. As a result, olefin polymers with high melt flow rate (MFR) can be obtained even with reduced hydrogen usage. Therefore, by using the olefin polymerization catalyst of the present invention in the production of olefin polymers, olefin polymers having the melt flow rate (MFR) necessary for molding can be produced with less hydrogen usage than conventional methods, thereby reducing the generation of low molecular weight polymer components. This is thought to improve the dispersibility of the ethylene propylene rubber component, and when compared under similar polymerization conditions, polymers with high rigidity (FM) and high impact resistance (IZOD) can be obtained.

[0100] The present invention provides a method for producing olefin polymers, characterized by performing polymerization of olefins using the olefin polymerization catalyst of the present invention, for example, the olefin polymerization catalyst of the present invention.

[0101] In the method for producing olefin polymers of the present invention, the polymerization of olefins may be homopolymerization or copolymerization. In the method for producing olefin polymers of the present invention, the olefins used for polymerization may be one or more selected from ethylene, propylene, 1-butene, 1-pentene, 4-methyl-1-pentene, vinylcyclohexane, etc., and among these, ethylene and propylene are preferred as olefins for polymerization.

[0102] When the olefin polymerization catalyst of the present invention is prepared in the presence of olefins (within the polymerization system), the ratio of each component used is arbitrary and not particularly limited, as long as it does not affect the effects of the present invention. However, it is generally preferable to contact the above-mentioned (II) organoaluminum compound at a rate of 1 to 2,000 moles per mole of total titanium atoms in the above-mentioned (I) solid catalyst component for olefin polymerization, and more preferably 50 to 1,000 moles. Furthermore, it is preferable to contact the above-mentioned (III) external electron-donating compound at a rate of 0.002 to 10,000 moles per mole of the above-mentioned (II) organoaluminum compound, more preferably 0.010 to 2,000 moles, and even more preferably 0.010 to 0.500 moles.

[0103] The order in which the components constituting the olefin polymerization catalyst of the present invention come into contact is arbitrary, but it is preferable to first charge (II) the organoaluminum compound into the polymerization system, then charge (III) the external electron-donating compound and bring them into contact, and then charge (I) the solid catalyst component for olefin polymerization and bring them into contact.

[0104] The method for producing olefin polymers of the present invention may be carried out in or without the presence of an organic solvent. Furthermore, olefin monomers such as propylene can be used in either gaseous or liquid form. 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. In addition, 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 step or in two or more steps.

[0105] In addition, when polymerizing olefins using the olefin polymerization catalyst of the present invention (also referred to as the main polymerization), it is preferable to perform prepolymerization prior to the main polymerization in order to further improve the catalytic activity, stereoregularity, and particle properties of the resulting polymer. In prepolymerization, the same olefins or monomers such as styrene as those used in the main polymerization can be used.

[0106] When performing prepolymerization, the order in which the components and monomers (olefins) constituting the olefin polymerization catalyst of the present invention come into contact is arbitrary, but preferably, in a prepolymerization system set up in an inert gas atmosphere or an olefin gas atmosphere, (II) an organoaluminum compound is first charged in, then (III) an external electron-donating compound is charged and brought into contact, then (I) a solid catalyst component for olefin polymerization is charged and brought into contact, and then a mixture of one or more olefins such as propylene and other olefins is brought into contact.

[0107] In the method for producing olefin polymers of the present invention, the polymerization methods include slurry polymerization using an inert hydrocarbon compound solvent such as cyclohexane or heptane, bulk polymerization using a solvent such as liquefied propylene, and gas-phase polymerization using substantially no solvent, with bulk polymerization or gas-phase polymerization being preferred.

[0108] When copolymerizing propylene with monomers of other α-olefins, there are two main types: random copolymerization, in which propylene and a small amount of ethylene are used as comonomers and polymerization is carried out in one step; and so-called propylene-ethylene block copolymerization, in which propylene is homopolymerized in the first step (first polymerization tank), and copolymerization of propylene with other α-olefins such as ethylene is carried out in the second step (second polymerization tank) or more (multi-stage polymerization tank). Block copolymerization of propylene with other α-olefins is preferred.

[0109] A block copolymer obtained by block copolymerization is a polymer containing segments in which the monomer composition of two or more monomers changes continuously. It refers to a form in which two or more polymer chains (segments) with different primary structures, such as monomer species, comonomer species, comonomer composition, comonomer content, comonomer arrangement, and stereoregularity, are linked together in a single molecular chain.

[0110] In the method for producing olefin polymers of the present invention, the block copolymerization reaction between propylene and other α-olefins can usually be carried out in the presence of an olefin polymerization catalyst (A) by first contacting propylene alone or propylene with a small amount of α-olefin (such as ethylene) in the preceding step, and then contacting propylene with α-olefin (such as ethylene) in the subsequent step. The polymerization reaction in the preceding step may be repeated multiple times, or the polymerization reaction in the subsequent step may be repeated multiple times to carry out a multi-stage reaction.

[0111] In the block copolymerization reaction between propylene and other α-olefins, it is preferable to perform polymerization in the first stage by adjusting the polymerization temperature and time so that the proportion of the polypropylene portion (in the final copolymer) is 20 to 90% by mass, and then in the second stage, introduce propylene and ethylene or other α-olefins so that the proportion of the rubber portion (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 even more preferably 75 to 80°C. 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 above copolymerization reaction, either a continuous polymerization method or a batch polymerization method can be used, and the polymerization reaction may be carried out in one stage or in two or more stages. Furthermore, the polymerization time (residence time in the reactor) is preferably 1 minute to 5 hours at each polymerization stage in the preceding or succeeding stages, or even in continuous polymerization. Examples of polymerization methods include slurry polymerization using inert hydrocarbon compounds such as cyclohexane and heptane as solvents, bulk polymerization using solvents such as liquefied propylene, and gas-phase polymerization using substantially no solvent. Bulk polymerization or gas-phase polymerization is preferred.

[0112] In the method for producing olefin polymers of the present invention, hydrogen gas and olefins are supplied in a ratio such that the melt flow rate (MFR) of the propylene polymer obtained in homopolymerization is 350 g / 10 min or less. By supplying hydrogen gas and olefins in such a ratio, an olefin polymer with an appropriate melt flow rate (MFR) can be obtained.

[0113] The melt flow rate (MFR) of the olefin homopolymer obtained by the method for producing olefin polymers of the present invention is appropriately selected depending on the application, but for example, it is 0.1 to 1000 g / 10 minutes, preferably 10 to 500 g / 10 minutes, and more preferably 50 to 350 g / 10 minutes.

[0114] In this application, the melt flow rate (MFR) refers to the value measured according to ASTM D 1238 and JIS K 7210.

[0115] Next, the present invention will be described in more detail with reference to examples, but these are merely illustrative and not intended to limit the present invention.

[0116] (Production Example 1) Synthesis of Solid Catalyst Component (I) for Olefin Polymerization Containing Succinate Diester Compound and Phthalate Diester Compound A solid catalyst component for olefin polymerization was prepared by the following method using diethyl diisopropylsuccinate, a succinate diester compound, and dibutyl phthalate, a phthalate diester compound, in combination as internal electron-donating compounds. (i) A 500 ml flask equipped with a stirring device and thoroughly purged with nitrogen gas was filled with 20 ml of titanium tetrachloride (182.4 mmol) and 40 ml of toluene to form a mixed solution. (ii) Next, a suspension formed using 10.0 g (87.2 mmol) of diethoxymagnesium, 45 ml of toluene, and 2.4 ml (9.0 mmol) of dibutyl phthalate was added to the mixed solution, which was maintained at a liquid temperature of -6°C. (iii) The initial contact solution was heated, and 1.2 mL (2.2 mmol) of diethyl diisopropylsuccinate was added at 60°C during the heating process. The temperature was then raised further to 100°C, and the mixture was reacted for 90 minutes while maintaining this temperature. After the reaction was complete, the supernatant was removed, and the first contact product, which was the reaction product, was washed four times with 85 mL of toluene at 100°C. (iv) Next, 84 mL of toluene and 16 mL (145.6 mmol) of titanium tetrachloride were added to the first contact product, and the temperature was raised to 110°C. The mixture was reacted for 120 minutes. After the reaction was complete, the supernatant was removed. This process was repeated three times to obtain the final contact product. Subsequently, the obtained final contact product was washed eight times with 70 mL of n-heptane at 40°C, and the solid and liquid were separated to obtain a solid catalyst component (solid catalyst component (I) for polymerization of olefins containing succinic acid diester compound and phthalic acid diester compound). The solid-liquid components obtained were separated, and the titanium content, dibutyl phthalate, and succinate diester compound (ID) content in the obtained solid was measured to be 1.81% by mass, 12.9% by mass, and 4.3% by mass, respectively. The properties of the obtained solid catalyst component (I) are shown in Table 1.

[0117] The titanium content in the solid catalyst component, the content of diethyl diisopropyl succinate (which corresponds to the succinate diester compound that is an internally electron-donating compound), and the content of dibutyl phthalate (as a phthalate diester compound), as well as their physical properties, were measured using the method described below.

[0118] <Titanium content in solid catalyst components> The titanium content in the solid catalyst components was measured according to the method of JIS 8311-1997.

[0119] <Content of Internally Electron-Donating Compounds> The content of internally electron-donating compounds was determined by measuring using gas chromatography (Shimadzu Corporation, GC-2014) under the following conditions. The number of moles of internally electron-donating compounds was determined from the gas chromatography 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-1 ms, GL Sciences Co., Ltd.) Detector: FID (Flame Ionization Detector) Carrier gas: Helium, flow rate 7.0 ml / min Measurement temperature: Vaporization chamber 280°C, column 170°C, detector 280°C

[0120] (Production Example 2) Synthesis of Solid Catalyst Component (a) for Olefin Polymerization Containing a Succinate Diester Compound As an internal electron-donating compound, diethyl diisopropylsuccinate, a succinate 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 stirring device and thoroughly purged with nitrogen gas was filled with 60 ml of titanium tetrachloride (545.8 mmol) and 75 ml of toluene to form a mixed solution. (ii) Next, a suspension formed using 30.0 g (262.2 mmol) of diethoxymagnesium, 90 ml of toluene, and 4.5 ml (16.8 mmol) of diisopropylsuccinate was added to the mixed solution, which was maintained at a liquid temperature of -6°C. (iii) The initial contact solution was heated, and 4.5 mL (16.8 mmol) of diethyl diisopropylsuccinate was added at 60°C during the heating process. The temperature was then raised further to 100°C, and the reaction was maintained at this temperature for 90 minutes. After the reaction was complete, the supernatant was removed, and the first contact product, which was the reaction product, was washed four times with 225 mL of toluene at 90°C. (iv) Next, 150 mL of toluene and 30 mL (272.9 mmol) of titanium tetrachloride were added to the first contact product, and the temperature was raised to 115°C and the reaction was carried out for 60 minutes. After the reaction was complete, the supernatant was removed, and this procedure was repeated three times to obtain the final contact product. Subsequently, the obtained final contact product was washed six times with 225 mL of n-heptane at 40°C, and the solid and liquid were separated to obtain a solid catalyst component (solid catalyst component for polymerization of olefins containing succinic acid diester compound (a)). The solid-liquid components obtained were separated, and the titanium content and succinate diester compound (ID) content in the obtained solid were measured to be 3.08% by mass and 19.8% by mass, respectively.

[0121] (Production Example 3) Synthesis of Solid Catalyst Component (b) for Polymerization of Olefins Containing Phthalate Diester Di-n-butyl phthalate, a phthalate diester compound, was used as the internal electron-donating compound, and a solid catalyst component for polymerization of olefins was prepared by the following method. (i) A 500 ml flask equipped with a stirring device and thoroughly purged with nitrogen gas was filled with 105 ml (952.0 mmol) of titanium tetrachloride and 75 ml of toluene to form a mixed solution. (ii) Next, a suspension formed using 30.0 g (262.2 mmol) of diethoxymagnesium, 135 ml of toluene, and 9.2 ml (39.5 mmol) of di-n-butyl phthalate was added to the mixed solution, which was maintained at a liquid temperature of -10°C. (iii) The initial contact-containing solution was heated to 110°C and the reaction was carried out for 180 minutes while maintaining the same temperature. After the reaction was complete, the supernatant was removed and the first contact product, which was the reaction product, was washed four times with 250 mL of toluene at 100°C. (iv) Next, 185 mL of toluene and 30 mL (272.0 mmol) of titanium tetrachloride were added to the first contact product and the temperature was raised to 110°C and the reaction was carried out for 120 minutes to obtain the final contact product. Then, the obtained final contact product was washed eight times with 188 mL of n-heptane at 40°C and the solid-liquid was separated to obtain a solid catalyst component (d) for polymerization of phthalate diester-containing olefins. The solid-liquid of the obtained solid catalyst component was separated and the titanium content and phthalate diester compound content in the obtained solid were measured to be 2.5% by mass and 12.2% by mass, respectively.

[0122] (Example 1) <Preparation of external donor mixture and ethylene-propylene copolymer catalyst> Tetraethoxysilane and dicyclopentylbis(ethylamino) were collected in a molar ratio of 70:30 in a heat-resistant glass bottle containing a stirrer tip, stirred and mixed with a magnetic stirrer, and diluted with n-heptane to prepare an external donor mixture. Next, 2.2 mmol of triethylaluminum, a total of 0.22 mmol of the external donor mixture (calculated in terms of silicon atoms), and a total of 10.9 mg of the above solid catalyst component (I) (0.0055 mmol in terms of titanium atoms) were charged into a 2.0 liter autoclave with a stirrer, which was completely purged with nitrogen gas, to prepare an ethylene-propylene copolymer catalyst.

[0123] <Ethylene-Propylene Copolymerization> In an autoclave equipped with a stirrer containing the ethylene-propylene copolymerization catalyst prepared above, 15 moles (1.2 liters) of liquefied propylene and hydrogen gas at 0.20 MPa (partial pressure) were charged. Prepolymerization was carried out at 20°C for 5 minutes, then the temperature was increased, and the first stage of propylene homopolymerization (homo-stage polymerization) was carried out at 70°C for 45 minutes. After returning to atmospheric pressure, the inside of the autoclave (reactor) was purged with nitrogen, and the autoclave was weighed. The polymerization activity of the homo-stage (first stage) (homo-activity, g-PP / g-cat) was calculated by subtracting the tare mass of the autoclave. A portion of the generated polymer was separated for evaluation of polymerization performance and polymer properties. Next, ethylene and propylene were added to the autoclave (reactor) in a molar ratio of 1.0 / 1.5, respectively. The temperature was then raised to 70°C, and ethylene, propylene, and hydrogen were introduced at gas supply rates (liters / minute) of 1.6 / 2.4 / 0.09 respectively. The reaction was carried out under conditions of 1.2 MPa and 70°C to obtain an ethylene-propylene copolymer.

[0124] <Polymerization activity per gram of solid catalyst component> The polymerization activity per gram of solid catalyst component was calculated using the following formula: Polymerization activity (g / g-cat) = Mass of polymer (g) / Mass of solid catalyst component (g)

[0125] <Melt Flow Rate (MFR)> The melt flow rate (MFR) of olefin polymers was measured according to ASTM D 1238 and JIS K 7210.

[0126] <Blocking rate (mass%)> The blocking rate of the ethylene-propylene copolymer was calculated using the following formula (8): Blocking rate (mass%) = {(I (g) - G (g)) / (I (g) - F (g))} × 100 (8) Here, I is the autoclave mass (g) after the copolymerization reaction is complete, G is the autoclave mass (g) after the homopolypropylene polymerization is complete and unreacted monomers have been removed, and F is the autoclave mass (g).

[0127] <Flexural Modulus (FM)> Using NEX-III-3EG manufactured by Nissei Plastic Industrial Co., Ltd., an injection-molded test specimen with a thickness of 4.0 mm, a width of 10.0 mm, and a length of 170.0 mm was prepared under the conditions of a molding temperature of 180°C and a mold temperature of 40°C. The flexural modulus (FM) of the olefin polymer was measured according to JIS K7171 at a measurement ambient temperature of 23°C (unit: MPa).

[0128] <Impact Resistance (IZOD)> The impact resistance (IZOD) of olefin polymers was measured in accordance with JIS K 7110 ("Method of Izod Impact Test For Rigid Plastics") (unit: kJ / m2). 0.10 wt% IRGANOX 1010 (BASF) and 0.10 wt% IRGAFOS 168 (BASF) were added to ethylene-propylene copolymer, and this mixture was kneaded in a twin-screw kneader to form granules, obtaining ethylene-propylene copolymer pellets. The ethylene-propylene copolymer pellets were introduced into an injection molding machine (mold temperature: 40°C, cylinder temperature: 180°C) and injection molded to prepare specimens for property measurement. The specimen was cut and processed as described below, conditioned for more than 72 hours in a temperature-controlled chamber maintained at 23°C, and the Izod impact strength of the specimen was measured using an impact testing machine No. 258-L (with low-temperature chamber) manufactured by Yasuda Seiki Seisakusho. • Specimen shape: ISO 180 / 1A, thickness: 4.0 mm, width: 8.0 mm, length: 80.0 mm • Notch shape: A-type notch formed using a die mold with a notch (radius: 0.25 mm) • Temperature: 23°C • Impact velocity: 3.5 m / sec • Nominal pendulum energy: 2.75 J (23°C)

[0129] (Comparative Example 1) Except that solid catalyst component (b) for olefin polymerization containing a phthalate diester compound was used instead of solid catalyst component (I) containing a succinate diester compound and a phthalate diester compound as the solid catalyst component, the ethylene-propylene copolymer was prepared and ethylene-propylene copolymer was obtained in the same manner as in Example 1.

[0130] (Comparative Example 2) An ethylene-propylene copolymer catalyst was prepared in the same manner as in Example 1, except that a solid catalyst component (a) for olefin polymerization containing a succinate diester compound was used instead of a solid catalyst component (I) containing a succinate diester compound and a phthalate diester compound as the solid catalyst component. Furthermore, ethylene-propylene copolymerization was carried out in the same manner as in Example 1 to obtain an ethylene-propylene copolymer.

[0131]

[0132] According to the present invention, sufficient melt flowability can be obtained even with a small amount of hydrogen used during polymerization. Therefore, when compared under similar polymerization conditions, it is possible to produce olefin polymers that are more rigid and impact-resistant than those obtained using conventional catalysts for olefin polymerization, thus enabling the inexpensive production of olefin polymers.

Claims

1. (I) At least magnesium, titanium, halogen, and as an internal electron donor compound, at least the following general formula (1): (In the formula, R １ and R ２ are each independently a linear alkyl group having 1 to 12 carbon atoms, a branched alkyl group having 3 to 12 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms, a cycloalkenyl group having 3 to 12 carbon atoms, or an aromatic hydrocarbon group having 6 to 20 carbon atoms, which may be the same as or different from each other, and R ３ , R ４ , R ５ and R ６ are each independently a hydrogen atom, a halogen atom, a linear alkyl group having 1 to 12 carbon atoms, a branched alkyl group having 3 to 12 carbon atoms, a vinyl group, a linear or branched alkenyl group having 3 to 12 carbon atoms, a linear or branched halogen-substituted alkyl group having 2 to 12 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms, a cycloalkenyl group having 3 to 12 carbon atoms, an aromatic hydrocarbon group having 6 to 20 carbon atoms, a nitrogen-containing group, a phosphorus-containing group, and a silicon-containing group, which may be the same as or different from each other.) One or more compounds selected from the succinic acid diester compounds represented by the formula, and the following general formula (2): (In the formula, R ７ represents an alkyl group having 1 to 8 carbon atoms or a halogen atom, R ８ and R ９ are alkyl groups having 1 to 12 carbon atoms, which may be the same or different, and the number n of the substituent R ７ is 0, 1 or 2. When n is 2, R ７ may be the same or different.) A solid catalyst component for olefin polymerization containing one or more compounds selected from the phthalic acid diester compounds represented by the formula, (II) an organoaluminum compound, and (III) as an external electron donor compound, at least the following general formula (3): Si(OR １０ )(OR １１ )(OR １２ )(OR １３ ) (3) (In the formula, R １０ , R １１ , R １２ and R １３ (wherein C1 to C8 is a linear alkyl group or a branched alkyl group having C3 to C8, and they may be the same or different from each other.) One or more compounds selected from alkoxysilane compounds represented by the following general formula (4): R １４ R １５ Si (NHR １６ ) (NHR １７ ) (4) (wherein, R １４ and R １５ R is a linear alkyl group having 1 to 8 carbon atoms, a branched alkyl group having 3 to 12 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms, a cycloalkenyl group having 3 to 12 carbon atoms, or an aromatic hydrocarbon group having 6 to 20 carbon atoms, and they may be the same or different from each other. １６ and R １７ A catalyst for olefin polymerization, characterized by containing one or more compounds selected from (alkylamino)alkylsilane compounds represented by (wherein C1 is an alkyl group having 1 to 8 carbon atoms, which may be the same or different from each other), and 2. The succinate diester compound represented by the general formula (1) is diethyl succinate, diethyl 2,3-dimethyl succinate, diethyl 2,3-diethyl succinate, diethyl 2,3-di-n-propyl succinate, diethyl 2,3-diisopropyl succinate, diethyl 2,3-di-n-butyl succinate, diethyl 2,3-diisobutyl succinate, diisobutyl 2,3-diisopropyl succinate, di-n-butyl 2,3-diisopropyl succinate, diethyl 2,3-dicyclohexyl-2-methyl succinate, 2,3- Diisobutyl dicyclohexyl-2-methylsuccinate, diethyl 2,3-diisopropyl-2-cyanosuccinate, di-n-butyl 2,3-diisopropyl-2-cyanosuccinate, di-n-butyl 2,3-diisopropyl-2-cyanosuccinate, diisobutyl 2,3-dicyclopentyl-2-cyanosuccinate, diethyl 2,3-dicyclopentyl-2-cyanosuccinate, di-n-butyl 2,3-dicyclopentyl-2-cyanosuccinate, diisobutyl 2,3- Diethyl dicyclohexyl-2-cyanosuccinate, di-n-butyl 2,3-dicyclohexyl-2-cyanosuccinate, diisobutyl 2,3-dicyclohexyl-2-cyanosuccinate, diethyl 2-cyclopentyl-3-cyclohexyl-2-cyanosuccinate, 1-isobutyl 4-ethyl 2,3-diisopropyl-2-cyanosuccinate, 1-n-butyl 4-ethyl 2,3-diisopropyl-2-cyanosuccinate, diethyl 2-isopropyl-3-methyl-2-cyanosuccinate, 2-isopropyl-3-ethyl The catalyst for polymerization of olefins according to claim 1, characterized in that it is at least one selected from the group consisting of -2-cyanosuccinate diethyl, 2-isopropyl-3-n-propyl-2-cyanosuccinate diethyl, 2-isopropyl-3-butyl-2-cyanosuccinate diethyl, 2-isopropyl-3-phenyl-2-cyanosuccinate diethyl, 2-cyclohexyl-3-isopropyl-2-cyanosuccinate diethyl, and 2-isopropyl-3-phenyl-2-cyanosuccinate 1-ethyl-4-isobutyl.

3. The phthalate diester compound represented by the general formula (2) is dimethyl phthalate, diethyl phthalate, di-n-propyl phthalate, diisopropyl phthalate, di-n-butyl phthalate, diisobutyl phthalate, ethylmethyl phthalate, methyl(isopropyl) phthalate, ethyl(n-propyl) phthalate, ethyl(n-butyl) phthalate, ethyl(isobutyl) phthalate, di-n-pentyl phthalate, diisopentyl phthalate, dineopentyl phthalate, dihexyl phthalate, di-n-heptyl phthalate, di-n-octyl phthalate, bis(2,2-dimethylhexyl) phthalate, bis(2-ethylhexyl) phthalate, di-n-nonyl phthalate, diisodecyl phthalate, bis(2,2-dimethylheptyl) phthalate, n-butyl(isohexyl) phthalate, n-butyl(2-ethylhexyl) phthalate The catalyst for polymerization of olefins according to claim 1, characterized in that it is at least one selected from the group consisting of n-pentylhexyl phthalate, n-pentyl(isohexyl) phthalate, isopentyl(heptyl) phthalate, n-pentyl(2-ethylhexyl) phthalate, n-pentyl(isononyl) phthalate, isopentyl(n-decyl) phthalate, n-pentylundecyl phthalate, isopentyl(isohexyl) phthalate, n-hexyl(2,2-dimethylhexyl) phthalate, n-hexyl(2-ethylhexyl) phthalate, n-hexyl(isononyl) phthalate, n-hexyl(n-decyl) phthalate, n-heptyl(2-ethylhexyl) phthalate, n-heptyl(isononyl) phthalate, n-heptyl(neodecyl) phthalate, and 2-ethylhexyl(isononyl) phthalate.

4. The catalyst for polymerization of olefins according to claim 1, characterized in that the alkoxysilane compound represented by the general formula (3) is at least one selected from the group consisting of tetramethoxysilane, tetraethoxysilane, tetra(n-propoxy)silane, tetraisopropoxysilane, tetra(n-butoxy)silane, tetraisobutoxysilane, and tetrakis(2-ethylhexyloxy)silane.

5. The catalyst for polymerization of olefins according to claim 1, characterized in that the (alkylamino)alkylsilane compound represented by the general formula (4) is at least one selected from the group consisting of diisopropylbis(ethylamino)silane, dicyclopentylbis(ethylamino)silane, dicyclohexylbis(ethylamino)silane, cyclohexylmethylbis(ethylamino)silane, and cyclohexylcyclopentylbis(ethylamino)silane.

6. The catalyst for polymerization of olefins according to claim 1, characterized in that the molar ratio (Y / X), represented by the content (Y) of the (alkylamino)alkylsilane compound represented by general formula (4) to the content (X) of the alkoxysilane compound represented by general formula (3), is 1 / 99 to 50 / 50.

7. A method for producing an olefin polymer, characterized by polymerizing olefins using the olefin polymerization catalyst described in claim 1.

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