Olefin copolymerization solid catalyst component mixture, olefin copolymerization catalyst, and production method for olefin copolymer

Abstract

Provided is an olefin copolymerization solid catalyst component mixture that makes it possible to easily produce an olefin copolymer that has both excellent rigidity and excellent impact resistance relative to similar polymerization conditions.　An olefin copolymerization solid catalyst component mixture according to the present invention is characterized by containing a first olefin copolymerization solid catalyst component that includes magnesium, titanium, a halogen, and a succinic acid diester compound and a second olefin copolymerization solid catalyst component that includes magnesium, titanium, a halogen, and a phthalic acid diester compound, the first olefin copolymerization solid catalyst component content being at least 1 mass% but less than 37 mass% of the total of the first olefin copolymerization solid catalyst component content and the second olefin copolymerization solid catalyst component content.

Description

Solid catalyst component mixture for olefin copolymerization, catalyst for olefin copolymerization, and method for producing olefin copolymers

[0001] The present invention relates to a solid catalyst component mixture for olefin copolymerization, a catalyst for olefin copolymerization, and a method for producing olefin copolymers.

[0002] Conventionally, block copolymers such as propylene block copolymers have been obtained by copolymerizing olefins such as propylene using a catalyst for olefin copolymerization.

[0003] Among propylene block copolymers, propylene ethylene block copolymers in particular can be manufactured relatively inexpensively, but for broad applications, good mechanical properties such as rigidity and heat resistance are required.

[0004] A method has been reported for polymerizing olefins, such as polypropylene, which has high rigidity, by using a solid catalyst for olefin polymerization that contains a solid catalyst component for olefin polymerization, with 2,3-diisopropyl succinate diester as an internal electron donor, as a solid catalyst component (see Patent Document 1).

[0005] Japanese Patent Publication No. 2013-533367

[0006] However, the inventors' investigations revealed that when homopolymerization or copolymerization of olefins is performed using a solid catalyst component for olefin polymerization containing a succinate diester compound such as 2,3-diisopropyl succinate diester as an internal electron-donating compound, the rigidity of the resulting polymer increases, but the melt flowability decreases. Therefore, in order to obtain a homopolymer or copolymer of olefins with practical melt flowability using a solid catalyst component for olefin polymerization containing a succinate diester compound as an internal electron-donating compound, a large amount of hydrogen must be used during polymerization. In this case, the reaction becomes hydrogen-rich, making it easy for low molecular weight components to be generated, which tends to reduce the impact resistance of the resulting polymer.

[0007] Under these circumstances, the present invention aims to provide a solid catalyst component mixture for olefin copolymerization, a catalyst for olefin copolymerization, and a method for producing olefin copolymers, which can easily produce olefin copolymers that exhibit excellent rigidity and impact resistance when compared under similar polymerization conditions, and that achieve both properties simultaneously.

[0008] In order to solve the above technical problems, the inventors conducted extensive research and found that the above technical problems can be solved by using a solid catalyst component mixture for olefin copolymerization, which is obtained by mixing a first solid catalyst component for olefin copolymerization containing magnesium, titanium, halogen, and succinate diester compound with a second solid catalyst component for olefin copolymerization containing magnesium, titanium, halogen, and phthalate diester compound in a predetermined ratio. Based on this finding, the present invention was completed.

[0009] In other words, the present invention provides a mixture of solid catalyst components for olefin copolymerization characterized by comprising: (i) a first solid catalyst component for olefin copolymerization comprising magnesium, titanium, halogen and succinate diester compound; and a second solid catalyst component for olefin copolymerization comprising magnesium, titanium, halogen and phthalate diester compound, wherein the proportion of the first solid catalyst component for olefin copolymerization to the total content of the first and second solid catalyst components for olefin copolymerization is 1% by mass or more and less than 37% by mass; (ii) the mixture of solid catalyst components for olefin copolymerization described in (i) above, wherein the content of the succinate diester compound is 0.1 to 10.0% by mass on a solid content basis; (iii) (I) the mixture of solid catalyst components for olefin copolymerization described in (i) or (ii) above; and (II) the following general formula (1) R １ ｐ AlQ ３－ｐ (1) (wherein, R １ Q is an alkyl group having 1 to 6 carbon atoms, Q is a hydrogen atom or a halogen atom, p is 0 < p ≤ 3, and R １ If multiple R １may be the same as or different from each other. When there are a plurality of Qs, each Q may be the same as or different from each other. ), and a catalyst for copolymerizing olefins, characterized by containing one or more organoaluminum compounds selected from the compounds represented by (iv) (I) the solid catalyst component mixture for copolymerizing olefins described in (i) or (ii) above, (II) the following general formula (1) R １ ｐ AlQ ３－ｐ (1) (In the formula, R １ is an alkyl group having 1 to 6 carbon atoms, Q is a hydrogen atom or a halogen atom, p is 0 < p ≦ 3, and when there are a plurality of R １ , each R １ may be the same as or different from each other. When there are a plurality of Qs, each Q may be the same as or different from each other. ), and one or more organoaluminum compounds selected from the compounds represented by (III) as an external electron donor compound, the following general formula (2) R ２ R ３ Si(NHR ４ )(NHR ５ ) (2) (In the formula, R ２ and R ３ are 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 may be the same as or different from each other, and R ４ and R ５ ​​​​​​​​​​​​​R is a group selected from a linear or branched alkyl group having 1 to 12 carbon atoms, a substituted or unsubstituted cycloalkyl group, a phenyl group, an allyl group, and an aralkyl group, and may contain a heteroatom. ７ and R ８ R is a hydrogen atom or any group selected from a linear or branched alkyl group having 1 to 12 carbon atoms, a substituted or unsubstituted cycloalkyl group, a phenyl group, an allyl group, and an aralkyl group, which may contain heteroatoms and may be the same or different from each other. ７ and R ８ They may be bonded together to form a ring shape, R ７ and R ８ They may be the same or different. Also, R ９ R is a group selected from alkyl groups, cycloalkyl groups, phenyl groups, vinyl groups, allyl groups, and aralkyl groups having 1 to 12 carbon atoms, and may contain heteroatoms. ９ The present invention provides: (iii) a catalyst for copolymerizing olefins as described above, comprising one or more aminoalkoxysilane compounds represented by ) if there are multiple such compounds, they may be the same or different from each other; (v) a method for producing an olefin copolymer characterized by copolymerizing olefins using the catalyst for copolymerizing olefins as described above (iii) or (iv); and (vi) a method for producing an olefin copolymer as described above (v), wherein the copolymerization of olefins is a copolymerization of propylene and ethylene.

[0010] According to the present invention, it is possible to provide a solid catalyst component mixture for olefin copolymerization, a catalyst for olefin copolymerization, and a method for producing olefin copolymers, which can easily produce olefin copolymers that exhibit excellent rigidity and impact resistance when compared under similar polymerization conditions, and that achieve both properties simultaneously.

[0011] First, the solid catalyst component mixture for olefin copolymerization according to the present invention will be described. The solid catalyst component mixture for olefin copolymerization according to the present invention is characterized in that it comprises a first solid catalyst component for olefin copolymerization containing magnesium, titanium, halogen, and succinate diester compound, and a second solid catalyst component for olefin copolymerization containing magnesium, titanium, halogen, and phthalate diester compound, wherein the content of the first solid catalyst component for olefin copolymerization in relation to the total content of the first and second solid catalyst components for olefin copolymerization is 1% by mass or more and less than 37% by mass.

[0012] The solid catalyst component mixture for olefin copolymerization according to the present invention includes a first solid catalyst component for olefin copolymerization. The first solid catalyst component for olefin copolymerization constituting the solid catalyst component mixture for olefin copolymerization according to the present invention can be a catalytic reaction product obtained by contacting and reacting raw material components that serve as sources of magnesium, titanium, and halogen with a succinic acid diester compound, which is an internally electron-donating compound, in an organic solvent. Specifically, a magnesium compound and a tetravalent titanium halogen compound can be used as raw material components that serve as sources of magnesium, titanium, and halogen, and a catalytic reaction product obtained by contacting these raw materials with an internally electron-donating compound containing a succinic acid diester compound can be an example.

[0013] Examples of the above magnesium compounds include one or more selected from dialkoxymagnesium, magnesium dihalides, and alkoxymagnesium halides. Among the above magnesium compounds, dialkoxymagnesium or magnesium dihalides are preferred, and specifically include dimethoxymagnesium, diethoxymagnesium, dipropoxymagnesium, dibutoxymagnesium, ethoxymethoxymagnesium, ethoxypropoxymagnesium, butoxyethoxymagnesium, magnesium dichloride, magnesium dibromide, magnesium diodide, etc., with diethoxymagnesium and magnesium dichloride being particularly preferred.

[0014] Among the magnesium compounds mentioned above, dialkoxymagnesium may be obtained by reacting metallic magnesium with an alcohol in the presence of a halogen or a halogen-containing metallic compound.

[0015] The above-mentioned dialkoxymagnesium is preferably in granular or powder form, and may be of an irregular shape or spherical.

[0016] When spherical dialkoxymagnesium is used, a copolymer 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 copolymerization operation and suppressing the occurrence of blockages and other issues caused by fine particles contained in the generated copolymer powder.

[0017] The spherical dialkoxymagnesium mentioned above does not necessarily have to be perfectly spherical; elliptical or potato-shaped forms can also be used.

[0018] 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.

[0019] 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. Moreover, 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. 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.

[0020] 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.

[0021] In the solid catalyst component for olefin copolymerization according to the present invention, the magnesium compound 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 magnesium compound with a specific surface area within the above range, a solid catalyst component for olefin copolymerization having a desired specific surface area can be easily prepared.

[0022] In this application, the specific surface area of ​​the magnesium compound refers to the value measured by the BET method. Specifically, the specific surface area of ​​the magnesium compound is measured by the BET method (automatic measurement) using a Mountech Automatic SurfaceArea 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.

[0023] The above magnesium compound is preferably in solution or suspension form during the reaction, as this allows the reaction to proceed smoothly.

[0024] If the magnesium compound is a solid, it can be dissolved in a solvent that has the ability to solubilize magnesium compounds to obtain a solution, or it can be suspended in a solvent that does not have the ability to solubilize magnesium compounds to obtain a suspension. If the magnesium compound is a liquid, it may be used as is as a solution, or it may be further dissolved in a solvent that has the ability to solubilize magnesium compounds before being used as a solution.

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

[0026] In the solid catalyst component for olefin copolymerization that constitutes the catalyst for olefin copolymerization according to the present invention, the tetravalent titanium halogen compound, which is a raw material component that serves as a source of titanium and halogen, is not particularly limited, but the following general formula (4) Ti(OR １０ ) ｑ X ４－ｑ(4) (wherein, R １０ It is preferable that the compound is one or more compounds selected from the titanium halide or alkoxy titanium halide group represented by (where is an alkyl group having 1 to 4 carbon atoms, X is a halogen atom such as a chlorine atom, a bromine atom, or an iodine atom, and q is 0 ≤ q ≤ 3).

[0027] In the general formula (4) above, q is 0 ≤ r ≤ 3, and specifically, q can be 0, 1, 2, or 3.

[0028] Examples of titanium halides represented by the above general formula (4) 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 (4) 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.

[0029] In the first solid catalyst component for olefin copolymerization constituting the solid catalyst mixture for olefin copolymerization according to the present invention, the succinate diester compound is the following general formula (5); (In the formula, R １１ and R １２ R is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and they may be the same or different from each other. １３ and R １４ One or more compounds can be selected from those represented by (where C1 is a linear alkyl group or branched alkyl group having 2 to 4 carbon atoms, and they may be the same or different from each other).

[0030] In the compound represented by the above general formula (5), R １１ and R １２ R is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and they may be the same or different from each other. １１ or R １２ When R is an alkyl group having 1 to 4 carbon atoms, specifically, examples include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, or an isobutyl group. In the compound represented by the above general formula (5), R １３ and R １４ R is a linear alkyl group or branched alkyl group having 2 to 4 carbon atoms, and may be the same or different from each other. １３ and R １４ When the group is a linear alkyl group or branched alkyl group having 2 to 4 carbon atoms, specific examples include an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, or an isobutyl group.

[0031] In the first solid catalyst component for olefin copolymerization constituting the solid catalyst component mixture for olefin copolymerization according to the present invention, the succinate diester compound is a dialkyl succinate ester represented by the above general formula (5), for example: 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; 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; One or more can be selected from di-n-butyl succinate, di-n-butyl 2,3-dimethylsuccinate, di-n-butyl 2,3-diethylsuccinate, di-n-butyl 2,3-di-n-propylsuccinate, di-n-butyl 2,3-diisopropylsuccinate, di-n-butyl 2,3-diisobutylsuccinate, di-n-butyl succinate; diisobutyl succinate, diisobutyl 2,3-dimethylsuccinate, diisobutyl 2,3-diethylsuccinate, diisobutyl 2,3-di-n-propylsuccinate, diisobutyl 2,3-diisopropylsuccinate, diisobutyl 2,3-di-n-butylsuccinate, diisobutyl 2,3-diisobutylsuccinate;Among these dialkyl succinate esters, 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-diisopropyl succinate diisopropyl, 2,3-diisopropyl succinate di-n-butyl, 2,3-diisopropyl succinate di-n-butyl, 2,3-diisopropyl succinate diisobutyl, and 2,3-diisopropyl succinate diisobutyl are preferably used.

[0032] The first solid catalyst component for olefin copolymerization constituting the solid catalyst component mixture for olefin copolymerization according to the present invention preferably has a succinic acid diester compound content of 5 to 28% by mass, more preferably 10 to 24% by mass, and even more preferably 15 to 20% by mass, when calculated on a solid content basis. The first solid catalyst component for olefin copolymerization constituting the solid catalyst component mixture for olefin copolymerization according to the present invention preferably has a succinic acid diester compound content of 0.019 to 0.108 mol%, more preferably 0.039 to 0.093 mol%, and even more preferably 0.058 to 0.077 mol%, when calculated on a solid content basis.

[0033] The first solid catalyst component for olefin copolymerization constituting the solid catalyst component mixture for olefin copolymerization according to the present invention has a ratio (D1 / T) of the content of the succinic acid diester compound (D1) to the content of titanium (T) that is preferably 3.5 to 6.6 by mass, more preferably 4.1 to 6.0, and even more preferably 4.8 to 5.4. The first solid catalyst component for olefin copolymerization constituting the solid catalyst component mixture for olefin copolymerization according to the present invention has a ratio (D1 / T) of the content of the succinic acid diester compound (D1) to the content of titanium (T) that is preferably 0.3 to 1.3 by molar ratio, more preferably 0.5 to 1.2, and even more preferably 0.7 to 1.1.

[0034] In the first solid catalyst component for olefin copolymerization that constitutes the solid catalyst component mixture for olefin copolymerization according to the present invention, the ratio (D1 / T) of the content of the succinate diester compound (D1) to the content of titanium (T) when calculated on a solid content basis is within the above range, so that when subjected to copolymerization of olefins, olefin copolymers with excellent flexural modulus (FM) can be easily produced without reducing impact resistance.

[0035] The first solid catalyst component for olefin copolymerization constituting the solid catalyst component mixture for olefin copolymerization according to the present invention contains a succinic acid diester compound as an essential component as an internal electron-donating compound, but may also contain other internal electron-donating compounds (hereinafter referred to as "other internal electron-donating compounds" as appropriate).

[0036] Other internally electron-donating compounds include one or more selected from carbonates, acid halides, acid amides, nitriles, acid anhydrides, diether compounds, and carboxylic acid esters.

[0037] Examples of other internally electron-donating compounds include one or more selected from ether carbonate compounds, cycloalkane dicarboxylic acid diesters, cycloalkene dicarboxylic acid diesters, malonic acid diesters, alkyl-substituted malonic acid diesters, maleic acid diesters, and other carboxylic acid diesters. More specifically, one or more selected from ether carbonate compounds such as (2-ethoxyethyl)methyl carbonate, (2-ethoxyethyl)ethyl carbonate, and (2-ethoxyethyl)phenyl carbonate, dialkylmalonic acid diesters such as diisobutylmalonate dimethyl and diisobutylmalonate diethyl, and cycloalkane dicarboxylic acid diesters such as cyclohexane-1,2-dicarboxylic acid dimethyl are more preferred.

[0038] On the other hand, the first solid catalyst component for olefin copolymerization constituting the solid catalyst component mixture for olefin copolymerization according to the present invention is preferably such that the content of the phthalate diester compound is 0.2% by mass or less (0.0 to 0.2% by mass), more preferably 0.1% by mass or less (0.0 to 0.1% by mass), and even more preferably 0.0% by mass (substantially free of phthalate diester compounds (below the detection limit)).

[0039] In this application, the content ratio of succinate diester compounds, other internally electron-donating compounds added as needed, and (described later) phthalate diester compounds contained in the solid catalyst component for olefin copolymerization refer to values ​​obtained by first heating and vacuum drying the solid catalyst component for olefin copolymerization to completely remove solvent components in order to convert it to solid content, then hydrolyzing it, and then extracting succinate diester compounds, other internally electron-donating compounds added as needed, and phthalate diester compounds using an aromatic solvent, and measuring this solution by gas chromatography FID (Flame Ionization Detector). As stated above, in this application, "converted to solid content" means calculating the content ratio of each component based on the solid content after completely removing liquid components such as solvents.

[0040] The first solid catalyst component for olefin copolymerization constituting the solid catalyst component mixture for olefin copolymerization according to the present invention preferably contains titanium atoms in an amount of 2.0 to 5.0% by mass, more preferably 2.5 to 4.5% by mass, and even more preferably 3.5 to 4.5% by mass. The first solid catalyst component for olefin copolymerization constituting the solid catalyst component mixture for olefin copolymerization according to the present invention preferably contains magnesium atoms in an amount of 15.0 to 25.0% by mass, more preferably 16.0 to 23.0% by mass, even more preferably 17.0 to 22.0% by mass, and even more preferably 17.0 to 21.0% by mass. The first solid catalyst component for olefin copolymerization constituting the solid catalyst component mixture for olefin copolymerization according to the present invention preferably contains halogen in an amount of 50.0 to 70.0% by mass on an atomic basis, more preferably 55.0 to 68.0% by mass, even more preferably 58.0 to 67.0% by mass, and even more preferably 60.0 to 66.0% by mass.

[0041] In this application, the titanium atom content in the solid catalyst component for olefin copolymerization refers to the value measured using the method described in JIS 8311-1997 "Method for Determinating Titanium in Titanium Ore" (redox titration), with the solid catalyst component for olefin copolymerization having been preheated and dried under reduced pressure to completely remove solvent components.

[0042] Furthermore, in this application, the magnesium atom content in the solid catalyst component for olefin copolymerization refers to the value measured by the EDTA titration method, in which the solid catalyst component for olefin copolymerization, which has been preheated and dried under reduced pressure to completely remove solvent components, is dissolved in hydrochloric acid solution and titrated with EDTA solution.

[0043] Furthermore, in this application, the halogen atom content in the solid catalyst component for olefin copolymerization refers to the value measured by a silver nitrate titration method, in which a predetermined amount of the solid catalyst component for olefin copolymerization, which has been preheated and dried under reduced pressure to completely remove solvent components, is treated with a mixed solution of sulfuric acid and pure water to obtain an aqueous solution, and then the halogen is titrated with a silver nitrate standard solution.

[0044] The first solid catalyst component for olefin copolymerization that constitutes the solid catalyst component mixture for olefin copolymerization in the present invention comprises magnesium, titanium, halogen, and succinate diester compounds, and optionally other internally electron-donating compounds, and may further contain polysiloxane.

[0045] The first solid catalyst component for olefin copolymerization in the present invention, which constitutes the solid catalyst component mixture for olefin copolymerization, contains polysiloxane. This allows for easy improvement of the stereoregularity or crystallinity of the resulting polymer when olefins are polymerized, and furthermore, the fine powder content of the resulting polymer can be easily reduced. Polysiloxane is a polymer having siloxane bonds (-Si-O- bonds) in its main chain, and is also called silicone oil. Its viscosity at 25°C is 0.02 to 100.00 cm². ２ / s (2 to 10,000 centistokes), more preferably 0.03 to 5.00 cm ２ It is a linear, partially hydrogenated, cyclic, or modified polysiloxane having a length of 3 to 500 centistokes at room temperature, and being liquid or viscous at room temperature.

[0046] Examples of linear polysiloxanes include dimethylpolysiloxane and methylphenylpolysiloxane; examples of partially hydrogenated polysiloxanes include methylhydrogenpolysiloxane with a hydrogenation rate of 10-80%; and examples of cyclic polysiloxanes include one or more selected from hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, 2,4,6-trimethylcyclotrisiloxane, and 2,4,6,8-tetramethylcyclotetrasiloxane.

[0047] The solid catalyst component mixture for olefin copolymerization according to the present invention includes a second solid catalyst component for olefin copolymerization along with the first solid catalyst component for olefin copolymerization described above. The second solid catalyst component for olefin copolymerization constituting the solid catalyst component mixture for olefin copolymerization according to the present invention can be a catalytic reaction product obtained by contacting and reacting raw material components that serve as sources of magnesium, titanium, and halogen with a phthalate diester compound, which is an internally electron-donating compound, in an organic solvent. Specifically, a catalytic reaction product can be obtained by using a magnesium compound and a tetravalent titanium halogen compound as raw material components that serve as sources of magnesium, titanium, and halogen, and contacting these raw materials with an internally electron-donating compound containing a phthalate diester compound.

[0048] Specific examples of the above-mentioned magnesium compounds and tetravalent titanium halogen compounds are the same as those listed in the description of the first solid catalyst component for olefin copolymerization.

[0049] In the second solid catalyst component for olefin copolymerization constituting the solid catalyst mixture for olefin copolymerization according to the present invention, phthalate diesters are preferred as the phthalate diester compound. Examples of the above phthalate diesters include one or more selected from dimethyl phthalate, diethyl phthalate, di-n-propyl phthalate, diisopropyl phthalate, di-n-butyl phthalate, diisobutyl phthalate, methyl ethyl phthalate, (ethyl) n-propyl phthalate, ethyl isopropyl phthalate, (ethyl) n-butyl phthalate, ethyl isobutyl phthalate, and the like.

[0050] The second solid catalyst component for olefin copolymerization that constitutes the solid catalyst component mixture for olefin copolymerization according to the present invention preferably has a phthalate diester compound content of 8.0 to 20.0% by mass, more preferably 9.0 to 17.5% by mass, and even more preferably 10.0 to 15.0% by mass, when calculated on a solid content basis. The second solid catalyst component for olefin copolymerization that constitutes the solid catalyst component mixture for olefin copolymerization according to the present invention preferably has a phthalate diester compound content of 2.7 to 5.6 mol%, more preferably 3.6 to 5.3 mol%, and even more preferably 4.5 to 5.0 mol%, when calculated on a solid content basis.

[0051] The second solid catalyst component for olefin copolymerization that constitutes the solid catalyst component mixture for olefin copolymerization according to the present invention preferably has a ratio (D2 / T) of the content of the phthalate diester compound (D2) to the content of titanium (T) that is 0.025 to 0.072 by mass, more preferably 0.030 to 0.063, and even more preferably 0.035 to 0.054. The second solid catalyst component for olefin copolymerization that constitutes the solid catalyst component mixture for olefin copolymerization according to the present invention preferably has a ratio (D2 / T) of the content of the phthalate diester compound (D2) to the content of titanium (T) that is 0.3 to 1.3 by molar, more preferably 0.5 to 1.2, and even more preferably 0.7 to 1.1.

[0052] In the second solid catalyst component for olefin copolymerization that constitutes the solid catalyst component mixture for olefin copolymerization according to the present invention, the ratio (D2 / T) of the phthalate diester compound content (D2) to the titanium content (T) when calculated on a solid content basis is within the above range, thereby enabling the easy production of olefin copolymers with even better flexural modulus (FM) when subjected to olefin copolymerization.

[0053] The second solid catalyst component for olefin copolymerization, which constitutes the solid catalyst component mixture for olefin copolymerization according to the present invention, contains a phthalate diester compound as an essential component as an internal electron-donating compound. However, it may also contain other internal electron-donating compounds, and examples of such other internal electron-donating compounds are the same as those listed in the description of the first solid catalyst component for olefin copolymerization above.

[0054] The second solid catalyst component for olefin copolymerization that constitutes the solid catalyst component for olefin copolymerization according to the present invention is preferably such that the content of the succinate diester compound is 0.2% by mass or less (0.0 to 0.2% by mass), more preferably 0.1% by mass or less (0.0 to 0.1% by mass), and even more preferably 0.0% by mass (substantially free of succinate diester (below the detection limit)).

[0055] The second solid catalyst component for olefin copolymerization constituting the solid catalyst component mixture for olefin copolymerization according to the present invention preferably contains titanium atoms in an amount of 2.0 to 5.0% by mass, more preferably 2.5 to 4.5% by mass, and even more preferably 3.5 to 4.5% by mass. The second solid catalyst component for olefin copolymerization constituting the solid catalyst component mixture for olefin copolymerization according to the present invention preferably contains magnesium atoms in an amount of 15.0 to 25.0% by mass, more preferably 16.0 to 23.0% by mass, even more preferably 17.0 to 22.0% by mass, and even more preferably 17.0 to 21.0% by mass. The second solid catalyst component for olefin copolymerization constituting the solid catalyst component mixture for olefin copolymerization according to the present invention preferably contains halogen in an amount of 50.0 to 70.0% by mass on an atomic basis, more preferably 55.0 to 68.0% by mass, even more preferably 58.0 to 67.0% by mass, and even more preferably 60.0 to 66.0% by mass.

[0056] The method for measuring the content ratio of each component of the second solid catalyst component for olefin copolymerization described above is as described in the description of the first solid catalyst component for olefin copolymerization.

[0057] The second solid catalyst component for olefin copolymerization that constitutes the solid catalyst component mixture for olefin copolymerization according to the present invention may contain a polysiloxane, and specific examples of polysiloxanes are the same as those described in the description of the first solid catalyst component for olefin copolymerization.

[0058] The solid catalyst component mixture for olefin copolymerization according to the present invention has a ratio of the content of the first solid catalyst component for olefin copolymerization to the total content of the first solid catalyst component for olefin copolymerization and the second solid catalyst component for olefin copolymerization of 1% by mass or more and less than 37% by mass, preferably 5% by mass or more and 35% by mass or less, and more preferably 8% by mass or more and 32% by mass or less.

[0059] Furthermore, the solid catalyst component mixture for olefin copolymerization according to the present invention means a mixture containing only the first solid catalyst component for olefin copolymerization and the second solid catalyst component for olefin copolymerization.

[0060] The solid catalyst component mixture for olefin copolymerization according to the present invention contains the first solid catalyst component for olefin copolymerization in a lower proportion than the second solid catalyst component for olefin copolymerization. Therefore, even with a small amount of hydrogen used during the polymerization of olefins, the resulting polymer exhibits sufficiently high melt flowability, suppresses the generation of low molecular weight components due to hydrogen-heavy reaction conditions, and enables the more effective production of olefin copolymers that combine high rigidity and impact resistance.

[0061] In the solid catalyst component mixture for olefin copolymerization according to the present invention, a succinic acid diester compound is used as the internal electron-donating compound constituting the first solid catalyst component for olefin copolymerization, while a phthalic acid diester compound is used as the internal electron-donating compound constituting the second solid catalyst component for olefin copolymerization. In the solid catalyst component mixture for olefin copolymerization according to the present invention, the content of the succinic acid diester compound is preferably 0.1 to 10.0% by mass, more preferably 0.5 to 8.0% by mass, and even more preferably 1.0 to 6.0% by mass, on a solid content basis. Furthermore, in the solid catalyst component mixture for olefin copolymerization according to the present invention, the content of the phthalic acid diester compound is preferably 4.0 to 20.0% by mass, more preferably 6.0 to 18.0% by mass, and even more preferably 8.0 to 12.0% by mass, on a solid content basis. In the solid catalyst component mixture for olefin copolymerization according to the present invention, the content ratios of succinate diester compounds and phthalate diester compounds are within the above range, thereby enabling the easy production of olefin copolymers that exhibit both high rigidity and impact resistance when subjected to olefin copolymerization.

[0062] The inventors have found that by using a first solid catalyst component for olefin copolymerization that contains a succinate diester compound as an internal electron-donating compound, and a second solid catalyst component for olefin copolymerization that uses a phthalate diester compound as an internal electron-donating compound, and by using a mixture containing the first and second solid catalyst components in predetermined proportions instead of the solid catalyst component of conventional olefin copolymerization catalysts, it is possible to produce olefin copolymers that exhibit both high rigidity and impact resistance when subjected to olefin copolymerization. Based on this finding, the inventors have completed the present invention.

[0063] A mixture of solid catalyst components for olefin copolymerization containing multiple internally electron-donating compounds is thought to produce multiple olefin copolymers when subjected to copolymerization of olefins. However, since olefin copolymers with significantly different physical properties generally do not mix well, it is generally difficult to put such mixtures into practical use. On the other hand, in the solid catalyst component mixture for olefin copolymerization according to the present invention, by subjecting a mixture containing a first solid catalyst component for olefin copolymerization and a second solid catalyst component for olefin copolymerization in predetermined proportions to copolymerization of olefins, the first solid catalyst component for olefin copolymerization produces a first olefin copolymer that is highly rigid and has a broad molecular weight distribution. This first olefin copolymer with a broad molecular weight distribution is thought to exhibit high compatibility with the second olefin copolymer, which has excellent impact resistance and is produced by the second solid catalyst component for olefin copolymerization. The resulting olefin copolymer (a mixture of the first and second olefin copolymers) is expected to exhibit high rigidity primarily due to the first olefin copolymer and high impact resistance primarily due to the second olefin copolymer. In this case, since the solid catalyst component mixture for olefin copolymerization according to the present invention has a reduced content of the first olefin copolymer solid catalyst component compared to the second olefin copolymer solid catalyst component, it is expected that even with a small amount of hydrogen used during olefin polymerization, the resulting polymer will exhibit sufficiently high melt flowability, suppress the generation of low molecular weight components due to hydrogen-heavy reaction conditions, and enable the easy production of olefin copolymers that achieve both high rigidity and impact resistance (a balance between the two).

[0064] As described above, when mixing multiple types of olefin polymers, polymers with significantly different physical properties generally tend not to mix well. Depending on the olefin polymers to be mixed, this may require special mixing equipment with superior stirring power, incur significant energy costs, and increase the number of steps, making it difficult to easily produce olefin polymers with desired properties. In contrast, the present invention employs a specific mixture of solid catalyst components for olefin copolymerization instead of conventionally used solid catalyst components for olefin copolymerization, enabling the easy production of olefin copolymers that combine high rigidity and impact resistance without incurring significant energy costs or increasing the number of steps.

[0065] The solid catalyst component mixture for olefin copolymerization according to the present invention may be prepared by pre-mixing the first solid catalyst component for olefin copolymerization and the second solid catalyst component for olefin copolymerization and using the mixture in the copolymerization of olefins, or the first solid catalyst component for olefin copolymerization and the second solid catalyst component for olefin copolymerization may be separately charged into the copolymerization system of olefins and used as a mixture within the polymerization system.

[0066] The first solid catalyst component for olefin copolymerization and the second solid catalyst component for olefin copolymerization constituting the solid catalyst component mixture for olefin copolymerization according to the present invention can each be produced by conventionally known methods. The first solid catalyst component for olefin copolymerization and the second solid catalyst component for olefin copolymerization constituting the solid catalyst component mixture for olefin copolymerization according to the present invention differ in that they each contain either a succinate diester compound or a phthalate diester compound as an essential component as an internal electron-donating compound, but they are common in many other respects. Therefore, the methods for producing the first solid catalyst component for olefin copolymerization and the second solid catalyst component for olefin copolymerization also differ in that they each use either a succinate diester compound or a phthalate diester compound as an essential component as an internal electron-donating compound, but are common in many other respects.

[0067] The first or second solid catalyst component for olefin copolymerization constituting the solid catalyst component mixture for olefin copolymerization according to the present invention is preferably prepared by bringing the above-mentioned dialkoxymagnesium, titanium halogen compound, and internal electron-donating compound (containing either a succinate diester compound or a phthalate diester compound as an essential component) into contact with each other in the presence of an inert organic solvent, as may be further necessary with other components.

[0068] 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 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 selected from hexane, heptane, octane, ethylcyclohexane, mineral oil, toluene, xylene, and ethylbenzene are preferred, and particularly preferably one or more selected from hexane, heptane, ethylcyclohexane, and toluene.

[0069] As a method for producing a solid catalyst component for olefin copolymerization that constitutes the catalyst for olefin copolymerization according to the present invention, a method is used to prepare a first solid catalyst component for olefin copolymerization or a second solid catalyst component for olefin copolymerization by contacting dialkoxymagnesium, a titanium halogen compound, and an internal electron-donating compound (containing either a succinic acid diester compound or a phthalic acid diester compound as an essential component) with each other, wherein the titanium halogen compound is contacted with dialkoxymagnesium multiple times, and when the titanium halogen compound is first contacted with dialkoxymagnesium, 1.5 to 10.0 moles of the titanium halogen compound are used per mole of dialkoxymagnesium, the total amount of titanium compound used is 5.0 to 18.0 moles per mole of dialkoxymagnesium, and furthermore, the amount of succinic acid diester compound or phthalic acid diester compound used is 0.10 to 0.20 moles per mole of dialkoxymagnesium, thereby obtaining the desired solid catalyst component for olefin copolymerization (hereinafter referred to as method for producing the solid catalyst component a).

[0070] In method a for producing the solid catalyst component, the titanium halogen compound is brought into contact with dialkoxymagnesium multiple times. When the titanium halogen compound is brought into contact with dialkoxymagnesium for the first time, it is preferable to use 1.5 to 10.0 moles of the titanium halogen compound per mole of dialkoxymagnesium, 2.0 to 8.0 moles per mole of dialkoxymagnesium, and more preferably 2.0 to 5.0 moles per mole of dialkoxymagnesium.

[0071] In method a for producing the solid catalyst component, by controlling the amount of titanium halogen compound used relative to dialkoxymagnesium within the above range, a solid catalyst component for olefin copolymerization that exhibits high activity with a small amount of titanium halogen compound can be prepared.

[0072] In method a for producing the solid catalyst component, the total amount of titanium compound used is 5.0 to 18.0 moles per mole of dialkoxymagnesium, preferably 5.0 to 15.0 moles per mole of dialkoxymagnesium, and more preferably 5.0 to 10.0 moles per mole of dialkoxymagnesium.

[0073] In method a for producing the solid catalyst component, by controlling the total amount of titanium compound used per mole of dialkoxymagnesium within the above range, it is possible to prepare a carrier that can optimally support titanium halogen compounds and succinate diester compounds while ensuring sufficiently high activity.

[0074] In method a for producing the solid catalyst component, it is preferable to use 0.10 to 0.20 moles of a succinate diester compound or a phthalate diester compound per mole of dialkoxymagnesium, 0.10 to 0.18 moles of a succinate diester compound or a phthalate diester compound per mole of dialkoxymagnesium, and more preferably 0.10 to 0.15 moles of a succinate diester compound or a phthalate diester compound per mole of dialkoxymagnesium.

[0075] In method a for producing the solid catalyst component, by controlling the amount of succinate diester compound or phthalate diester compound used per mole of dialkoxymagnesium within the above range, it is possible to sufficiently support the succinate diester compound or phthalate diester compound on the support while suppressing excessive support of the titanium halogen compound on the support.

[0076] More specifically, as a method a for producing a solid catalyst component, for example, a method can be given in which a dialkoxymagnesium and a titanium halogen compound are suspended in an inert hydrocarbon solvent with a succinic acid diester compound or a phthalic acid diester compound, contacted for a predetermined time while heating, and then a titanium halogen compound is added to the resulting suspension and contacted while heating to obtain a solid product, and the solid product is washed with a hydrocarbon solvent to obtain the target solid catalyst component for olefin copolymerization.

[0077] The heating temperature is preferably 70 to 150°C, more preferably 80 to 120°C, and even more preferably 90 to 110°C. The heating time is preferably 30 to 240 minutes, more preferably 60 to 180 minutes, and even more preferably 60 to 120 minutes.

[0078] There are no particular restrictions on the number of times the titanium halogen compound is added to the above suspension. If the titanium halogen compound is added to the above suspension multiple times, the heating temperature for each addition should be within the above range, and the heating time for each addition should be within the above range.

[0079] In addition, in the above preparation method, while adding a succinate diester compound or a phthalate diester compound as an internal electron-donating compound, other internal electron-donating compounds may be added further. Furthermore, the above contact may be carried out in the presence of other reaction reagents or surfactants, such as silicon, phosphorus, or aluminum.

[0080] According to the present invention, it is possible to provide a solid catalyst component mixture for olefin copolymerization that, when compared under similar polymerization conditions, exhibits excellent rigidity and impact resistance, and allows for the simple production of olefin copolymers that achieve both.

[0081] Next, the catalyst for olefin copolymerization according to the present invention will be described. The catalyst for olefin copolymerization according to the present invention comprises (I) a mixture of solid catalyst components for olefin copolymerization according to the present invention and (II) the following general formula (1) R １ ｐ AlQ ３－ｐ (1) (wherein, R １ The compound is characterized by containing one or more organoaluminum compounds selected from compounds represented by (where is an alkyl group having 1 to 6 carbon atoms, Q is a hydrogen atom or a halogen atom, and p is 0 < p ≤ 3).

[0082] In the catalyst for copolymerization of olefins according to the present invention, (I) the details of the solid catalyst component mixture for copolymerization of olefins according to the present invention are as described above.

[0083] The catalyst for olefin copolymerization according to the present invention is an organoaluminum compound, (II) the following general formula (1); R １ ｐ AlQ ３－ｐ (1) (wherein, R １ Q is an alkyl group having 1 to 6 carbon atoms, Q is a hydrogen atom or a halogen, p is 0 < p ≤ 3, and R １ If multiple R １ The compounds include one or more selected from the compounds represented by (which may be identical or different from each other, and if there are multiple Qs, each Q may be identical or different from each other).

[0084] In the compound represented by the above general formula (1), p is 0 < p ≤ 3, and specifically, p can be 1, 2, or 3.

[0085] Specific examples of organoaluminum compounds represented by the above general formula (1) include one or more 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 selected from alkylaluminum halides such as diethylaluminum chloride, trialkylaluminum such as triethylaluminum, tri-n-butylaluminum, and triisobutylaluminum is preferred, and more preferably, one or more selected from triethylaluminum and triisobutylaluminum.

[0086] The catalyst for copolymerization of olefins according to the present invention preferably contains (III) an external electron-donating compound.

[0087] In the catalyst for copolymerization of olefins according to the present invention, (III) as an external electron-donating compound, the following general formula (2) R ２ R ３ Si (NHR ４ ) (NHR ５ ) (2) (wherein, R ２ and R３ 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. ４ and R ５ One or more (alkylamino)alkylsilane compounds represented as (where C1 to C8 are alkyl groups that may be the same or different from each other) can be listed.

[0088] In an (alkylamino)alkylsilane compound represented by general formula (2), R ２ and R ３ 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. ２ and R ３ Examples include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, neopentyl group, cyclopentyl group, n-hexyl group, cyclohexyl group, or 2-ethylhexyl group. In the (alkylamino)alkylsilane compound represented by general formula (2), R ４ and R ５ 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. ４ and R ５ 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.

[0089] As the (alkylamino)alkylsilane compound represented by the general formula (2), specifically, diisopropylbis(ethylamino)silane, dicyclopentylbis(ethylamino)silane, dicyclohexylbis(ethylamino)silane, cyclohexylmethylbis(ethylamino)silane, cyclohexylcyclopentylbis(ethylamino)silane, etc. can be mentioned.

[0090] Further, in the catalyst for copolymerizing olefins according to the present invention, as the (III) external electron donating compound, the following general formula (3): R ６ ｒ Si(NR ７ R ８ )(OR ｓ )(3) (In the formula, r is 0 to 2, s is 1 to 3, and r + s is 1 to 3. R ９ )(3) (In the formula, r is 0 to 2, s is 1 to 3, and r + s is 1 to 3. R ４－（ｒ＋ｓ） is any group selected from a linear or branched alkyl group having 1 to 12 carbon atoms, a substituted or unsubstituted cycloalkyl group, a phenyl group, an allyl group, and an aralkyl group, and may contain a hetero atom. R ６ is any group selected from a linear or branched alkyl group having 1 to 12 carbon atoms, a substituted or unsubstituted cycloalkyl group, a phenyl group, an allyl group, and an aralkyl group, and may contain a hetero atom. R ７ and R ８ are each a hydrogen atom or any group selected from a linear or branched alkyl group having 1 to 12 carbon atoms, a substituted or unsubstituted cycloalkyl group, a phenyl group, an allyl group, and an aralkyl group, and may contain a hetero atom, and may be the same or different from each other. R ７ and R ８ may be bonded to form a cyclic shape, and R ７ and R ８ may be the same or different. Further, R ９ is any group selected from an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group, a phenyl group, a vinyl group, an allyl group, and an aralkyl group, and may contain a hetero atom. When there are a plurality of R ９ , they may be the same or different from each other.) One or more selected from aminoalkoxysilane compounds represented by can be mentioned.

[0091] In the aminoalkoxysilane compound represented by the general formula (3), R ６R is a linear alkyl group having 1 to 12 carbon atoms or a branched alkyl group having 3 to 12 carbon atoms, a substituted or unsubstituted cycloalkyl group, a phenyl group, an allyl group, and an aralkyl group, preferably any group selected from a linear alkyl group having 1 to 8 carbon atoms, a branched alkyl group having 3 to 12 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 12 carbon atoms, or an aromatic hydrocarbon group having 6 to 20 carbon atoms, and may contain a heteroatom. In an aminoalkoxysilane compound represented by general formula (3), R ７ and R ８ R is a hydrogen atom or any group selected from a linear alkyl group having 1 to 12 carbon atoms, preferably 1 to 6 carbon atoms, or a branched alkyl group having 3 to 6 carbon atoms, a substituted or unsubstituted cycloalkyl group, or an aromatic hydrocarbon group having 6 to 20 carbon atoms, and may contain heteroatoms, and may be the same or different from each other. ７ and R ８ They may be joined together to form a ring shape. ６ Examples 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 an aminosilane compound represented by general formula (3), R ７ and R ８ R is a linear alkyl group having 1 to 12 carbon atoms, preferably 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. ７ and R ８ Examples include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, n-pentyl group, neopentyl group, and n-hexyl group. In an aminoalkoxysilane compound represented by general formula (3), R ９ R is an alkyl group having 1 to 12 carbon atoms, preferably a linear alkyl group having 1 to 6 carbon atoms, a branched alkyl group having 3 to 6 carbon atoms, a cycloalkyl group having 3 to 6 carbon atoms, a vinyl group, or an aromatic hydrocarbon group having 6 to 12 carbon atoms, and may contain heteroatoms. ９ If there are multiple instances, they may be identical or different from one another.９ Examples of these groups include methyl, ethyl, n-propyl, isopropyl, n-butyl or isobutyl, n-pentyl, neopentyl, n-hexyl, cyclopentyl, cyclohexyl, vinyl, and phenyl groups. In the aminoalkoxysilane compound represented by general formula (3), r is 0 to 2, preferably 1 to 2, and s is 1 to 3, preferably 1 to 2. Also, r+s is 1 to 3, preferably 1 to 2.

[0092] Examples of aminoalkoxysilane compounds represented by general formula (3) include alkylaminotrialalkoxysilane with r=0, s=1, bis(alkylamino)dialkoxysilane with r=0, s=2, tris(alkylamino)alkoxysilane with r=0, s=3, alkyl(alkylamino)dialkoxysilane with r=1, s=1, alkylbis(alkylamino)alkoxysilane with r=1, s=2, and dialkyl(alkylamino)alkoxysilane with r=2, s=1, preferably r=0, s=1 and R ７ and R ８ Either one of them is a hydrogen atom monoalkylaminotrialkoxysilane or r=0, s=1 and R ７ and R ８ Both are dialkylaminotrialkoxysilanes selected from linear or branched alkyl groups having 1 to 12 carbon atoms, substituted or unsubstituted cycloalkyl groups, phenyl groups, allyl groups, and aralkyl groups, more preferably dialkylaminotrialkoxysilanes such as dimethylaminotriethoxysilane, diethylaminotrimethoxysilane, diethylaminotriethoxysilane, diethylaminotri-n-propoxysilane, di-n-propylaminotriethoxysilane, methyl-n-propylaminotriethoxysilane, methyl-t-butylaminotriethoxysilane, ethyl-n-propylaminotriethoxysilane, ethylisopropylaminotriethoxysilane, and methylethylaminotriethoxysilane, and particularly preferably dimethylaminotriethoxysilane, diethylaminotrimethoxysilane, and diethylaminotriethoxysilane.

[0093] The catalyst for olefin copolymerization according to the present invention comprises (I) a solid catalyst component for olefin copolymerization according to the present invention, (II) an organoaluminum compound represented by general formula (1), and optionally (III) an external electron-donating compound, i.e., a contact thereof. The catalyst for olefin copolymerization according to the present invention may be prepared by contacting (I) a solid catalyst component for olefin copolymerization according to the present invention, (II) an organoaluminum compound represented by general formula (1), and optionally (III) an external electron-donating compound in the absence of olefins, or, as described below, by contacting them in the presence of olefins (within the polymerization system).

[0094] In the olefin copolymerization catalyst according to 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 mixture of (I) solid catalyst components for olefin copolymerization contains 1 to 2,000 moles of (II) organoaluminum compound per mole of titanium atoms, and more preferably 50 to 1,000 moles. Furthermore, the olefin copolymerization catalyst according to the present invention preferably contains 0.002 to 10,000 moles of (III) external electron-donating compound per mole of (II) organoaluminum compound, more preferably 0.010 to 2,000 moles, and even more preferably 0.010 to 0.500 moles.

[0095] According to the present invention, it is possible to provide a catalyst for olefin copolymerization that exhibits excellent rigidity and impact resistance when compared under similar polymerization conditions, and that enables the simple production of olefin copolymers that achieve both.

[0096] Next, a method for producing olefin copolymers according to the present invention will be described. The method for producing olefin copolymers according to the present invention is characterized by performing copolymerization of olefins using the olefin copolymerization catalyst according to the present invention.

[0097] In the method for producing olefin copolymers according to the present invention, the olefins to be polymerized can be two or more α-olefins selected from α-olefins having 2 to 20 carbon atoms, and more preferably two or more α-olefins selected from ethylene, propylene, 1-butene, 1-pentene, 4-methyl-1-pentene, vinylcyclohexane, etc. In the above olefin copolymer, if one of the olefins to be polymerized is propylene, the other olefin copolymerized with propylene can be one or more selected from ethylene, 1-butene, 1-pentene, 4-methyl-1-pentene, vinylcyclohexane, etc., and more preferably one or more selected from ethylene and 1-butene, with ethylene being more preferred.

[0098] In the method for producing olefin copolymers according to the present invention, the olefins are typically copolymerized by contacting the olefin copolymerization catalyst according to the present invention with two or more olefins.

[0099] When the catalyst for olefin copolymerization according to 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 organoaluminum compound represented by the above-mentioned general formula (1) at a rate of 1 to 2000 moles per mole of titanium atoms in the above-mentioned solid catalyst component mixture for olefin copolymerization, and more preferably 50 to 1000 moles. Furthermore, it is preferable to contact an external electron-donating compound selected from the compounds represented by the above-mentioned general formula (2) or general formula (3) at a rate of 0.002 to 10,000 moles per mole of the above-mentioned organoaluminum compound, more preferably 0.01 to 2 moles, and even more preferably 0.010 to 0.500 moles.

[0100] The order in which the components constituting the above-mentioned olefin copolymerization catalyst come into contact is arbitrary, but preferably, the above-mentioned organoaluminum compound is first charged into the polymerization system, then, if necessary, an external electron-donating compound is charged and brought into contact, and then the above-mentioned solid catalyst component mixture for olefin copolymerization is charged and brought into contact. The above-mentioned solid catalyst component mixture for olefin copolymerization may be a mixture of the first solid catalyst component for olefin copolymerization and the second solid catalyst component for olefin copolymerization that is charged into the polymerization system, or the first solid catalyst component for olefin copolymerization and the second solid catalyst component for olefin copolymerization may be charged separately and then mixed in the polymerization system.

[0101] The method for producing olefin copolymers according to 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 copolymerization 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.

[0102] In addition, when polymerizing olefins using the olefin copolymerization catalyst according to 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.

[0103] When performing prepolymerization, the order in which the components constituting the olefin copolymerization catalyst and the monomers (olefins) are brought into contact is arbitrary, but preferably, an organoaluminum compound is first charged into a prepolymerization system set in an inert gas atmosphere or an olefin gas atmosphere, then the above-mentioned solid catalyst component mixture for olefin copolymerization is charged and brought into contact, and then olefins such as propylene are brought into contact, either alone or as a mixture of olefins such as propylene and one or more other olefins. When an external electron-donating compound is further charged into the prepolymerization system in the above prepolymerization, an organoaluminum compound is first charged into a prepolymerization system set in an inert gas atmosphere or an olefin gas atmosphere, then the external electron-donating compound is charged and brought into contact, and then the above-mentioned solid catalyst component mixture for olefin copolymerization is brought into contact, and then olefins such as propylene are brought into contact, either alone or as a mixture of olefins such as propylene and one or more other olefins.

[0104] In the method for producing olefin copolymers according to 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.

[0105] 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.

[0106] 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.

[0107] In the method for producing olefin copolymers according to the present invention, the block copolymerization reaction between propylene and other α-olefins can usually be carried out by first contacting propylene alone or propylene with a small amount of α-olefin (such as ethylene) in the presence of the olefin copolymerization catalyst according to the present invention, and then contacting propylene with α-olefin (such as ethylene) in the subsequent step. The polymerization reaction in the first 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.

[0108] 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, and even more preferably 65 to 80°C, and the polymerization pressure is preferably 10 MPa or less, more preferably 6 MPa or less, and even more preferably 5 MPa or less. In the 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.

[0109] In particular, ethylene-propylene block copolymers contain EPR components (polymerization components of ethylene and propylene), and when EPR components seep onto the surface of polymer particles, the particles become sticky (adhesive) and their fluidity deteriorates. Since poor particle fluidity reduces the operability of polymer manufacturing facilities, it is desirable to select a polymer manufacturing method that can suppress the seepage of EPR components onto the particle surface.

[0110] In the olefin copolymer obtained by the manufacturing method according to the present invention, the flexural modulus (FM), which is an indicator of stiffness, can be easily controlled to a desired range.

[0111] In this application, the flexural modulus (FM) of the copolymer refers to the value measured at a measurement ambient temperature of 23°C, in accordance with JIS K7171, using an injection-molded test specimen measuring 4.0 mm in thickness, 10.0 mm in width, and 170.0 mm in length, prepared using NEX-III-3EG manufactured by Nissei Plastic Industrial Co., Ltd., under conditions of a molding temperature of 180°C and a mold temperature of 40°C (unit: MPa).

[0112] In the olefin copolymer obtained by the manufacturing method according to the present invention, the IZOD impact strength, which is an indicator of impact resistance, can be easily controlled to a desired range.

[0113] In this application, the IZOD impact strength of an olefin copolymer refers to the value measured by the following method. <Method for measuring IZOD impact strength> 0.10% by weight of IRGANOX 1010 (manufactured by BASF) and 0.10% by weight of IRGAFOS 168 (manufactured by BASF) are added to the olefin copolymer, and the mixture is kneaded in a twin-screw kneader to form granules to obtain olefin copolymer pellets. Next, the obtained olefin copolymer pellets are introduced into an injection molding machine (mold temperature: 40°C, cylinder temperature: 180°C) and injection molded to prepare a specimen for property measurement. The above-mentioned characteristic measurement specimens are cut to the shape shown below, conditioned in a temperature-controlled chamber maintained at 23°C for 72 hours or more, and then notched using an automatic notching machine (manufactured by Yasuda Seiki Seisakusho Co., Ltd.). Subsequently, the IZOD impact strength of the notched characteristic measurement specimens is measured at 23°C using an IZOD impact strength tester (Yasuda Seiki Seisakusho Co., Ltd., Impact Tester No. 258-L (with low-temperature chamber)) under the following measurement conditions, based on JIS K 7110 ("Method of Izod Impact Test For Rigid Plastics") (unit: kJ / m). ２). ) . Specimen shape for characteristic measurement: 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)

[0114] The olefin copolymer obtained by the manufacturing method according to the present invention satisfies the above-mentioned IZOD impact strength requirements, and therefore can easily exhibit excellent impact resistance.

[0115] According to the present invention, it is possible to provide a method for producing olefin copolymers that exhibit excellent rigidity and impact resistance when compared under similar polymerization conditions, thereby achieving both.

[0116] 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.

[0117] (Performance Evaluation) In the examples and comparative examples, each performance evaluation was performed according to the method described below.

[0118] <Titanium Atom Content> The titanium atom content was measured according to the method of JIS 8311-1997 using a solid catalyst component for olefin copolymerization from which solvent components had been completely removed by preheating and vacuum drying.

[0119] <Content of internally electron-donating compounds> The content of internally electron-donating compounds (succinate diester compounds and phthalate diester compounds) was determined by hydrolyzing solid catalyst components for olefin copolymerization, from which solvent components had been completely removed by preheating and vacuum drying. The internally electron-donating compounds were then extracted using an aromatic solvent, and this solution was measured using gas chromatography (GC-14B, Shimadzu Corporation) under the following conditions (gas chromatography FID method). The number of moles of each component was determined from the gas chromatography measurement results using a calibration curve that had been measured at known concentrations beforehand. [Measurement Conditions] Column: Packed column (φ2.6 × 2.1 m, Silicone SE-30 10%, Chromosorb WAW DMCS 80 / 100, manufactured by GL Sciences Co., Ltd.) Detector: FID (Flame Ionization Detector) Carrier gas: Helium, flow rate 40 mL / min Measurement temperature: Vaporization chamber 280°C, column 225°C, detector 280°C

[0120] <Polymerization Activity> The polymerization activity per gram of mixed solid catalyst components was determined by the following formula (α): Polymerization activity (g / g-cat) = Mass of polymer (g) / Mass of solid catalyst component mixture (g) (α)

[0121] <Melting Flow Rate (MFR)> The melt flow rate (MFR) (g / 10 min), which indicates the melting flowability of the polymer, was measured in accordance with ASTM D 1238 and JIS K 7210.

[0122] <Blocking Rate (Mass %)> The blocking rate of the olefin copolymer was calculated using the following formula: Blocking rate (Mass %) = {(I (g) - G (g)) / (I (g) - F (g))} × 100 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).

[0123] <Flexural Modulus (FM)> Using NEX-III-3EG manufactured by Nissei Plastic Industrial Co., Ltd., an injection-molded test specimen (thickness 4.0 mm, width 10.0 mm, length 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 polymer was measured at a measurement ambient temperature of 23°C in accordance with JIS K7171.

[0124] <Method for Measuring IZOD Impact Strength> 0.10% by weight of IRGANOX 1010 (manufactured by BASF) and 0.10% by weight of IRGAFOS 168 (manufactured by BASF) are added to an olefin copolymer. These mixtures are kneaded in a twin-screw kneader to form granules, thereby obtaining olefin copolymer pellets. Next, the obtained olefin copolymer pellets are introduced into an injection molding machine (mold temperature: 40°C, cylinder temperature: 180°C) and injection molded to prepare specimens for characteristic measurement. The above-mentioned characteristic measurement specimens are cut to the shape shown below, conditioned in a temperature-controlled chamber maintained at 23°C for 72 hours or more, and then notched using an automatic notching machine (manufactured by Yasuda Seiki Seisakusho Co., Ltd.). Subsequently, the IZOD impact strength of the notched characteristic measurement specimens is measured at 23°C using an IZOD impact strength tester (Yasuda Seiki Seisakusho Co., Ltd., Impact Tester No. 258-L (with low-temperature chamber)) under the following measurement conditions, based on JIS K 7110 ("Method of Izod Impact Test For Rigid Plastics") (unit: kJ / m). ２ ). ) . Specimen shape for characteristic measurement: 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)

[0125] (Production Example 1) 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 (545.8 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, 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 17.4% by mass, respectively.

[0126] (Production Example 2) Synthesis of Solid Catalyst Component (b) for Polymerization of Olefins Containing a Phthalate Diester Compound Di-n-propyl 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-propyl phthalate was added to the mixed solution, which was maintained at a liquid temperature of -10°C. (iii) The above initial contact-containing solution was reacted at 110°C for 180 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 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 and liquid were separated to obtain a solid catalyst component (solid catalyst component for polymerization of olefins containing phthalate diester compound (b)). The solid and liquid of the obtained solid catalyst component were 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.

[0127] (Example 1) <Preparation of Ethylene-Propylene Copolymerization Catalyst> Solid catalyst component (a) for olefin polymerization containing succinate diester compound and solid catalyst component (b) for olefin polymerization containing phthalate diester compound were collected in a heat-resistant glass bottle in a mass ratio of (a) to (b) = 10:90, and then mixed by shaking to obtain a solid catalyst component mixture. The composition of the obtained solid catalyst component mixture is shown in Table 1. Next, an ethylene-propylene copolymerization catalyst was prepared by charging 2.2 mmol of triethylaluminum, 0.22 mmol of dicyclopentylbis(ethylamino)silane (calculated in terms of silicon atoms), and a total of 6.2 mg (0.0031 mmol in terms of titanium atoms) of the above solid catalyst component mixture (A) into a 2.0 liter autoclave with a stirrer that was completely purged with nitrogen gas.

[0128] <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 (homopolymerization) was carried out at 70°C for 45 minutes to obtain a homopolymer. 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 homopolymer (first stage) (homoactivity, 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, liquefied ethylene and liquefied propylene were introduced into the autoclave (reactor) in such a molar ratio of ethylene / propylene to 1.5 / 1.0. The temperature was then raised to 70°C, and liquefied ethylene, liquefied propylene, and hydrogen gas were introduced in such a ratio of ethylene / propylene / hydrogen to 1.6 / 2.4 / 0.09 based on the gas supply rate per minute (liters / minute). The reaction was carried out at 1.2 MPa and 70°C, adjusting the time to achieve a block rate of approximately 30% by mass, thereby obtaining an ethylene-propylene copolymer. In the above polymerization reaction, polymerization activity (homoactivity and copolymer activity), melt flow rate (MFR) of the homopolymer and copolymer, block rate of the copolymer, flexural modulus (FM) of the copolymer, and IZOD impact strength (IZOD) of the copolymer were measured. The results are shown in Table 2.

[0129] (Example 2) In the preparation of the ethylene-propylene copolymer catalyst, the mixing ratio of the succinic acid diester compound-containing solid catalyst component for olefin polymerization (a) and the phthalic acid diester compound-containing solid catalyst component for olefin polymerization (b) was changed to a mass ratio of succinic acid diester compound-containing solid catalyst component for olefin polymerization (a):phthalic acid diester compound-containing solid catalyst component for olefin polymerization (b) = 30:70, and the total amount of the solid catalyst component mixture charged was set to 5.9 mg (0.0031 mmol in terms of titanium atoms). Except for these changes, the ethylene-propylene copolymer catalyst was prepared and ethylene-propylene copolymerization was carried out in the same manner as in Example 1 to obtain an ethylene-propylene copolymer. The composition of the solid catalyst component mixture obtained in this example is shown in Table 1. In the above polymerization reaction, the polymerization activity (homoactivity and copolymer activity), melt flowability (MFR) of the homopolymer and copolymer, block ratio of the copolymer, flexural modulus (FM) of the copolymer, and IZOD impact strength (IZOD) of the copolymer were measured. The results are shown in Table 2.

[0130] (Example 3) In the preparation of the ethylene-propylene copolymer catalyst, the same molar amount of diethylaminotriethoxysilane was used instead of dicyclopentylbis(ethylamino)silane in the preparation of the ethylene-propylene copolymer catalyst and ethylene-propylene copolymerization was carried out in the same manner as in Example 1 to obtain an ethylene-propylene copolymer. The composition of the solid catalyst component mixture obtained in this example is shown in Table 1. In the above polymerization reaction, polymerization activity (homoactivity and copolymer activity), melt flowability (MFR) of the homopolymer and copolymer, block ratio of the copolymer, flexural modulus (FM) of the copolymer, and IZOD impact strength (IZOD) of the copolymer were measured. The results are shown in Table 2.

[0131] (Comparative Example 1) In the preparation of the ethylene-propylene copolymer catalyst, the only difference was that the solid catalyst component for olefin polymerization containing a succinic acid diester compound (a) was not used as the solid catalyst component, and only the solid catalyst component for olefin polymerization containing a phthalic acid diester compound (b) was used in an amount equivalent to 0.0031 millimoles of titanium atoms. The ethylene-propylene copolymer catalyst was prepared and ethylene-propylene copolymerization was carried out in the same manner as in Example 1 to obtain an ethylene-propylene copolymer. The composition of the solid catalyst component mixture obtained in this comparative example is shown in Table 1. In the above polymerization reaction, polymerization activity (homoactivity and copolymer activity), melt flowability (MFR) of the homopolymer and copolymer, block ratio of the copolymer, flexural modulus (FM) of the copolymer, and IZOD impact strength (IZOD) of the copolymer were measured. The results are shown in Table 2.

[0132] (Comparative Example 2) In the preparation of the ethylene-propylene copolymer catalyst, the mixing ratio of the succinic acid diester compound-containing solid catalyst component for olefin polymerization (a) and the phthalic acid diester compound-containing solid catalyst component for olefin polymerization (b) was changed by mass ratio to succinic acid diester compound-containing solid catalyst component for olefin polymerization (a):phthalic acid diester compound-containing solid catalyst component for olefin polymerization (b) = 70:30, and the total amount of the solid catalyst component mixture charged was set to 9.2 mg (0.0055 mmol in terms of titanium atoms). Except for these changes, the ethylene-propylene copolymer catalyst was prepared and ethylene-propylene copolymerization was carried out in the same manner as in Example 1 to obtain an ethylene-propylene copolymer. The composition of the solid catalyst component mixture obtained in this comparative example is shown in Table 1. In the above polymerization reaction, the polymerization activity (homoactivity and copolymerization activity), melt flowability (MFR) of the homopolymer and copolymer, block ratio of the copolymer, flexural modulus (FM) of the copolymer, and IZOD impact strength (IZOD) of the copolymer were measured. The results are shown in Table 2.

[0133] (Example 4) In the ethylene-propylene copolymerization, the copolymerization time was shortened to achieve a blocking rate of approximately 20% by mass, except that the reaction was carried out in the same manner as in Example 1. The ethylene-propylene copolymerization catalyst was prepared and ethylene-propylene copolymerization was performed to obtain an ethylene-propylene copolymer. The composition of the solid catalyst component mixture obtained in this example is shown in Table 3. In the above polymerization reaction, the polymerization activity (homoactivity and copolymerization activity), melt flowability (MFR) of the homopolymer and copolymer, blocking rate of the copolymer, flexural modulus (FM) of the copolymer, and IZOD impact strength (IZOD) of the copolymer were measured. The results are shown in Table 4.

[0134] (Comparative Example 3) In ethylene-propylene copolymerization, the copolymerization time was shortened to achieve a blocking rate of approximately 20% by mass. Except for this, the preparation of the ethylene-propylene copolymerization catalyst and ethylene-propylene copolymerization were carried out in the same manner as in Comparative Example 1 to obtain an ethylene-propylene copolymer. The composition of the solid catalyst component mixture obtained in this comparative example is shown in Table 3. In the above polymerization reaction, polymerization activity (homoactivity and copolymerization activity), melt flowability (MFR) of the homopolymer and copolymer, blocking rate of the copolymer, flexural modulus (FM) of the copolymer, and IZOD impact strength (IZOD) of the copolymer were measured. The results are shown in Table 4.

[0135] (Example 5) In the ethylene-propylene copolymerization, the ethylene-propylene copolymerization catalyst was prepared and ethylene-propylene copolymerization was carried out in the same manner as in Example 2, except that the copolymerization time was shortened so that the blocking rate was approximately 20% by mass. The composition of the solid catalyst component mixture obtained in this example is shown in Table 3. In the above polymerization reaction, the polymerization activity (homoactivity and copolymerization activity), melt flowability (MFR) of the homopolymer and copolymer, blocking rate of the copolymer, flexural modulus (FM) of the copolymer, and IZOD impact strength (IZOD) of the copolymer were measured. The results are shown in Table 4.

[0136]

[0137]

[0138] ​

[0139]

[0140] Tables 1 to 4 show that in Examples 1 to 5, a mixture of solid catalyst components for olefin copolymerization was used, in which a first solid catalyst component for olefin copolymerization containing magnesium, titanium, halogen, and succinic acid diester compound and a second solid catalyst component for olefin copolymerization containing magnesium, titanium, halogen, and phthalic acid diester compound were used, with the proportion of the first solid catalyst component to the total content of the first and second solid catalyst components being 1% by mass or more and less than 37% by mass. As a result, when compared under similar polymerization conditions (when comparing olefin copolymers with similar block rates), both the flexural modulus (FM) and IZOD impact strength were high, indicating that olefin copolymers with both high rigidity and impact resistance could be easily produced.

[0141] On the other hand, as can be seen from Tables 1 to 4, in Comparative Examples 1 to 3, the proportion of the first solid catalyst component for olefin copolymerization to the total content of the first and second solid catalyst components for olefin copolymerization is outside the range of 1% by mass or more and less than 37% by mass. Therefore, when compared under similar polymerization conditions (when comparing olefin copolymers with similar block ratios), the flexural modulus (FM) is low (Comparative Examples 1 and 3), the IZOD impact strength is low (Comparative Example 2), and it is clear that it is not possible to produce olefin copolymers that achieve both high rigidity and impact resistance.

[0142] According to the present invention, it is possible to provide a solid catalyst component mixture for olefin copolymerization, a catalyst for olefin copolymerization, and a method for producing olefin copolymers, which can easily produce olefin copolymers that exhibit excellent rigidity and impact resistance when compared under similar polymerization conditions, and that achieve both properties simultaneously.

Claims

1. A solid catalyst mixture for olefin copolymerization comprising a first solid catalyst component for olefin copolymerization containing magnesium, titanium, halogen, and succinate diester compound, and a second solid catalyst component for olefin copolymerization containing magnesium, titanium, halogen, and phthalate diester compound, wherein the proportion of the first solid catalyst component to the total content of the first and second solid catalyst components for olefin copolymerization is 1% by mass or more and less than 37% by mass.

2. The solid catalyst component mixture for olefin copolymerization according to claim 1, wherein the content of the succinate diester compound is 0.1 to 10.0% by mass on a solid content basis.

3. (I) A mixture of solid catalyst components for olefin copolymerization according to claim 1 or claim 2 and (II) the following general formula (1) R １ ｐ AlQ ３－ｐ (1) (wherein, R １ Q is an alkyl group having 1 to 6 carbon atoms, Q is a hydrogen atom or a halogen atom, p is 0 < p ≤ 3, and R １ If multiple R １ A catalyst for olefin copolymerization characterized by containing one or more organoaluminum compounds selected from compounds represented by (which 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).

4. (I) The solid catalyst component mixture for olefin copolymerization according to claim 1 or claim 2, (II) the following general formula (1) R １ ｐ AlQ ３－ｐ (1) (In the formula, R １ is an alkyl group having 1 to 6 carbon atoms, Q is a hydrogen atom or a halogen atom, p is 0 < p ≤ 3, and when there are a plurality of R １ , each R １ may be the same as or different from each other, and when there are a plurality of Q, each Q may be the same as or different from each other.) and one or more organoaluminum compounds selected from the compounds represented by the formula, and (III) as an external electron donor compound, the following general formula (2) R ２ R ３ Si(NHR ４ )(NHR ５ ) (2) (In the formula, R ２ and R ３ are 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 may be the same as or different from each other, and R ４ and R ５ are alkyl groups having 1 to 8 carbon atoms and may be the same as or different from each other.) and the (alkylamino)alkylsilane compound represented by the following general formula (3) R ６ ｒ Si(NR ７ R ８ ) ｓ (OR ９ ) ４－（ｒ＋ｓ） (3) (In the formula, r is 0 to 2, s is 1 to 3, and r + s is 1 to 3. R ６ is any group selected from a linear or branched alkyl group having 1 to 12 carbon atoms, a substituted or unsubstituted cycloalkyl group, a phenyl group, an allyl group, and an aralkyl group, and may contain a hetero atom. R ７ and R ８ R is a group selected from a hydrogen atom or a linear or branched alkyl group having 1 to 12 carbon atoms, a substituted or unsubstituted cycloalkyl group, a phenyl group, an allyl group, and an aralkyl group, and may contain heteroatoms, and may be the same or different from each other. ７ and R ８ They may be bonded together to form a ring shape, R ７ and R ８ They may be the same or different. Also, R ９ R is a group selected from alkyl groups, cycloalkyl groups, phenyl groups, vinyl groups, allyl groups, and aralkyl groups having 1 to 12 carbon atoms, and may contain heteroatoms. ９ The catalyst for copolymerization of olefins according to item 3 above, comprising one or more aminoalkoxysilane compounds represented by (if there are multiple, they may be the same or different from each other).

5. A method for producing an olefin copolymer, characterized by performing copolymerization of olefins using the olefin copolymerization catalyst described in claim 3 or claim 4.

6. The method for producing an olefin copolymer according to claim 5, wherein the copolymerization of the olefins is a copolymerization of propylene and ethylene.

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