Catalyst for olefin polymerization and method for producing olefin polymer

Abstract

This catalyst for olefin polymerization includes: (I) a solid catalyst component for olefin polymerization that includes at least magnesium, titanium, a halogen, and an internal electron donating compound; (II) an organic aluminum compound; and (III) an external electron donating compound, said catalyst for olefin polymerization being characterized in that in the solid catalyst for olefin polymerization, at least one or more compounds selected from first internal electron donating compounds and one or more compounds selected from second internal electron donating compounds are present as the internal electron donating compound, and at least an alkoxysilane compound and one or more compounds selected from amino silane compounds are present as the external electron donating compound. The present invention is able to provide a catalyst for olefin polymerization with which it is possible to produce an olefin polymer having excellent melt flow properties and high stiffness with a small amount of hydrogen used, as well as a method for producing an olefin polymer using said catalyst for olefin polymerization.

Description

Catalyst for olefin polymerization and method for producing olefin polymers

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

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

[0003] Polypropylene resin compositions are lightweight, highly moldable, and possess excellent chemical stability, including heat resistance and chemical resistance of molded articles. They are also very cost-effective, making them one of the most important plastic materials used in many fields. Furthermore, in fields such as automotive parts, high-rigidity polypropylene is desired for thin-walled, lightweight applications.

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

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

[0006] Japanese Patent Publication No. 2013-533367

[0007] However, when polymerizing olefins using a solid catalyst component containing diethyl succinate as an internal electron-donating compound, the rigidity increases, but the melt flowability decreases. Therefore, in order to obtain polymers with practical melt flowability using a succinate diester compound as the internal electron-donating compound, there was a problem in that a large amount of hydrogen had to be used during polymerization.

[0008] Therefore, the present invention aims to provide a catalyst for olefin polymerization that can produce olefin polymers with excellent melt flow properties and high rigidity using a small amount of hydrogen, and a method for producing olefin polymers using the same.

[0009] In order to solve the above technical problems, the present inventors conducted extensive research and found that by using a succinic acid diester compound and an internally electron-donating compound other than succinic acid diester as internally electron-donating compounds for the solid catalyst component for olefin polymerization, and by using an alkoxysilane compound represented by general formula (1) and an (alkylamino)alkylsilane compound represented by general formula (2) as externally electron-donating compounds to be combined with the solid catalyst component for olefin polymerization, sufficient melt flowability can be obtained even with a small amount of hydrogen used during polymerization. Based on this finding, the present invention was completed.

[0010] In other words, the present invention is a catalyst for olefin polymerization comprising: (1) (I) a solid catalyst component for olefin polymerization comprising at least magnesium, titanium, halogen and an internal electron-donating compound; (II) an organoaluminum compound; and (III) an external electron-donating compound, wherein the solid catalyst for olefin polymerization contains at least a first internal electron-donating compound and a second internal electron-donating compound as internal electron-donating compounds, the first internal electron-donating compound being one or more compounds selected from succinate diester compounds, the second internal electron-donating compound being one or more compounds selected from phthalate diester compounds and diester compounds other than succinate diester compounds, ether carbonate compounds and polyol ester compounds, and the external electron-donating compound being at least the following general formula (1): Si(OR １ ) ( OR ２ ) ( OR ３ ) ( OR ４ ) (1) (wherein, R １ , R ２ , R ３ and R ４is a linear alkyl group having 1 to 8 carbon atoms or a branched alkyl group having 3 to 8 carbon atoms, which may be the same or different from each other. ), and one or more compounds selected from alkoxysilane compounds represented by the following general formula (2): R ５ R ６ Si(NHR ７ )(NHR ８ )(2) (In the formula, R ５ and R ６ 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, which may be the same or different from each other, and R ７ and R ８A catalyst for the polymerization of olefins, characterized in that there is one or more compounds selected from (alkylamino)alkylsilane compounds represented by (1 to 8 C1) (where (1) is a linear alkyl group having 1 to 8 C1 or a branched alkyl group having 3 to 8 C1, and they may be the same or different from each other. (2) The catalyst for the polymerization of olefins according to claim 1, characterized in that the diester compound other than the phthalate diester compound and succinate diester compound is one or more compounds selected from the group consisting of malonic acid diester compounds, cyclohexanedicarboxylic acid ester compounds, cyclohexenedicarboxylic acid ester compounds, citraconic acid diester compounds, phenylenedibenzoate compounds, ether carbonate compounds, and polyol ester compounds. (3) The catalyst for polymerization of olefins according to (1), characterized in that, as the (I) solid catalyst component for polymerization of olefins, it contains a first internal electron-donating compound-containing solid catalyst component for polymerization of olefins (a1) which contains magnesium, titanium, halogen and the first internal electron-donating compound as an internal electron-donating compound, and a second internal electron-donating compound-containing solid catalyst component for polymerization of olefins (a2) which contains the second internal electron-donating compound as a magnesium, titanium, halogen and an internal electron-donating compound, and as the (III) external electron-donating compound, it contains an alkoxysilane compound represented by the general formula (1) and an (alkylamino)alkylsilane compound represented by the general formula (2). (4) The catalyst for polymerization of olefins according to (1), characterized in that the (I) solid catalyst component for polymerization of olefins contains magnesium, titanium, halogen and an internal electron-donating compound, the first internal electron-donating compound and the second internal electron-donating compound, as the internal electron-donating compound, and the (III) external electron-donating compound contains an alkoxysilane compound represented by the general formula (1) and an (alkylamino)alkylsilane compound represented by the general formula (2).(5) The catalyst for polymerization of olefins according to (1), characterized in that the alkoxysilane compound represented by general formula (1) is at least one selected from the group consisting of tetramethoxysilane, tetraethoxysilane, tetra(n-propoxy)silane, tetraisopropoxysilane, tetra(n-butoxy)silane, tetraisobutoxysilane, and tetrakis(2-ethylhexyloxy)silane. (6) The catalyst for polymerization of olefins according to (1), characterized in that the (alkylamino)alkylsilane compound represented by general formula (2) is at least one selected from the group consisting of diisopropylbis(ethylamino)silane, dicyclopentylbis(ethylamino)silane, dicyclohexylbis(ethylamino)silane, cyclohexylmethylbis(ethylamino)silane, and cyclohexylcyclopentylbis(ethylamino)silane. (7) The catalyst for polymerization of olefins according to (1), characterized in that the molar ratio (Y / X) of the content (Y) of the (alkylamino)alkylsilane compound represented by general formula (2) to the content (X) of the alkoxysilane compound represented by general formula (1) is 1 / 99 to 50 / 50. (8) A method for producing an olefin polymer, characterized in that the polymerization of olefins is carried out using the catalyst for polymerization of olefins according to (1).

[0011] According to the present invention, it is possible to provide a catalyst for olefin polymerization that can produce olefin polymers with excellent melt flow properties and high rigidity using a small amount of hydrogen, and a method for producing olefin polymers using the same.

[0012] The olefin polymerization catalyst of the present invention is a catalyst for olefin polymerization comprising: (I) a solid catalyst component for olefin polymerization comprising at least magnesium, titanium, halogen and an internal electron-donating compound; (II) an organoaluminum compound; and (III) an external electron-donating compound, wherein the solid catalyst for olefin polymerization contains at least a first internal electron-donating compound and a second internal electron-donating compound as internal electron-donating compounds, the first internal electron-donating compound being one or more compounds selected from succinate diester compounds, the second internal electron-donating compound being one or more compounds selected from phthalate diester compounds and diester compounds other than succinate diester compounds, ether carbonate compounds and polyol ester compounds, and the external electron-donating compound being at least the following general formula (1): Si(OR １ ) ( OR ２ ) ( OR ３ ) ( OR ４ ) (1) (wherein, R １ , R ２ , R ３ and R ４ (wherein C1 is a linear alkyl group having 1 to 8 carbon atoms or a branched alkyl group having 3 to 8 carbon atoms, and they may be the same or different from each other.) One or more compounds selected from alkoxysilane compounds represented by the following general formula (2): R ５ R ６ Si (NHR ７ ) (NHR ８ ) (2) (wherein, R ５ and R ６ 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. ７ and R ８The catalyst for polymerization of olefins is characterized by the presence of one or more compounds selected from (alkylamino)alkylsilane compounds represented by (wherein C1-C8 is a linear alkyl group or a branched alkyl group having C3-C8, and they may be the same or different from each other).

[0013] Furthermore, the present invention provides for the following forms of olefin polymerization catalysts: (I) a form containing a first internal electron-donating compound-containing solid catalyst component for olefin polymerization (a1) containing a first internal electron-donating compound and a second internal electron-donating compound-containing solid catalyst component for olefin polymerization (a2) containing a second internal electron-donating compound; and a form containing a first internal electron-donating compound and a second internal electron-donating compound-containing solid catalyst component for olefin polymerization (b) containing a first internal electron-donating compound and a second internal electron-donating compound.

[0014] In other words, the first embodiment of the present invention is an olefin polymerization catalyst comprising: (I) a solid catalyst component for olefin polymerization containing at least magnesium, titanium, halogen and an internally electron-donating compound, comprising at least a first internally electron-donating compound-containing solid catalyst component for olefin polymerization (a1) and a second internally electron-donating compound-containing solid catalyst component for olefin polymerization (a2); (II) an organoaluminum compound; and (III) an externally electron-donating compound comprising at least an alkoxysilane compound represented by general formula (1) and an (alkylamino)alkylsilane compound represented by general formula (2).

[0015] Furthermore, the second embodiment of the olefin polymerization catalyst of the present invention is an olefin polymerization catalyst comprising: (I) a solid catalyst component for olefin polymerization containing at least a first internal electron-donating compound and a second internal electron-donating compound (b) as a solid catalyst component for olefin polymerization containing at least magnesium, titanium, halogen and an internal electron-donating compound; (II) an organoaluminum compound; and (III) an external electron-donating compound comprising at least an alkoxysilane compound represented by general formula (1) and an (alkylamino)alkylsilane compound represented by general formula (2).

[0016] The first embodiment of the olefin polymerization catalyst of the present invention contains, as a solid catalyst component for olefin polymerization, (I) at least a first internally electron-donating compound-containing solid catalyst component for olefin polymerization (a1) and a second internally electron-donating compound-containing solid catalyst component for olefin polymerization (a2).

[0017] The first solid catalyst component (a1) for olefin polymerization containing a first internal electron-donating compound according to the first embodiment of the present invention is a solid catalyst component for olefin polymerization containing at least magnesium, titanium, halogen, and a first internal electron-donating compound, wherein the first internal electron-donating compound is one or more compounds selected from succinate diester compounds.

[0018] Examples of solid catalyst components (a1) for polymerization of olefins containing a first internal electron-donating compound include a catalytic reaction product obtained by bringing a raw material component that serves as a source of magnesium, a raw material component that serves as a source of titanium and halogen, and a first internal electron-donating compound, which is an internal electron-donating compound, into contact with each other in an organic solvent. Specifically, examples include using dialkoxymagnesium as the raw material component that serves as the source of magnesium, and a tetravalent titanium-halogen compound as the raw material component that serves as the source of titanium and halogen, and bringing these raw materials into contact with an internal electron-donating compound containing a first internal electron-donating compound.

[0019] In the solid catalyst component for polymerization of olefins containing a first internally electron-donating compound (a1), the solid catalyst component for polymerization of olefins containing a second internally electron-donating compound (a2), and the solid catalyst component for polymerization of olefins containing the first internally electron-donating compound and the second internally electron-donating compound (b), the dialkoxymagnesium, which is the raw material component that serves as the source of magnesium, can be one or more compounds selected from magnesium dihalides, dialkylmagnesium, alkylmagnesium halides, dialkoxymagnesium, diaryloxymagnesium, alkoxymagnesium halides, or fatty acid magnesium. Among these magnesium compounds, magnesium dihalides, a mixture of magnesium dihalides and dialkoxymagnesium, and dialkoxymagnesium are preferred, with dialkoxymagnesium being particularly preferred.

[0020] Examples of dialkoxymagnesium include dimethoxymagnesium, diethoxymagnesium, dipropoxymagnesium, dibutoxymagnesium, ethoxymethoxymagnesium, ethoxypropoxymagnesium, and butoxyethoxymagnesium. These dialkoxymagnesiums may also be obtained by reacting metallic magnesium with an alcohol in the presence of a halogen or a halogen-containing metal compound. Furthermore, one or more of the above-mentioned dialkoxymagnesiums can be used in combination.

[0021] The above-mentioned dialkoxymagnesium is preferably in granular or powder form, and may be of an irregular shape or spherical.

[0022] When spherical dialkoxymagnesium is used, a polymer powder with a better particle shape (more spherical) and a narrower particle size distribution can be obtained, improving the handling of the polymer powder generated during the polymerization operation and suppressing the occurrence of blockages and other problems caused by fine particles contained in the generated polymer powder.

[0023] The spherical dialkoxymagnesium particles described above do not necessarily have to be perfectly spherical; elliptical or potato-shaped particles can also be used. Specifically, the particle shape is such that the ratio of the major axis diameter l to the minor axis diameter w (l / w) is 3 or less, preferably 1 to 2, and more preferably 1 to 1.5.

[0024] 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.

[0025] Furthermore, regarding the particle size distribution of dialkoxymagnesium, it is preferable to have a narrow particle size distribution with few fine and coarse particles. Specifically, when measured using a laser scattering diffraction particle size analyzer, it is preferable that 20% or less of the particles have a particle size of 5.0 μm or less, and more preferably 10% or less. On the other hand, when measured using a laser scattering diffraction particle size analyzer, it is preferable that 20% or less of the particles have a particle size of 100.0 μm or more, and more preferably 10% or less. Furthermore, when the particle size distribution is expressed as ln(D90 / D10), it is preferable that it is 3 or less, and more preferably 2 or less. Here, D90 represents the particle size that accounts for 90% of the integrated particle size in the volume integrated particle size distribution when measured using a laser scattering diffraction particle size analyzer. Also, D10 represents the particle size that accounts for 10% of the integrated particle size in the volume integrated particle size distribution when measured using a laser scattering diffraction particle size analyzer.

[0026] 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.

[0027] Dialkoxymagnesium has a specific surface area of ​​5 m². ２ Preferably, it is 5 to 50 m ２ It is more preferable that the amount is / g, and 10 to 40m ２ A value of / g is even more preferable. By using a dialkoxymagnesium with a specific surface area within the above range, a solid catalyst component for olefin polymerization having a desired specific surface area can be easily prepared.

[0028] In this application, the specific surface area of ​​dialkoxymagnesium refers to the value measured by the BET method. Specifically, the specific surface area of ​​dialkoxymagnesium is the value measured by the BET method (automatic measurement) using a Mounttech Automatic Surface Area Analyzer HM model-1230 in the presence of a mixed gas of nitrogen and helium, after the sample has been vacuum-dried at 50°C for 2 hours.

[0029] The above-mentioned dialkoxymagnesium is preferably in solution or suspension form during the reaction, as this allows the reaction to proceed smoothly.

[0030] If the above-mentioned dialkoxymagnesium is a solid, it can be dissolved in a solvent that has the ability to solubilize dialkoxymagnesium to obtain a solution of dialkoxymagnesium, or suspended in a solvent that does not have the ability to solubilize dialkoxymagnesium to obtain a suspension of dialkoxymagnesium. If the dialkoxymagnesium is a liquid, it may be used as is as a solution of dialkoxymagnesium, or it may be further dissolved in a solvent that has the ability to solubilize dialkoxymagnesium to obtain a solution of dialkoxymagnesium.

[0031] Compounds that can solubilize solid dialkoxymagnesium 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 dialkoxymagnesium include one or more solvents selected from saturated hydrocarbon solvents and unsaturated hydrocarbon solvents that do not dissolve dialkoxymagnesium.

[0032] In the solid catalyst component for polymerization of olefins containing a first internally electron-donating compound (a1), the solid catalyst component for polymerization of olefins containing a second internally electron-donating compound (a2), and the solid catalyst component for polymerization of olefins containing the first internally electron-donating compound and the second internally electron-donating compound (b), 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 (3): Ti(OR ９ ) ｐ X ４－ｐ (3) (wherein, R ９ It is preferable that the compound is one or more compounds selected from the group consisting of titanium halides and alkoxy titanium halides represented by (where represents an alkyl group having 1 to 4 carbon atoms, X represents a halogen atom such as a chlorine atom, a bromine atom, or an iodine atom, and p is 0 ≤ p ≤ 3).

[0033] In the general formula (3) above, p is 0 ≤ p ≤ 3, and specifically, p can be 0, 1, 2, or 3.

[0034] Examples of titanium halides represented by the above general formula (3) include one or more compounds selected from titanium tetrachloride, titanium tetrabromide, titanium tetraiodide, etc. Examples of alkoxy titanium halides represented by the above general formula (3) include one or more compounds 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 for tetravalent titanium halogen compounds, titanium tetrahalide is preferred, and titanium tetrachloride is more preferred. These titanium compounds may be used individually or in combination of two or more.

[0035] The solid catalyst component (a1) for polymerization of olefins containing the first internal electron-donating compound contains the first internal electron-donating compound as the internal electron-donating compound.

[0036] The first internal electron-donating compound is one or more compounds selected from succinate diester compounds. Examples of succinate diester compounds include the following general formula (5):

[0037]

[0038] (In general formula (5), R １１ and R １２ R is an atom or group selected from hydrogen atoms, halogen atoms, linear alkyl groups having 1 to 12 carbon atoms, branched alkyl groups having 3 to 12 carbon atoms, vinyl groups, linear or branched alkenyl groups having 3 to 12 carbon atoms, linear or branched halogen-substituted alkyl groups having 2 to 12 carbon atoms, cycloalkyl groups having 3 to 12 carbon atoms, cycloalkenyl groups having 3 to 12 carbon atoms, aromatic hydrocarbon groups having 6 to 20 carbon atoms, nitrogen-containing groups, phosphorus-containing groups, and silicon-containing groups, and may be the same or different from each other. １３ and R １４Examples of succinic acid diester compounds are those represented by (where each is independently a linear alkyl group having 1 to 12 carbon atoms, a branched alkyl group having 3 to 12 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms, a cycloalkenyl group having 3 to 12 carbon atoms, or an aromatic hydrocarbon group having 6 to 20 carbon atoms, which may be the same as or different from each other). The presence of a succinic acid diester compound, which is the first internal electron-donating compound, as an internal electron-donating compound in the olefin polymerization catalyst is preferable because it increases the rigidity of the resulting polymer.

[0039] In a succinic acid diester compound represented by general formula (5), R １１ and R １２ This is an atom or group selected from a hydrogen atom, a halogen atom, a linear alkyl group having 1 to 12 carbon atoms, a branched alkyl group having 3 to 12 carbon atoms, a vinyl group, a linear alkenyl group or branched alkenyl group having 3 to 12 carbon atoms, a linear or branched halogen-substituted alkyl group having 2 to 12 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms, a cycloalkenyl group having 3 to 12 carbon atoms, an aromatic hydrocarbon group having 6 to 20 carbon atoms, a nitrogen-containing group, a phosphorus-containing group, and a silicon-containing group, preferably a linear alkyl group having 1 to 4 carbon atoms, a branched alkyl group having 3 to 5 carbon atoms, or a nitrogen-containing group, which may be the same or different from each other. １１ and R １２ When is a linear alkyl group having 2 to 4 carbon atoms or a branched alkyl group having 3 to 5 carbon atoms, specific examples include ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, n-pentyl group, isopentyl group, and neopentyl group. １１ and R １２ When R is a nitrogen-containing group, specifically, examples include an amino group and a cyano group. In a succinic acid diester compound represented by general formula (5), R １３ and R １４Each of these is independently a linear alkyl group having 1 to 12 carbon atoms, a branched alkyl group having 3 to 12 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms, a cycloalkenyl group having 3 to 12 carbon atoms, or an aromatic hydrocarbon group having 6 to 20 carbon atoms, preferably a linear alkyl group or branched alkyl group having 1 to 4 carbon atoms, and they may be the same or different from each other. １３ and R １４ When the alkyl group has 1 to 4 carbon atoms, specific examples include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, or an isobutyl group.

[0040] The succinate diester compounds are not particularly limited and include, 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 2,3-diisopropyl succinate, di-n-propyl 2,3-diisobutyl succinate; Diisopropyl succinate, diisopropyl 2,3-dimethylsuccinate, diisopropyl 2,3-diethylsuccinate, diisopropyl 2,3-di-n-propylsuccinate, diisopropylsuccinate, diisopropyl 2,3-di-n-butylsuccinate, diisopropyl 2,3-diisobutylsuccinate; di-n-butyl succinate, di-n-butyl 2,3-dimethylsuccinate, di-n-butyl 2,3-diethylsuccinate, di-n-butyl 2,3-diisopropylsuccinate, di-n-butyl 2,3-diisopropylsuccinate, di-n-butyl 2,3-diisobutylsuccinate; Diisobutyl succinate, 2,3-dimethylsuccinate, 2,3-diethylsuccinate, 2,3-di-n-propylsuccinate, 2,3-diisopropylsuccinate, 2,3-di-n-butylsuccinate, 2,3-diisobutylsuccinate; 2,3-Diisopropyl-2-cyanosuccinate diethyl, 2,3-Diisopropyl-2-cyanosuccinate di-n-butyl, 2,3-Diisopropyl-2-cyanosuccinate di-n-butyl, 2,3-Diisopropyl-2-cyanosuccinate diisobutyl, 2,3-Dicyclopentyl-2-cyanosuccinate diethyl, 2,3-Dicyclopentyl-2-cyanosuccinate di-n-butyl, 2,3-Dicyclopentyl-2-cyanosuccinate diisobutyl, 2,3-Dicyclohexyl-2-cyanosuccinate diethyl, 2,3-Dicyclohexyl-2-cyanosuccinate di-n-butyl, 2,3-Dicyclohexyl-2-cyanosuccinate diisobutyl, 2-cyclopentyl-3-cyclohexyl-2-cyanosuccinate diethyl, 2,3-diisopropyl-2-cyanosuccinate 1-isobutyl 4-ethyl, 2,3-diisopropyl-2-cyanosuccinate 1-n-butyl 4-ethyl, 2-isopropyl-3-methyl-2-cyanosuccinate diethyl, 2-isopropyl-3-ethyl-2-cyanosuccinate diethyl, 2 Examples include one or more compounds selected from diethyl isopropyl-3-n-propyl-2-cyanosuccinate, diethyl 2-isopropyl-3-butyl-2-cyanosuccinate, diethyl 2-isopropyl-3-phenyl-2-cyanosuccinate, diethyl 2-cyclohexyl-3-isopropyl-2-cyanosuccinate, and 1-ethyl-4-isobutyl 2-isopropyl-3-phenyl-2-cyanosuccinate. Among these succinate diesters, diethyl succinate, di-n-propyl succinate, di-n-butyl succinate, diisobutyl succinate, 2,3-di-n-propyl succinate diethyl, 2,3-diisopropyl succinate diethyl, 2,3-di-n-propyl succinate di-n-propyl, 2,3-diisopropyl succinate di-n-propyl, 2,3-diisopropyl succinate diisopropyl, 2,3-di-n-propyl succinate di-n-butyl succinate, 2,3-diisopropyl succinate di- n-butyl, diisobutyl 2,3-di-n-propylsuccinate, diisobutyl 2,3-diisopropylsuccinate, diethyl 2,3-diisopropyl-2-cyanosuccinate, 1-isobutyl 4-ethyl 2,3-diisopropyl-2-cyanosuccinate, diethyl 2-isopropyl-3-methyl-2-cyanosuccinate, diethyl 2-isopropyl-3-ethyl-2-cyanosuccinate, diethyl 2-cyclopentyl-3-isopropyl-2-cyanosuccinate, and di-n-butyl 2,3-diisopropyl-2-cyanosuccinate are preferably used.

[0041] Furthermore, succinate diester compounds may be used alone or in combination of two or more types.

[0042] The solid catalyst component (a1) for polymerization of olefins containing the first internal electron-donating compound contains the first internal electron-donating compound as an essential component, but may also contain other internal electron-donating compounds (hereinafter referred to as "other internal electron-donating compounds" as appropriate) as internal electron-donating compounds other than the first internal electron-donating compound.

[0043] Other internally electron-donating compounds include one or more compounds selected from carbonates, acid halides, acid amides, nitriles, acid anhydrides, and carboxylic acid esters.

[0044] Examples of other internally electron-donating compounds include one or more compounds selected from ether carbonate compounds, polyol ester compounds, cycloalkane dicarboxylic acid diesters, cycloalkene dicarboxylic acid diesters, alkyl-substituted malonic acid diesters, maleic acid diesters, and other carboxylic acid diesters. More specifically, one or more compounds selected from ether carbonate compounds such as (2-ethoxyethyl)methyl carbonate, (2-ethoxyethyl)ethyl carbonate, and (2-ethoxyethyl)phenyl carbonate, polyol ester compounds such as 9,9-bis(benzoyloxymethyl)fluorene, and cycloalkane dicarboxylic acid diesters such as cyclohexane-1,2-dicarboxylic acid diethyl are preferred.

[0045] In the solid catalyst component (a1) for olefin polymerization containing a first internal electron-donating compound, the content of the first internal electron-donating compound in the total amount of components, when calculated on a solid content basis, is 8.0 to 24.0% by mass, preferably 12.0 to 22.0% by mass, and more preferably 14.0 to 20.0% by mass. By having the content of the first internal electron-donating compound in the total amount of components, when calculated on a solid content basis, within the above range, the molecular weight distribution of the olefin polymer can be broadened and its rigidity can be increased during olefin polymerization. On the other hand, if the content of the first internal electron-donating compound in the total amount of components, when calculated on a solid content basis, is less than the above range, the molecular weight distribution will not be sufficiently broad, and if it exceeds the above range, the polymerization activity will be low.

[0046] In the first internally electron-donating compound-containing solid catalyst component (a1) for olefin polymerization, the titanium atom content in the total amount of components, when calculated on a solid content basis, is 1.0 to 6.0% by mass, preferably 1.5 to 5.0% by mass, and more preferably 2.0 to 4.5% by mass.

[0047] In the first internally electron-donating compound-containing solid catalyst component (a1) for olefin polymerization, the halogen atom content in the total amount of components, when calculated on a solid content basis, is 50.0 to 70.0% by mass, preferably 55.0 to 68.0% by mass, and more preferably 58.0 to 67.0% by mass.

[0048] In the first internally electron-donating compound-containing solid catalyst component (a1) for olefin polymerization, the magnesium atom content in the total amount of components, when calculated on a solid content basis, is 15.0 to 25.0% by mass, preferably 16.0 to 23.0% by mass, and more preferably 16.0 to 22.0% by mass.

[0049] The solid catalyst component (a1) for polymerization of olefins containing the first internal electron-donating compound is preferably prepared by contacting the above-mentioned dialkoxymagnesium, titanium halogen compound, and first internal electron-donating compound in the presence of an inert organic solvent.

[0050] In the present invention, the above-mentioned inert organic solvent is preferably one that dissolves titanium halogen compounds but does not dissolve dialkoxymagnesium. Specifically, examples include one or more solvents selected from saturated hydrocarbon organic 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-mentioned inert organic solvent is preferably a saturated hydrocarbon compound or aromatic hydrocarbon compound that is liquid at room temperature and has a boiling point of about 50 to 200°C. Among these, one or more solvents selected from hexane, heptane, octane, ethylcyclohexane, mineral oil, toluene, xylene, and ethylbenzene are preferred, and one or more solvents selected from hexane, heptane, ethylcyclohexane, and toluene are particularly preferred.

[0051] In this application, the titanium content in the solid catalyst component for olefin polymerization refers to the value measured according to the method (redox titration) described in JIS 8311-1997 "Method for determining titanium in titanium ore".

[0052] Furthermore, in this application, the magnesium content in the solid catalyst component for olefin polymerization refers to the value measured by the EDTA titration method, in which the solid catalyst component for olefin polymerization is dissolved in a hydrochloric acid solution and titrated with an EDTA solution.

[0053] Furthermore, in this application, the halogen content in the solid catalyst component for olefin polymerization refers to the value measured by a silver nitrate titration method, in which the solid catalyst component is treated with a mixed solution of sulfuric acid and pure water to make an aqueous solution, a predetermined amount is taken, and the halogen is titrated with a silver nitrate standard solution.

[0054] Furthermore, in this application, the content of succinate diester compounds in the solid catalyst component for olefin polymerization and the content of other internally electron-donating compounds added as needed refer to values ​​obtained by hydrolyzing the solid catalyst component for olefin polymerization, extracting the succinate diester compounds and other internally electron-donating compounds added as needed using an aromatic solvent, and measuring this solution by gas chromatography-FID (Flame Ionization Detector).

[0055] The first internally electron-donating compound-containing solid catalyst component (a1) for olefin polymerization can be suitably produced by the method for producing the first internally electron-donating compound-containing solid catalyst component (a1) described below.

[0056] Next, a method for producing the first internally electron-donating compound-containing solid catalyst component (a1) for olefin polymerization will be described.

[0057] A method for producing a solid catalyst component (a1) for olefin polymerization containing a first internal electron-donating compound is to bring together and react a raw material component that serves as a source of magnesium, a raw material component that serves as a source of titanium and halogen, and a first internal electron-donating compound, which is an internal electron-donating compound, in an organic solvent. Specifically, a method is to use dialkoxymagnesium as the raw material component that serves as the source of magnesium, and a tetravalent titanium-halogen compound as the raw material component that serves as the source of titanium and halogen, and bring together these raw materials and an internal electron-donating compound containing the first internal electron-donating compound to obtain a solid catalyst component (a1) for olefin polymerization containing a first internal electron-donating compound.

[0058] The contact of the above components is preferably carried out in an inert gas atmosphere, with moisture removed, in a container equipped with a stirrer, while stirring. The temperature at which the above components are brought into contact is preferably around room temperature when simply bringing the components into contact and stirring to mix them, or when dispersing or suspending them for modification treatment, but it is preferably in a relatively low temperature range, preferably in the range of -20 to 30°C. Furthermore, when a solid product is obtained by reacting the components at a high temperature while they are in contact, it is preferably a relatively high temperature range, preferably in the range of 40 to 130°C. If the reaction temperature is below 40°C, the reaction will not proceed sufficiently, and as a result the performance of the prepared solid catalyst component will be insufficient, and if it exceeds 130°C, evaporation of the solvent used will become significant, making it difficult to control the reaction. The reaction time after contact is preferably 1 minute or more, more preferably 10 minutes or more, and even more preferably 30 minutes or more.

[0059] The following provides a more specific example of the order in which each component is brought into contact when producing the first internally electron-donating compound-containing solid catalyst component (a1) for olefin polymerization. (1) Magnesium compound → internally electron-donating compound → inert organic solvent → tetravalent titanium halogen compound → (intermediate cleaning → inert organic solvent → tetravalent halogen compound) → final cleaning (2) Magnesium compound → inert organic solvent → internally electron-donating compound → tetravalent halogen compound → (intermediate cleaning → inert organic solvent → tetravalent titanium halogen compound) → final cleaning (3) Magnesium compound → tetravalent halogen compound → inert organic solvent → internally electron-donating compound → (intermediate cleaning → inert organic solvent → internally electron-donating compound → tetravalent titanium halogen compound) → final cleaning (4) Magnesium compound → tetravalent titanium halogen compound → inert organic solvent → internally electron-donating compound → (intermediate cleaning → inert organic solvent → tetravalent titanium halogen compound → internally electron-donating compound) → final cleaning (5) Magnesium compound → tetravalent halogen compound → inert organic solvent → internally electron-donating compound → (intermediate cleaning → inert organic solvent → internally electron-donating compound → tetravalent titanium halogen compound) → final cleaning (6) Magnesium compound → inert organic solvent → tetravalent titanium halogen compound → internal electron-donating compound → (intermediate washing → inert organic solvent → tetravalent titanium halogen compound → internal electron-donating compound) → final washing (7) Magnesium compound → inert organic solvent → internal electron-donating compound → tetravalent titanium halogen compound → (intermediate washing → internal electron-donating compound → inert organic solvent → tetravalent titanium halogen compound) → final washing (8) Magnesium compound → inert organic solvent → internal electron-donating compound → tetravalent titanium halogen compound → (intermediate washing → internal electron-donating compound → inert organic solvent → tetravalent titanium halogen compound) → final washing

[0060] In the above contact examples (1) to (8), "→" indicates the order of contact. For example, "magnesium compound → internal electron-donating compound" means that the magnesium compound and the internal electron-donating compound are brought into contact in this order. In addition, in the above contact examples (1) to (8), the steps enclosed in double brackets (《 》) indicate steps that can be repeated multiple times as needed, and the activity is further improved by repeating the steps enclosed in double brackets. The tetravalent halogen compound and inert organic solvent used in the steps enclosed in double brackets may be newly added or may be residues from the previous step. When adding a tetravalent titanium halogen compound, the tetravalent titanium halogen compound used in the step enclosed in double brackets may be newly added or may be residues of the tetravalent halogen compound from the previous step. In the above contact examples (1) to (8), it is preferable to perform the intermediate and final washing using a hydrocarbon compound that is liquid at room temperature, and it is preferable to wash the products obtained at each contact stage in steps other than the intermediate and final washing steps shown in the above contact examples (1) to (8).

[0061] A particularly preferred preparation method for producing the first internally electron-donating compound-containing solid catalyst component (a1) for olefin polymerization is the method described in (2), (4), (6) above, that is, a method in which a magnesium compound, dialkoxymagnesium, is suspended in an inert organic solvent such as toluene, heptane, or cyclohexane, and then titanium tetrachloride, a tetravalent titanium halogen compound, is added to the resulting suspension and brought into contact with it, and before or after contact with the suspension, one or more first internally electron-donating compounds, which are internally electron-donating compounds, are brought into contact with the suspension at -20 to 130°C and reacted. In this case, it is desirable to carry out a maturation reaction at a low temperature before or after contact with the suspension.

[0062] The solid obtained in this way may, if necessary, be washed with a liquid hydrocarbon compound at room temperature (pre-washing), then contacted with a tetravalent titanium halogen compound in the presence of the hydrocarbon compound, and the reaction treatment may be carried out at 40 to 130°C. The resulting reactant may then be washed with a liquid hydrocarbon compound at room temperature (post-washing) to obtain the desired solid catalyst component for olefin polymerization. The above pre-washing and reaction between the pre-washed product and the tetravalent titanium halogen compound may be repeated multiple times.

[0063] The preferred conditions for the above processing or washing are as follows: <Conditions for low-temperature aging reaction before or after contact with the internal electron-donating compound> The low-temperature aging temperature is preferably -20 to 70°C, more preferably -10 to 50°C, and even more preferably -5 to 30°C. The low-temperature aging time is preferably 1 minute to 6 hours, more preferably 5 minutes to 4 hours, and even more preferably 10 minutes to 3 hours.

[0064] <Reaction conditions in the step before intermediate washing> In the step before intermediate washing, the reaction temperature of the magnesium compound, internal electron-donating compound, and tetravalent titanium halogen compound in the inert organic solvent is preferably 0 to 130°C, more preferably 40 to 120°C, and even more preferably 50 to 115°C. The reaction time is preferably 0.5 to 6 hours, more preferably 0.5 to 5 hours, and even more preferably 1 to 4 hours.

[0065] <Cleaning conditions during intermediate and final cleaning> The cleaning temperature is preferably 0 to 110°C, more preferably 30 to 100°C, and even more preferably 30 to 90°C. The number of cleaning cycles is preferably 1 to 20, more preferably 1 to 15, and even more preferably 1 to 10. The hydrocarbon compounds used in the intermediate and final cleaning cycles that are liquid at room temperature are preferably aromatic hydrocarbon compounds or saturated hydrocarbon compounds that are liquid at room temperature (20°C). Specifically, aromatic hydrocarbon compounds include toluene, xylene, and ethylbenzene, and saturated hydrocarbon compounds include hexane, heptane, cyclohexane, and methylcyclohexane. Preferably, aromatic hydrocarbon compounds are used in the intermediate cleaning cycle, and saturated hydrocarbon compounds are used in the final cleaning cycle.

[0066] The ratio of each component used in the production of the solid catalyst component (a1) for polymerization of olefins containing the first internal electron-donating compound cannot be specified in general terms as it varies depending on the preparation method. However, for example, per mole of magnesium compound, the first internal electron-donating compound is preferably 0.01 to 10 moles, more preferably 0.01 to 1 mole, and even more preferably 0.02 to 0.6 moles; the tetravalent titanium halogen compound is preferably 0.5 to 100 moles, more preferably 0.5 to 50 moles, and even more preferably 1 to 10 moles; and the inert organic solvent is preferably 0.001 to 500 moles, more preferably 0.001 to 100 moles, and particularly preferably 0.005 to 10 moles.

[0067] Furthermore, in the above preparation method, other internal electron-donating compounds may be used in combination with the first internal electron-donating compound. In addition, the above contact may be carried out in the presence of other reaction reagents or surfactants, such as silicon, phosphorus, or aluminum.

[0068] In the method for producing the first internally electron-donating compound-containing solid catalyst component (a1) for olefin polymerization, preferred embodiments of the obtained first internally electron-donating compound-containing solid catalyst component (a1) are as described in detail in the description of the first internally electron-donating compound-containing solid catalyst component (a1) for olefin polymerization.

[0069] The solid catalyst component (a2) for olefin polymerization containing a second internal electron-donating compound according to the first embodiment of the present invention is a solid catalyst component for olefin polymerization that contains at least magnesium, titanium, halogen, and a second internal electron-donating compound as the internal electron-donating compound.

[0070] Examples of solid catalyst components (a2) for olefin polymerization containing a second internal electron-donating compound include a catalytic reaction product obtained by bringing a raw material component that serves as a source of magnesium, a raw material component that serves as a source of titanium and halogen, and a second internal electron-donating compound, which is an internal electron-donating compound, into contact with each other in an organic solvent and reacting them. Specifically, examples include using dialkoxymagnesium as the raw material component that serves as the source of magnesium, and a tetravalent titanium-halogen compound as the raw material component that serves as the source of titanium and halogen, and bringing these raw materials into contact with an internal electron-donating compound containing a second internal electron-donating compound.

[0071] In the second solid catalyst component for olefin polymerization containing an internally electron-donating compound (a2), the dialkoxymagnesium, which is a raw material component that serves as a source of magnesium, is the same as the dialkoxymagnesium, which is a raw material component that serves as a source of magnesium in the first solid catalyst component for olefin polymerization containing an internally electron-donating compound (a1).

[0072] In the second internally electron-donating compound-containing solid catalyst component for olefin polymerization (a2), the tetravalent titanium halogen compound, which is a raw material component that serves as a source of titanium and halogen, is the same as the tetravalent titanium halogen compound, which is a raw material component that serves as a source of titanium and halogen, in the first internally electron-donating compound-containing solid catalyst component for olefin polymerization (a1).

[0073] The solid catalyst component (a2) for polymerization of olefins containing a second internal electron-donating compound contains a second internal electron-donating compound as the internal electron-donating compound.

[0074] The second internal electron-donating compound is one or more compounds selected from "diester compounds other than phthalate diester compounds and succinate diester compounds," "ether carbonate compounds," and "polyol ester compounds." The presence of the second internal electron-donating compound as an internal electron-donating compound in the olefin polymerization catalyst allows for the production of polypropylene polymers with high MFR by using an appropriate external donor during polymerization.

[0075] Examples of diester compounds other than phthalate diester compounds and succinate diester compounds related to the second internal electron-donating compound include malonic acid diester compounds, alkylidene malonic acid diester compounds, cyclohexane dicarboxylic acid ester compounds, cyclohexene dicarboxylic acid ester compounds, citraconic acid diester compounds, and phenylenedibenzoate compounds. Preferably, alkylidene malonic acid diester compounds, cyclohexane dicarboxylic acid ester compounds, 1-cyclohexene-1,2-dicarboxylic acid ester compounds, 4-cyclohexene-1,2-dicarboxylic acid ester compounds, citraconic acid diester compounds, and phenylenedibenzoate compounds.

[0076] Furthermore, examples of secondary internal electron-donating compounds include ether carbonate compounds such as (2-ethoxyethyl)methyl carbonate, (2-ethoxyethyl)ethyl carbonate, (2-propoxyethyl)propyl carbonate, (2-butoxyethyl)butyl carbonate, (2-butoxyethyl)ethyl carbonate, (2-ethoxyethyl)propyl carbonate, (2-ethoxyethyl)phenyl carbonate, and (2-ethoxyethyl)p-methylphenyl carbonate. Examples of secondary internal electron-donating compounds include polyol ester compounds such as 9,9-bis(benzoyloxymethyl)fluorene, 9,9-bis((m-methoxybenzoyloxy)methyl)fluorene, 9,9-bis((m-chlorobenzoyloxy)methyl)fluorene, 9,9-bis((p-chlorobenzoyloxy)methyl)fluorene, 9,9-bis(cinnamoyloxymethyl)fluorene, 9-(benzoyloxymethyl)-9-(propionyloxymethyl)fluorene, 9,9-bis(propionyloxymethyl)fluorene, 9,9-bis(acryloyloxymethyl)fluorene, 9,9-bis(pivalyloxymethyl)fluorene, and 9,9-fluororange methanol dibenzoate.

[0077] Examples of malonic acid diester compounds include the following general formula (7):

[0078] R １８ R １９ C (COOR２０ ) (COOR ２１ ) (7)

[0079] (In general formula (7), R １８ and R １９ R may be any of the following: a hydrogen atom, a halogen atom, a linear alkyl group having 1 to 20 carbon atoms, a branched alkyl group having 3 to 20 carbon atoms, a cycloalkyl group or cycloalkenyl group having 3 to 20 carbon atoms, an aromatic hydrocarbon group having 6 to 12 carbon atoms, a vinyl group, a linear or branched alkenyl group having 3 to 20 carbon atoms, and an alkyl group having 1 to 10 carbon atoms substituted with one or two halogen atoms, and may be the same or different. ２０ and R ２１ Examples of malonic acid diester compounds represented by ) include a linear alkyl group having 1 to 20 carbon atoms, a branched alkyl group having 3 to 20 carbon atoms, a cycloalkyl group or cycloalkenyl group having 3 to 20 carbon atoms, an aromatic hydrocarbon group having 6 to 12 carbon atoms, a vinyl group, or a linear or branched alkenyl group having 3 to 20 carbon atoms, and these may be the same or different.

[0080] In the malonic acid diester compound represented by the above general formula (7), R １８ and R １９ When R is a halogen atom, the halogen atom can be a chlorine atom, a bromine atom, an iodine atom, or a fluorine atom, and preferably a chlorine atom or a bromine atom. １８ and R １９ The C3-C10 branched alkyl group containing one or more secondary, tertiary, or quaternary carbons is preferred, and isobutyl, t-butyl, isopentyl, and neopentyl groups are particularly preferred. Furthermore, in the malonic acid diester compound represented by the above general formula (7), the R is the ester residue of the carbonyl group. ２０ and R ２１ Alkyl groups are preferred, particularly linear alkyl groups having 1 to 8 carbon atoms or branched alkyl groups having 3 to 8 carbon atoms. Specifically, these include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, t-butyl group, n-pentyl group, isopentyl group, neopentyl group, n-heptyl group, 2,2-dimethylpentyl group, and isooctyl group.

[0081] The malonate diester compound is not particularly limited and includes, for example, unsubstituted malonate diesters such as diethyl malonate, di-n-propyl malonate, diisopropyl malonate, di-n-butyl malonate, diisobutyl malonate, di-n-pentyl malonate, dineopentyl malonate, and diisooctyl malonate; Dimethyl methylmalonate, diethyl methylmalonate, di-n-propyl methylmalonate, diisopropyl methylmalonate, di-n-butyl methylmalonate, diisobutyl methylmalonate, dineopentyl methylmalonate, diisooctyl methylmalonate, dimethyl ethylmalonate, diethyl ethylmalonate, di-n-propyl ethylmalonate, diisopropyl ethylmalonate, di-n-butyl ethylmalonate, diisobutyl ethylmalonate, dineopentyl ethylmalonate, diisooctyl ethylmalonate, dimethyl propylmalonate, diethyl isopropylmalonate, dipropyl isopropylmalonate, diisopropyl isopropylmalonate, di-n-butyl isopropylmalonate, diisobutyl isopropylmalonate Monoalkyl malonate diesters such as dineopentyl isopropyl malonate, diisooctyl isopropyl malonate, dimethyl isobutyl malonate, diethyl isobutyl malonate, di-n-propyl isobutyl malonate, diisopropyl isobutyl malonate, di-n-butyl isobutyl malonate, diisobutyl isobutyl malonate, dineopentyl isobutyl malonate, diisooctyl isobutyl malonate, dimethyl isopentyl malonate, diethyl isopentyl malonate, di-n-propyl isopentyl malonate, diisopropyl isopentyl malonate, di-n-butyl isopentyl malonate, diisobutyl isopentyl malonate, dineopentyl isopentyl isopentyl malonate, and diisooctyl isopentyl malonate;Dimethyl ethylcyclopentylmalonate, diethyl ethylcyclopentylmalonate, dimethyl diisopropylmalonate, diisopropylmalonate, diisopropyl malonate, di-n-propyl diisopropylmalonate, diisopropylmalonate, diisopropylmalonate, diisopropylmalonate, diisopropylmalonate, diisopropylmalonate, diisopropylmalonate, diisopropylmalonate, diisopropylmalonate, diisooctyl diisobutylmalonate, dimethyl diisobutylmalonate, diisobutylmalonate, diisobutylmalonate, diisobutylmalonate, diisobutylmalonate, diisobutylmalonate, diisobutylmalonate, diisobutylmalonate, diisobutylmalonate, diisobutylmalonate, diisobutylmalonate, diisobutylmalonate, diisobutylmalonate, diisobutylmalonate, diisobutylmalonate, diisobutylmalonate, diisobutylmalonate, diisobutylmalonate, diisobutylmalonate, diisobutylmalonate, diisobutylmalonate, diisobutylmalonate, diisobutylmalonate, diisobutylmalonate, diisobutylmalonate, diisobutylmalonate, diisobutylmalonate, diisobutylmalonate Examples of dialkyl malonate diesters include di-n-propyl diisopentylmalonate, diisopropyl diisopentylmalonate, di-n-butyl diisopentylmalonate, diisobutyl diisopentylmalonate, di-neopentyl diisopentylmalonate, diethyl isopropylisobutylmalonate, di-n-propyl isopropylisobutylmalonate, diisopropylisobutylmalonate, di-n-butyl isopropylisobutylmalonate, diisopropylisobutylmalonate, dineopentyl isopropylisopentylmalonate, dimethyl isopropylisopentylmalonate, diethyl isopropylisopentylmalonate, di-n-propyl isopropylisopentylmalonate, diisopropylisopentylmalonate, diisopropylisopentylmalonate, di-n-butyl isopropylisopentylmalonate, diisobutyl isopropylisopentylmalonate, and dineopentyl isopropylisopentylmalonate. Among the above, monoalkylmalonate diesters and dialkylmalonate diesters are preferred, and dialkylmalonate diesters such as ethylcyclopentylmalonate dimethyl, ethylcyclopentylmalonate diethyl, diisobutylmalonate dimethyl, diisobutylmalonate diethyl, and diisobutylmalonate diisopropyl are particularly preferred.

[0082] Furthermore, malonic acid diester compounds may be used alone or in combination of two or more types.

[0083] Examples of alkylidenemalonic acid diester compounds include the following general formula (8): R ２２ R ２３ C = C (COOR ２４ ) (COOR ２５ ) (8) (wherein, R ２２ and R ２３ R is independently a group or atom selected from a hydrogen atom, a halogen atom, a linear alkyl group having 1 to 20 carbon atoms, a branched alkyl group having 3 to 20 carbon atoms, a vinyl group, a linear or branched alkenyl group having 3 to 20 carbon atoms, a halogen-substituted alkyl group having 2 to 20 carbon atoms, a cycloalkyl group or cycloalkenyl group having 3 to 20 carbon atoms, an aromatic hydrocarbon group having 6 to 20 carbon atoms, a nitrogen-containing group, an oxygen-containing group, a phosphorus-containing group, and a silicon-containing group, provided that R ２２ and R ２３ They are either identical or different, and can optionally combine with each other to form a ring, R ２２ When R is a hydrogen atom or a methyl group ２３ It has two or more carbon atoms, R ２４ and R ２５ R is independently a linear alkyl group having 1 to 20 carbon atoms, a branched alkyl group having 3 to 20 carbon atoms, a vinyl group, a linear or branched alkenyl group having 3 to 20 carbon atoms, a cycloalkyl group or cycloalkenyl group having 3 to 20 carbon atoms, or an aromatic hydrocarbon group having 6 to 20 carbon atoms, provided that R ２４ and R ２５ One or more compounds selected from alkylidenemalonic acid diester compounds represented by (which are either the same or different).

[0084] In the alkylidenemalonic acid diester compound represented by the above general formula (8), R ２２ and R ２３ When is a halogen atom, the halogen atom is a chlorine atom, a bromine atom, an iodine atom, or a fluorine atom, preferably a chlorine atom, a bromine atom, or an iodine atom, and more preferably a chlorine atom or a bromine atom. ２２ and R ２３Examples include linear alkyl groups having 1 to 20 carbon atoms such as methyl group, ethyl group, n-propyl group, n-butyl group, n-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, n-nonyl group, and n-decyl group.

[0085] R ２２ and R ２３ Examples include branched alkyl groups having 3 to 20 carbon atoms and containing a secondary carbon atom or a tertiary carbon atom, such as isopropyl group, isobutyl group, t-butyl group, isopentyl group, and neopentyl group. R ２２ and R ２３ Examples include linear alkenyl groups having 3 to 20 carbon atoms such as n-propenyl group, n-butenyl group, n-pentenyl group, n-hexenyl group, n-heptenyl group, n-octenyl group, n-nonenyl group, and n-decenyl group. R ２２ and R ２３ Examples include branched alkenyl groups having 3 to 20 carbon atoms and containing a secondary carbon atom or a tertiary carbon atom, such as isopropenyl group, isobutenyl group, t-butenyl group, isopentyl group, and neopentyl group.

[0086] R ２２ and R ２３ Examples include linear or branched halogen-substituted alkyl groups having 2 to 20 carbon atoms such as methyl halide group, ethyl halide group, n-propyl halide group, isopropyl halide group, n-butyl halide group, isobutyl halide group, n-pentyl halide group, n-hexyl halide group, n-heptyl halide group, n-octyl halide group, nonyl halide group, and decyl halide group. Examples of the halogen atoms of these halogen-substituted alkyl groups include fluorine atom, chlorine atom, bromine atom, and iodine atom.

[0087] R ２２ and R ２３Examples include cycloalkyl groups having 3 to 20 carbon atoms such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, and cyclodecyl groups. R ２２ and R ２３ Examples include cycloalkenyl groups having 3 to 20 carbon atoms such as cyclopropenyl, cyclobutenyl, cyclopentenyl, cyclohexenyl, cycloheptenyl, cyclooctenyl, cyclononenyl, and cyclodecenyl groups.

[0088] R ２２ and R ２３ Examples include aromatic hydrocarbon groups having 6 to 20 carbon atoms such as phenyl, methylphenyl, dimethylphenyl, ethylphenyl, benzyl, 1-phenylethyl, 2-phenylethyl, 2-phenylpropyl, 1-phenylbutyl, 4-phenylbutyl, 2-phenylheptyl, tolyl, xylyl, and naphthyl groups.

[0089] R ２２ When is a hydrogen atom or a methyl group, the number of carbon atoms of R ２３ is 2 or more. R ２２ and R ２３ are optionally bonded to each other to form a ring. R ２２ R ２３ as well as R ２２ and R ２３ Examples of the ring formed by the carbon atoms bonded to include cycloalkyl rings, fluorenyl rings, indenyl rings, imidazole rings, piperidinyl rings, and the like.

[0090] R ２２ and R ２３ are preferably a hydrogen atom, a linear alkyl group having 1 to 6 carbon atoms, a branched alkyl group having 3 to 6 carbon atoms, a vinyl group, a linear or branched alkenyl group having 3 to 6 carbon atoms, a cycloalkyl group having 5 or 6 carbon atoms, a cycloalkenyl group having 5 or 6 carbon atoms, or an aromatic hydrocarbon group having 6 to 10 carbon atoms. R ２２is a linear alkyl group having a hydrogen atom or 1 to 6 carbon atoms, and R ２３ It is particularly preferable that the group is a linear alkyl group having 1 to 6 carbon atoms, a branched alkyl group having 3 to 6 carbon atoms, a cycloalkyl group having 5 or 6 carbon atoms, or an aromatic hydrocarbon group having 6 to 10 carbon atoms.

[0091] R ２４ and R ２５ It is preferable that the R is a linear alkyl group having 1 to 10 carbon atoms or a branched alkyl group having 3 to 8 carbon atoms. ２４ and R ２５ It is particularly preferable that the element is a linear alkyl group having 1 to 4 carbon atoms or a branched alkyl group having 3 or 4 carbon atoms.

[0092] Examples of alkylidenemalonate diester compounds include linear alkylidenemalonate diesters such as dimethyl propyridenemalonate, diethyl propyridenemalonate, di-n-propyl propyridenemalonate, diisobutyl propyridenemalonate, di-n-butyl propyridenemalonate, dimethyl butyridenemalonate, diethyl butyridenemalonate, di-n-propyl butyridenemalonate, diisobutyl butyridenemalonate, di-n-butyl butyridenemalonate, dimethyl pentyridenemalonate, diethyl pentyridenemalonate, di-n-propyl pentyridenemalonate, diisobutyl pentyridenemalonate, di-n-butyl pentyridenemalonate; linear alkylidenemalonate diesters such as dimethyl hexylidenemalonate, diethyl hexylidenemalonate, di-n-propyl hexylidenemalonate, diisobutyl hexylidenemalonate, and di-n-butyl hexylidenemalonate; (1-methylpropyridene) dimethyl malonate, (1-methylpropyridene) diethyl malonate, (1-methylpropyridene) di-n-propyl malonate, (1-methylpropyridene) diisobutyl malonate, (1-methylpropyridene) di-n-butyl malonate, (1-ethylpropyridene) diethyl malonate, (2-methylpropyridene) dimethyl malonate, (2-methylpropyridene) diethyl malonate, (2-methylpropyridene) di-n-propyl malonate, (2-methylpropyridene) diisobutyl malonate, (2-methylpropyridene) di-n-butyl malonate, (2,2-dimethylpropyridene) diethyl malonate; (2-methylbutylidene) dimethyl malonate Chil, (2-methylbutylidene) malonate diethyl, (2-methylbutylidene) malonate di-n-propyl, (2-methylbutylidene) malonate diisobutyl, (2-methylbutylidene) malonate di-n-butyl, (2-ethylbutylidene) malonate dimethyl, (2-ethylbutylidene) malonate diethyl, (2-ethylbutylidene) malonate di-n-propyl, (2-ethylbutylidene) malonate diisobutyl, (2-ethylbutylidene) malonate di-n-butyl, (2-ethylpentylidene) malonate dimethyl, (2-ethylpentylidene) malonate diethyl, (2-ethylpentylidene) malonate di-n-propyl, (2-ethylpentylidene) malonate diisobutyl,(2-ethylpentylidene) malonate di-n-butyl, (2-isopropylbutylidene) malonate dimethyl, (2-isopropylbutylidene) malonate diethyl, (2-isopropylbutylidene) malonate di-n-propyl, (2-isopropylbutylidene) malonate diisobutyl, (2-isopropylbutylidene) malonate di-n-butyl, (3-methylbutylidene) malonate dimethyl, (3-methylbutylidene) malonate diethyl, (3-methylbutylidene) malonate di-n-propyl, (3-methylbutylidene) malonate diisobutyl (3-methylbutylidene) malonate di-n-butyl, (2,3-dimethylbutylidene) malonate dimethyl, (2,3-dimethylbutylidene) malonate diethyl, (2,3-dimethylbutylidene) malonate di-n-propyl, (2,3-dimethylbutylidene) malonate diisobutyl, (2,3-dimethylbutylidene) malonate di-n-butyl, (2-n-propylbutylidene) malonate dimethyl, (2-n-propylbutylidene) malonate diethyl, (2-n-propylbutylidene) malonate di-n-propyl, (2-n-propylbutyl (2-n-propylbutylidene) malonate diisobutyl, (2-n-propylbutylidene) malonate di-n-butyl, (2-isobutyl-3-methylbutylidene) malonate dimethyl, (2-isobutyl-3-methylbutylidene) malonate diethyl, (2-isobutyl-3-methylbutylidene) malonate di-n-propyl, (2-isobutyl-3-methylbutylidene) malonate diisobutyl, (2-isobutyl-3-methylbutylidene) malonate di-n-butyl, (2-n-butylpentylidene) malonate dimethyl, (2-n-butylpentylidene) malonate diethyl (Linear alkylalkylidene) malonic acid diesters such as (2-n-butylpentylidene) di-n-propyl malonate, (2-n-butylpentylidene) diisobutyl malonate, (2-n-butylpentylidene) di-n-butyl malonate, (2-n-pentylhexyllidene) dimethyl malonate, (2-n-pentylhexyllidene) diethyl malonate, (2-n-pentylhexyllidene) di-n-propyl malonate, (2-n-pentylhexyllidene) diisobutyl malonate, (2-n-pentylhexyllidene) di-n-butyl malonate, (di-t-butylmethylene) dimethyl malonate,(Diisobutylmethylene)malonate diethyl, (diisobutylmethylene)malonate di-n-propyl, (diisobutylmethylene)malonate diisobutyl, (diisobutylmethylene)malonate di-n-butyl, (diisobutylmethylene)malonate dimethyl, (diisobutylmethylene)malonate diethyl, (diisobutylmethylene)malonate di-n-propyl, (diisobutylmethylene)malonate diisobutyl, (diisobutylmethylene)malonate di-n-butyl, (diisopropylmethylene)malonate dimethyl, (diisopropylmethylene)malonate diethyl, (diisopropylmethylene)malonate di-n-propyl, (diisopropylmethylene)malonate diisobutyl, (diisopropylmethylene)malonate di-n-butyl, etc. (branched alkylmethylene)malonate diesters; (Cyclohexylmethylene) dimethyl malonate, (Cyclohexylmethylene) diethyl malonate, (Cyclohexylmethylene) di-n-propyl malonate, (Cyclohexylmethylene) diisobutyl malonate, (Cyclohexylmethylene) di-n-butyl malonate, (Cyclopentylmethylene) dimethyl malonate, (Cyclopentylmethylene) diethyl malonate, (Cyclopentylmethylene) di-n-propyl malonate, (Cyclopentylmethylene) diisobutyl malonate, (Cyclopentylmethylene) di-n-butyl malonate, (Dicyclopentylmethylene) malonate Dimethyl malonate, diethyl (dicyclopentylmethylene)malonate, di-n-propyl (dicyclopentylmethylene)malonate, diisobutyl (dicyclopentylmethylene)malonate, di-n-butyl (dicyclopentylmethylene)malonate, dimethyl (dicyclohexylmethylene)malonate, diethyl (dicyclohexylmethylene)malonate, di-n-propyl (dicyclohexylmethylene)malonate, diisobutyl (dicyclohexylmethylene)malonate, di-n-butyl (dicyclohexylmethylene)malonate, etc. (cycloalkylmethylene)malonate diesters; (2-methylcyclohexylmethylene) dimethyl malonate, (2-methylcyclohexylmethylene) diethyl malonate, (2-methylcyclohexylmethylene) di-n-propyl malonate, (2-methylcyclohexylmethylene) diisobutyl malonate,(2-methylcyclohexylmethylene) malonate di-n-butyl; (2,6-dimethylcyclohexylmethylene) malonate dimethyl, (2,6-dimethylcyclohexylmethylene) malonate diethyl, (2,6-dimethylcyclohexylmethylene) malonate di-n-propyl, (2,6-dimethylcyclohexylmethylene) malonate diisobutyl, (2,6-dimethylcyclohexylmethylene) malonate di-n-butyl; (1-methyl-1-(2-methylcyclo (Alkyl-substituted cycloalkylmethylene) malonate diesters such as (1-methyl-1-(2-methylcyclohexyl)methylene) dimethyl malonate, (1-methyl-1-(2-methylcyclohexyl)methylene) diethyl malonate, (1-methyl-1-(2-methylcyclohexyl)methylene) di-n-propyl malonate, (1-methyl-1-(2-methylcyclohexyl)methylene) diisobutyl malonate, and (1-methyl-1-(2-methylcyclohexyl)methylene) di-n-butyl malonate; Benzylidenemalonate diesters such as dimethyl benzylidenemalonate, diethyl benzylidenemalonate, di-n-propyl benzylidenemalonate, ethyl n-propyl benzylidenemalonate, diisopropyl benzylidenemalonate, ethyl isopropyl benzylidenemalonate, diisobutyl benzylidenemalonate, ethyl isobutyl benzylidenemalonate, di-n-butyl benzylidenemalonate, ethyl n-butyl benzylidenemalonate, di-n-pentyl benzylidenemalonate, di-neopentyl benzylidenemalonate, di-n-hexyl benzylidenemalonate, di-n-octyl benzylidenemalonate, bis(2-ethylhexyl) benzylidenemalonate, and ethyl(2-ethylhexyl) benzylidenemalonate; (1-methylbenzylidene) dimethyl malonate, (1-methylbenzylidene) diethyl malonate, (1-methylbenzylidene) di-n-propyl malonate, (1-methylbenzylidene) diisobutyl malonate, (1-methylbenzylidene) di-n-butyl malonate, (1-ethylbenzylidene) dimethyl malonate, (1-ethylbenzylidene) diethyl malonate, (1-ethylbenzylidene) di-n-propyl malonate, (1-ethylbenzylidene) diisobutyl malonate, (1-ethylbenzylidene) di-n-butyl malonate,(1-n-propylbenzylidene) dimethyl malonate, (1-n-propylbenzylidene) diethyl malonate, (1-n-propylbenzylidene) di-n-propyl malonate, (1-n-propylbenzylidene) diisobutyl malonate, (1-n-propylbenzylidene) di-n-butyl malonate, (1-n-butylbenzylidene) dimethyl malonate, (1-n-butylbenzylidene) diethyl malonate, (1-n-butylbenzylidene) di-n-propyl malonate, (1-n-butylbenzylidene) diisobutyl malonate, (1-n-butylbenzylidene) di-n-butyl malonate, (1-n-pentylbenzylidene Linear alkyl benzylidene malonate diesters such as dimethyl malonate, diethyl malonate, di-n-propyl malonate, diisobutyl malonate, di-n-butyl malonate, dimethyl malonate, diethyl malonate, di-n-propyl malonate, diisobutyl malonate, and di-n-butyl malonate; (1-Isopropylbenzylidene)Dimethyl Malonate, (1-Isopropylbenzylidene)Diethyl Malonate, (1-Isopropylbenzylidene)Di-n-Propyl Malonate, (1-Isopropylbenzylidene)Diisobutyl Malonate, (1-Isopropylbenzylidene)Di-n-Butyl Malonate, (1-Isobutylbenzylidene)Dimethyl Malonate, (1-Isobutylbenzylidene)Diethyl Malonate, (1-Isobutylbenzylidene)Di-n-Propyl Malonate Pills, (1-isobutylbenzylidene)malonate diisobutyl, (1-isobutylbenzylidene)malonate di-n-butyl, (1-t-butylbenzylidene)malonate dimethyl, (1-t-butylbenzylidene)malonate diethyl, (1-t-butylbenzylidene)malonate di-n-propyl, (1-t-butylbenzylidene)malonate diisobutyl, (1-t-butylbenzylidene)malonate di-n-butyl, and other branched alkylbenzylidene malonate diesters; (2-methylphenylmethylene)malonate dimethyl,(2-methylphenylmethylene) diethyl malonate, (2-methylphenylmethylene) di-n-propyl malonate, (2-methylphenylmethylene) diisobutyl malonate, (2-methylphenylmethylene) di-n-butyl malonate, (4-methylphenylmethylene) dimethyl malonate; (2,6-dimethylphenylmethylene) dimethyl malonate, (2,6-dimethylphenylmethylene) diethyl malonate, (2,6-dimethylphenylmethylene) di-n-propyl malonate, (2,6-dimethylphenylmethylene) diiso Diethyl (alkyl-substituted phenylmethylene) malonates such as butyl, (2,6-dimethylphenylmethylene) di-n-butyl malonate, (1-methyl-1-(2-methylphenyl)methylene) dimethyl malonate, (1-methyl-1-(2-methylphenyl)methylene) diethyl malonate, (1-methyl-1-(2-methylphenyl)methylene) di-n-propyl malonate, (1-methyl-1-(2-methylphenyl)methylene) diisobutyl malonate, and (1-methyl-1-(2-methylphenyl)methylene) di-n-butyl malonate; Examples of (naphthylmethylene)malonic acid diesters include (naphthylmethylene) dimethyl malonate, (naphthylmethylene) diethyl malonate, (naphthylmethylene) di-n-propyl malonate, (naphthylmethylene) diisobutyl malonate, and (naphthylmethylene) di-n-butyl malonate. Examples of alkylidenemalonic acid diester compounds include benzylidenemalonate dimethyl, benzylidenemalonate diethyl, benzylidenemalonate di-n-propyl, benzylidenemalonate ethyl-n-propyl, benzylidenemalonate diisopropyl, benzylidenemalonate ethyl-isopropyl, benzylidenemalonate diisobutyl, benzylidenemalonate ethyl-isobutyl, benzylidenemalonate di-n-butyl, and benzylidenemalonic acid Benzylidenmalonate diesters such as ethyl n-butyl, di-n-pentyl benzylidenmalonate, di-neopentyl benzylidenmalonate, di-n-hexyl benzylidenmalonate, di-n-octyl benzylidenmalonate, bis(2-ethylhexyl) benzylidenmalonate, and ethyl(2-ethylhexyl) benzylidenmalonate are preferably used, as are diethyl benzylidenmalonate and di-n-propyl benzylidenmalonate.Ethyl n-propyl benzylidenemalonate, diisopropyl benzylidenemalonate, ethyl isopropyl benzylidenemalonate, diisobutyl benzylidenemalonate, ethyl isobutyl benzylidenemalonate, di-n-butyl benzylidenemalonate, ethyl n-butyl benzylidenemalonate, dineopentyl benzylidenemalonate, di-n-hexyl benzylidenemalonate, and diisooctyl benzylidenemalonate are particularly preferred.

[0093] Furthermore, alkylidenemalonate diester compounds may be used alone or in combination of two or more types.

[0094] The cyclohexanedicarboxylic acid ester compound is not particularly limited and includes, for example, dimethyl cyclohexane-1,2-dicarboxylate, diethyl cyclohexane-1,2-dicarboxylate, di-n-propyl cyclohexane-1,2-dicarboxylate, diisopropyl cyclohexane-1,2-dicarboxylate, ethyl n-butyl cyclohexane-1,2-dicarboxylate, ethyl isobutyl cyclohexane-1,2-dicarboxylate, di-n-butyl cyclohexane-1,2-dicarboxylate, diisobutyl cyclohexane-1,2-dicarboxylate, and cyclohexanedicarboxylate. Examples include compounds having a cycloalkane-1,2-dicarboxylic acid diester structure such as sun-1,2-dicarboxylate di-n-hexyl, cyclohexane-1,2-dicarboxylate di-n-heptyl, cyclohexane-1,2-dicarboxylate di-n-octyl, cyclohexane-1,2-dicarboxylate diisooctyl, and cyclohexane-1,2-dicarboxylate ethylisooctyl. Among these, cyclohexane-1,2-dicarboxylate diethyl, cyclohexane-1,2-dicarboxylate di-n-propyl, and cyclohexane-1,2-dicarboxylate diisopropyl Unsubstituted cycloalkane-1,2-dicarboxylic acid diesters such as cyclohexane-1,2-dicarboxylate ethyl n-butyl, cyclohexane-1,2-dicarboxylate ethyl isobutyl, cyclohexane-1,2-dicarboxylate di-n-butyl, cyclohexane-1,2-dicarboxylate diisobutyl, cyclohexane-1,2-dicarboxylate diisooctyl, and cyclohexane-1,2-dicarboxylate ethyl isooctyl, as well as 3-methylcyclohexane-1,2-dicarboxylate diethyl and 4-methylcyclohexane-1,2-dicarboxylate diethyl. Preferred are substituted cycloalkane dicarboxylic acid diesters in which some of the hydrogen atoms of the cycloalkyl structure are substituted with alkyl groups, such as 5-methylcyclohexane-1,2-dicarboxylate diethyl, 3,6-dimethylcyclohexane-1,2-dicarboxylate diethyl, and 3,6-dimethylcyclohexane-1,2-dicarboxylate di-n-butyl. Among these, cyclohexane-1,2-dicarboxylate diethyl, cyclohexane-1,2-dicarboxylate di-n-propyl, cyclohexane-1,2-dicarboxylate diisopropyl, and cyclohexane-1,Ethyl n-butyl 2-dicarboxylate, ethyl isobutyl cyclohexane-1,2-dicarboxylate, di-n-butyl cyclohexane-1,2-dicarboxylate, diisobutyl cyclohexane-1,2-dicarboxylate, diisooctyl cyclohexane-1,2-dicarboxylate, and ethyl isooctyl cyclohexane-1,2-dicarboxylate are more preferred.

[0095] Furthermore, cyclohexanedicarboxylic acid ester compounds may be used alone or in combination of two or more types.

[0096] Examples of cyclohexenedicarboxylic acid ester compounds include one or more compounds selected from substituted or unsubstituted 1-cyclohexene-1,2-dicarboxylic acid diesters in which alkoxycarbonyl groups are bonded to the 1st and 2nd positions of the cyclohexene ring of 1-cyclohexene, or substituted or unsubstituted 4-cyclohexene-1,2-dicarboxylic acid diesters in which alkoxycarbonyl groups are bonded to the 1st and 2nd positions of the cyclohexene ring of 4-cyclohexene.

[0097] The cyclohexenedicarboxylic acid ester compounds are not particularly limited and include, for example, 1-cyclohexene-1,2-dicarboxylate diethyl, 1-cyclohexene-1,2-dicarboxylate di-n-propyl, 1-cyclohexene-1,2-dicarboxylate di-n-butyl, 1-cyclohexene-1,2-dicarboxylate diisobutyl, 1-cyclohexene-1,2-dicarboxylate dineopentyl, 1-cyclohexene-1,2-dicarboxylate diisooctyl, 1-cyclohexene-1,2-dicarboxylate bis(2,2-dimethylhexyl), 4-cyclohexene-1,2-dicarboxylate diethyl, 4-cyclohexene-1,2-dicarboxylate di-n-propyl, 4-cyclohexene-1,2-dicarboxylate di-n-butyl, 4-cyclohexene-1,2-dicarboxylate diisobutyl, and 4-cyclohexene-1,2-dicarboxylate diethyl, 4-cyclohexene-1,2-dicarboxylate di-n-propyl, 4-cyclohexene-1,2-dicarboxylate diisobutyl, and 4-cyclohexene-1,2-dicarboxylate dipropyl Examples include dieopentyl nitrate, diisooctyl 4-cyclohexene-1,2-dicarboxylate, and bis(2,2-dimethylhexyl) 4-cyclohexene-1,2-dicarboxylate, among which 1-cyclohexene-1,2-dicarboxylate diethyl, 1-cyclohexene-1,2-dicarboxylate di-n-butyl, 1-cyclohexene-1,2-dicarboxylate diisobutyl, 1-cyclohexene-1,2-dicarboxylate dieopentyl, 1-cyclohexene-1,2-dicarboxylate diisooctyl, 4-cyclohexene-1,2-dicarboxylate diethyl, 4-cyclohexene-1,2-dicarboxylate di-n-butyl, 4-cyclohexene-1,2-dicarboxylate diisobutyl, 4-cyclohexene-1,2-dicarboxylate dieopentyl, and 4-cyclohexene-1,2-dicarboxylate diisooctyl.

[0098] Furthermore, cyclohexenedicarboxylic acid ester compounds may be used alone or in combination of two or more types.

[0099] The citraconate diester compound is not particularly limited, and examples include dimethyl citraconate, diethyl citraconate, di-n-propyl citraconate, diisopropyl citraconate, di-n-butyl citraconate, diisopropyl citraconate, di-n-butyl citraconate, diisobutyl citraconate, dineopentyl citraconate, diisooctyl citraconate, and bis(2,2-dimethylhexyl) citraconate. Among these, diethyl citraconate, di-n-butyl citraconate, diisobutyl citraconate, dineopentyl citraconate, and bis(2-ethylhexyl) citraconate are preferred.

[0100] Furthermore, the citraconic acid diester compounds may be used alone or in combination of two or more types.

[0101] Examples of phenylenedibenzoate compounds include the following general formula (9):

[0102]

[0103] (In general formula (9), R ２６ R represents an alkyl group or halogen atom having 1 to 8 carbon atoms. ２７ and R ２８ m 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 these may be the same or different from each other, and m is a substituent R ２６ The number is 0, 1, or 2, and when m is 1, R ２６ is an alkyl group, and when m is 2, R ２６ The compounds may be the same or different, but at least one of them is an alkyl group.) One or more compounds selected from phenylenediote compounds represented by ) are examples.

[0104] In a phenylenediote compound represented by general formula (9), R ２６ R is an alkyl group having 1 to 8 carbon atoms or a halogen atom, preferably a linear alkyl group having 1 to 8 carbon atoms or a branched alkyl group having 3 to 8 carbon atoms, or a halogen atom. ２６If is a halogen atom, the halogen atom can be one or more halogen atoms selected from fluorine, chlorine, bromine, and iodine atoms. ２６ When is a linear alkyl group having 1 to 8 carbon atoms or a branched alkyl group having 3 to 8 carbon atoms, examples of linear alkyl groups having 1 to 8 carbon atoms include one or more groups selected from methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, and n-octyl groups, and examples of branched alkyl groups having 3 to 8 carbon atoms include one or more groups selected from isopropyl, isobutyl, t-butyl, isopentyl, neopentyl, isohexyl, 2,2-dimethylbutyl, 2,2-dimethylpentyl, isooctyl, and 2,2-dimethylhexyl groups. ２６ Among the above, chlorine atoms, bromine atoms, methyl groups, ethyl groups, n-propyl groups, isopropyl groups, and isobutyl groups are preferred, and chlorine atoms, bromine atoms, methyl groups, and isobutyl groups are more preferred. ２７ and R ２８ These 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.

[0105] The phenylenediazole compound is not particularly limited, and for example, 1,2-phenylenediacetate, 1,2-phenylenediisopentanoate, 1,2-phenylenebis(2-ethylhexanoate), 1,2-phenylenedibenzoate, 4-chloro-1,2-phenylenediacetate, 4-chloro-1,2-phenylenediisopentanoate, 4-chloro-1,2-phenylenedibenzoate, 3-methyl-5-t-butyl-1,2-phenylenedibenzoate, 4-t-butyl-1,2-phenyleneacetate, 4-t-butyl-1,2-phenylenebis(2-ethylhexanoate), 4-t-butyl-1,2-phenylenedibenzoate, etc. are preferably used, and among these, 3-methyl-5-t-butyl-1,2-phenylenedibenzoate is more preferred.

[0106] Furthermore, phenylenediote compounds may be used alone or in combination of two or more types.

[0107] Examples of ether carbonate compounds include the following general formula (10):

[0108] R ２９ -OC(=O)-O-Z-OR ３０ (10)

[0109] (In general formula (10), R ２９ and R ３０ R represents a linear alkyl group having 1 to 20 carbon atoms, a branched alkyl group having 3 to 20 carbon atoms, a vinyl group, a linear alkenyl group or branched alkenyl group having 3 to 20 carbon atoms, a linear halogen-substituted alkyl group having 1 to 20 carbon atoms, a branched halogen-substituted alkyl group having 3 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, a cycloalkenyl group having 3 to 20 carbon atoms, an aromatic hydrocarbon group having 6 to 24 carbon atoms, a nitrogen-containing hydrocarbon group having 2 to 24 carbon atoms with a carbon atom at the end of the bond (excluding those with a C=N group at the end of the bond), and R ２９ and R ３０ The elements may be the same or different, and Z represents a bonding group that is bonded via a carbon atom or carbon chain.) One or more compounds selected from ether carbonate compounds represented by ) are examples.

[0110] In an ether carbonate compound represented by general formula (10), R ２９ and R ３０ When is a linear alkyl group having 1 to 20 carbon atoms, examples include methyl group, ethyl group, n-propyl group, n-butyl group, n-pentyl group, n-hexyl group, n-pentyl group, n-octyl group, n-nonyl group, n-decyl group, etc., and preferably a linear alkyl group having 1 to 12 carbon atoms. ２９ and R ３０When is a branched alkyl group having 3 to 20 carbon atoms, examples include alkyl groups having secondary or tertiary carbon atoms such as isopropyl group, isobutyl group, t-butyl group, isopentyl group, and neopentyl group, and preferably branched alkyl groups having 3 to 12 carbon atoms. ２９ and R ３０ When is a linear alkenyl group or a branched alkenyl group having 3 to 20 carbon atoms, examples include allyl group, 3-butenyl group, 4-hexenyl group, 5-hexenyl group, 7-octenyl group, 10-dodecenyl group, isopropenyl group, isobutenyl group, isopentenyl group, 2-ethyl-3-hexenyl group, and preferably a branched alkenyl group having 3 to 12 carbon atoms. ２９ and R ３０ When is a linear halogen-substituted alkyl group having 1 to 20 carbon atoms, examples include methyl halogenated group, ethyl halogenated group, n-propyl halogenated group, n-butyl halogenated group, n-pentyl halogenated group, n-hexyl halogenated group, n-pentyl halogenated group, n-octyl halogenated group, nonyl halogenated group, decyl halogenated group, halogen-substituted undecyl halogenated group, halogen-substituted dodecyl halogenated group, etc., and preferably a linear halogen-substituted alkyl group having 1 to 12 carbon atoms. ２９ and R ３０ When is a branched halogen-substituted alkyl group having 3 to 20 carbon atoms, examples include isopropyl halogenated group, isobutyl halogenated group, 2-ethylhexyl halogenated group, neopentyl halogenated group, etc., and preferably a branched halogen-substituted alkyl group having 3 to 12 carbon atoms. ２９ and R ３０ When is a cycloalkyl group having 3 to 20 carbon atoms, examples include cyclopropyl group, cyclobutyl group, cyclopentyl group, tetramethylcyclopentyl group, cyclohexyl group, methylcyclohexyl group, cycloheptyl group, cyclooctyl group, cyclononyl group, cyclodecyl group, butylcyclopentyl group, etc., and preferably a cycloalkyl group having 3 to 12 carbon atoms. ２９ and R ３０When is a cycloalkenyl group having 3 to 20 carbon atoms, examples include cyclopropenyl group, cyclopentenyl group, cyclohexenyl group, cyclooctenyl group, norbornene group, and preferably a cycloalkenyl group having 3 to 12 carbon atoms. ２９ and R ３０ When R is an aromatic hydrocarbon group having 6 to 24 carbon atoms, examples include phenyl group, methylphenyl group, dimethylphenyl group, ethylphenyl group, benzyl group, 1-phenylethyl group, 2-phenylethyl group, 2-phenylpropyl group, 1-phenylbutyl group, 4-phenylbutyl group, 2-phenylheptyl group, tolyl group, xylyl group, naphthyl group, 1,8-dimethylnaphthyl group, etc., and preferably an aromatic hydrocarbon group having 6 to 12 carbon atoms. In the compound represented by the general formula (10) above, R ２９ or R ３０ When the group contains a halogen atom, examples of halogen atoms include fluorine, chlorine, bromine, or iodine atoms, and preferably fluorine, chlorine, or bromine atoms. ２９ or R ３０ The bonding end of is R in the compound represented by general formula (10). ２９ or R ３０ R refers to the atom or group at the end of the oxygen atom to which it is bonded. ２９Preferably, the group is a linear alkyl group having 1 to 12 carbon atoms, a branched alkyl group having 3 to 12 carbon atoms, a vinyl group, a linear alkenyl group or branched alkenyl group having 3 to 12 carbon atoms, a linear halogen-substituted alkyl group having 1 to 12 carbon atoms, a branched halogen-substituted 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 12 carbon atoms. A kill group, a vinyl group, a linear alkenyl group or branched alkenyl group having 3 to 12 carbon atoms, a linear halogen-substituted alkyl group having 1 to 12 carbon atoms, a branched halogen-substituted 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 12 carbon atoms is more preferred, and a linear alkyl group having 1 to 12 carbon atoms, a branched alkyl group having 3 to 12 carbon atoms, and an aromatic hydrocarbon group having 6 to 12 carbon atoms are even more preferred. ３０ Examples include linear alkyl groups with 1 to 12 carbon atoms, branched alkyl groups with 3 to 12 carbon atoms whose bond ends are -CH2-, vinyl groups, linear alkenyl groups with 3 to 12 carbon atoms, and bond ends that are -CH2- ２ - A branched alkenyl group having 3 to 12 carbon atoms, a linear halogen-substituted alkyl group having 1 to 12 carbon atoms, and a bond end with -CH ２ - A branched halogen-substituted alkyl group having 3 to 12 carbon atoms, a linear halogen-substituted alkenyl group having 3 to 12 carbon atoms, and a bond end with -CH ２ A branched halogen-substituted alkenyl group having 3 to 12 carbon atoms, with the bond end being -CH ２ A cycloalkyl group having 4 to 12 carbon atoms, with a -CH bond at the end. ２ A cycloalkenyl group with 4 to 12 carbon atoms, with a -CH bond at the end. ２ A halogen-substituted cycloalkyl group having 4 to 12 carbon atoms, with the bond end being -CH ２ A halogen-substituted cycloalkenyl group having 4 to 12 carbon atoms, or a bond end with -CH ２ A C7-C12 aromatic hydrocarbon group is preferred, and a C1-C12 linear alkyl group with a -CH bond end is preferred. ２ A branched alkyl group with 3 to 12 carbon atoms, with a -CH bond at the end. ２A branched alkenyl group with 3 to 12 carbon atoms, where the bond end is -CH ２ A linear halogen-substituted alkyl group having 1 to 12 carbon atoms, with the bond end being -CH ２ A branched halogen-substituted alkyl group having 3 to 12 carbon atoms, with the bond end being -CH ２ A cycloalkyl group having 4 to 12 carbon atoms, with a -CH bond at the end. ２ A cycloalkenyl group having 4 to 12 carbon atoms, or a bond end with -CH ２ A more preferable is an aromatic hydrocarbon group having 7 to 12 carbon atoms, and a linear hydrocarbon group having 1 to 12 carbon atoms, with the bond end being -CH ２ A branched alkyl group having 3 to 12 carbon atoms, or a bond end with -CH ２ A more preferable aromatic hydrocarbon group having 7 to 12 carbon atoms is R. ３０ The bonding end of is R in the compound represented by general formula (10). ３０ This refers to the oxygen atom-side terminal to which it is bonded. In the ether carbonate compound represented by general formula (10), Z is the carbonate group and the ether group (OR ３０A divalent bonding group that bonds to a group, a bonding group that bonds via a carbon atom or a carbon chain, for example, a bonding group that bonds between two oxygen atoms to which Z is bonded by a carbon chain, and it is preferable that the carbon chain is composed of two carbon atoms. Z is a linear alkylene group having 2 to 20 carbon atoms, a branched alkylene group having 3 to 20 carbon atoms, a vinylene group, a linear alkenylene group or branched alkenylene group having 3 to 20 carbon atoms, a linear halogen-substituted alkylene group having 2 to 20 carbon atoms, a branched halogen-substituted alkylene group having 3 to 20 carbon atoms, a cycloalkylene group having 3 to 20 carbon atoms, a cycloalkenylene group having 3 to 20 carbon atoms, an aromatic hydrocarbon group having 6 to 24 carbon atoms, a nitrogen-containing hydrocarbon group having 1 to 24 carbon atoms, an oxygen-containing hydrocarbon group having 1 to 24 carbon atoms, or a phosphorus-containing hydrocarbon group having 1 to 24 carbon atoms, and is more preferably a bidentate bonding group selected from an ethylene group having 2 carbon atoms and a branched alkylene group having 3 to 12 carbon atoms (a bidentate bonding group means that the two oxygen atoms to which Z is bonded are connected by a carbon chain, and the carbon chain is composed of two carbon atoms). When Z is a linear alkylene group having 2 to 20 carbon atoms, examples include ethylene, trimethylene, tetramethylene, pentamethylene, hexamethylene, heptamethylene, octamethylene, nonamethylene, decamethylene, undecamethylene, and dodecamethylene groups, and preferably a linear alkylene group having 2 to 12 carbon atoms. More preferably, an ethylene group is used. Z is a branched alkylene group having 3 to 20 carbon atoms, such as 1-methylethylene, 2-methyltrimethylene, 2-methyltetramethylene, 2-methylpentamethylene, 3-methylhexamethylene, 4-methylheptamethylene, 4-methyloctamethylene, 5-methylnonameethylene, 5-methyldecamethylene, 6-methylundecamethylene, 7-methyldodecamethylene, 7-methyltridecamethylene, and more preferably a branched alkylene group having 3 to 12 carbon atoms, and more preferably 1-methylethylene, 2-methylethylene, and 1-ethylethylene.When Z is a linear alkenylene group or a branched alkenylene group having 3 to 20 carbon atoms, examples include propenylene group, butenylene group, hexenylene group, octenylene group, octadecenylene group, isopropenylene group, 1-ethylethenylene group, 2-methylpropenylene group, 2,2-dimethylbutenylene group, 3-methyl-2-butenylene group, 3-ethyl-2-butenylene group, 2-methyloctenylene group, 2,4-dimethyl-2-butenylene group, and preferably a linear alkenylene group having 3 to 12 carbon atoms or a branched alkenylene group having 3 to 12 carbon atoms with an etenylene group as the linking portion, and more preferably isopropenylene group and 1-ethylethenylene group. When Z is a linear halogen-substituted alkylene group having 2 to 20 carbon atoms, examples include dichloromethylene group, chloromethylene group, dichloromethylene group, tetrachloroethylene group, and preferably a linear halogen-substituted alkylene group having 3 to 12 carbon atoms, and more preferably a chloroethylene group, fluoroethylene group, dichloroethylene group, difluoroethylene group, tetrafluoroethylene group. When Z is a branched halogen-substituted alkylene group having 3 to 20 carbon atoms, examples include 1,2-bischloromethylethylene group, 2,2-bis(chloromethyl)propylene group, 1,2-bisdichloromethylethylene group, 1,2-bis(trichloromethyl)ethylene group, 2,2-dichloropropylene group, 1,1,2,2-tetrachloroethylene group, 1-trifluoromethylethylene group, 1-pentafluorophenylethylene group, and the like. Preferably, a branched halogen-substituted alkylene group having 3 to 12 carbon atoms is used, and more preferably, 1-chloroethylethylene group, 1-trifluoromethylethylene group, and 1,2-bis(chloromethyl)ethylene group are used.When Z is a cycloalkylene group having 3 to 20 carbon atoms, examples include cyclopentylene, cyclohexylene, cyclopropylene, 2-methylcyclopropylene, cyclobutylene, 2,2-dimethylcyclobutylene, 2,3-dimethylcyclopentylene, 1,3,3-trimethylcyclohexylene, and cyclooctylene. Preferably, a cycloalkylene group having 3 to 12 carbon atoms is used, and more preferably, a 1,2-cycloalkylene group or a hydrocarbon-substituted 1,2-cycloalkylene group is used. When Z is a cycloalkenylene group having 3 to 20 carbon atoms, examples include cyclopentenylene group, 2,4-cyclopentadienylene group, cyclohexenylene group, 1,4-cyclohexadienylene group, cycloheptenylene group, methylcyclopentenylene group, methylcyclohexenylene group, methylcycloheptenylene group, dicyclodecylene group, tricyclodecylene group, and the like. Preferably, a cycloalkenylene group having 3 to 12 carbon atoms is included, and more preferably, a 1,2-cycloalkenylene group or a hydrocarbon-substituted 1,2-cycloalkenylene group is included. When Z is an aromatic hydrocarbon group having 6 to 24 carbon atoms, examples include 1,2-phenylene group, 3-methyl-1,2-phenylene group, 3,6-dimethyl-1,2-phenylene group, 1,2-naphthylene group, 2,3-naphthylene group, 5-methyl-1,2-naphthylene group, 9,10-phenanthylene group, 1,2-anthracenylene group, and the like, and preferably an aromatic hydrocarbon group having 6 to 12 carbon atoms. When Z is a nitrogen atom-containing hydrocarbon group having 1 to 24 carbon atoms, examples include 1-dimethylaminoethylene group, 1,2-bisdimethylaminoethylene group, 1-diethylaminoethylene group, 2-diethylamino-1,3-propylene group, 2-ethylamino-1,3-propylene group, 4-dimethylamino-1,2-phenylene group, 4,5-bis(dimethylamino)phenylene group, and preferably a nitrogen atom-containing hydrocarbon group having 2 to 12 carbon atoms.When Z is an oxygen-containing hydrocarbon group having 1 to 24 carbon atoms, examples include 1-methoxyethylene group, 2,2-dimethoxy-1,3-propanylene group, 2-ethoxy-1,3-propanylene group, 2-t-butoxy-1,3-propanylene group, 2,3-dimethoxy-2,3-butylene group, 4-methoxy-1,2-phenylene group, and preferably an oxygen-containing hydrocarbon group having 2 to 12 carbon atoms. When Z is a phosphorus-containing hydrocarbon group having 1 to 24 carbon atoms, examples include 1-dimethylphosphinoethylene group, 2,2-bis(dimethylphosphino)-1,3-propanylene group, 2-diethylphosphino-1,3-propanylene group, 2-t-butoxymethylphosphino-1,3-propanylene group, 2,3-bis(diphenylphosphino)-2,3-butylene group, 4-methylphosphate-1,2-phenylene group, and preferably a phosphorus-containing hydrocarbon group having 1 to 12 carbon atoms. When Z is a cyclic group such as a cycloalkylene group, cycloalkenylene group, or aromatic hydrocarbon group, the two oxygen atoms to which Z is bonded are connected by a carbon chain, and a bonding group in which the carbon chain consists of two carbon atoms means that the two adjacent carbon chains within the cyclic carbon chain are the carbon chains between the two oxygen atoms to which Z is bonded.

[0111] The ether carbonate compound of general formula (10) is not particularly limited, and examples include 2-methoxyethyl methyl carbonate, 2-ethoxyethyl methyl carbonate, 2-propoxyethyl methyl carbonate, 2-(2-ethoxyethyloxy)ethyl methyl carbonate, 2-benzyloxyethyl methyl carbonate, (2-methoxypropyl)methyl carbonate, 2-ethoxypropyl methyl carbonate, 2-methyl(2-methoxy)butyl methyl carbonate, 2-methyl(2-ethoxy)butyl methyl carbonate, 2- Methyl (2-methoxy)pentyl methyl carbonate, 2-methyl (2-ethoxy)pentyl methyl carbonate, 1-phenyl (2-methoxy)propyl carbonate, 1-phenyl (2-ethoxy)propyl methyl carbonate, 1-phenyl (2-benzyloxy)propyl methyl carbonate, 1-phenyl (2-methoxy)ethyl methyl carbonate, 1-phenyl (2-ethoxy)ethyl methyl carbonate, 1-methyl-1-phenyl (2-methoxy)ethyl methyl carbonate, 1-methyl-1-phenyl (2-ethoxy) Tylmethyl carbonate, 1-methyl-1-phenyl(2-benzyloxy)ethyl methyl carbonate, 1-methyl-1-phenyl(2-(2-ethoxyethyloxy))ethyl methyl carbonate, 2-methoxyethyl ethyl carbonate, 2-ethoxyethyl ethyl carbonate, 1-phenyl(2-methoxy)ethyl ethyl carbonate, 1-phenyl(2-ethoxy)ethyl ethyl carbonate, 1-phenyl(2-propoxy)ethyl ethyl carbonate, 1-phenyl(2-butoxy)ethyl ethyl carbonate , 1-phenyl(2-isobutoxy)ethyl-ethyl carbonate, 1-phenyl(2-(2-ethoxyethyloxy))ethyl-ethyl carbonate, 1-methyl-1-phenyl(2-methoxy)ethyl-ethyl carbonate, 1-methyl-1-phenyl(2-ethoxy)ethyl-ethyl carbonate, 1-methyl-1-phenyl(2-propoxy)ethyl-ethyl carbonate, 1-methyl-1-phenyl(2-butoxy)ethyl-ethyl carbonate, 1-methyl-1-phenyl(2-isobutyloxy)ethyl-ethyl carbonate,1-Methyl-1-phenyl(2-benzyloxy)ethyl-ethyl carbonate, 1-Methyl-1-phenyl(2-(2-ethoxyethyloxy))ethyl-ethyl carbonate, 2-methoxyethyl phenyl carbonate, 2-ethoxyethyl phenyl carbonate, 2-propoxyethyl phenyl carbonate, 2-butoxyethyl phenyl carbonate, 2-isobutyloxyethyl phenyl carbonate, 2-benzyloxyethyl phenyl carbonate, 2-(2-ethoxyethyloxy)ethyl phenyl carbonate, 2-methoxyethyl-p - Methylphenyl carbonate, 2-ethoxyethyl-p-methylphenyl carbonate, 2-propoxyethyl-p-methylphenyl carbonate, 2-butoxyethyl-p-methylphenyl carbonate, 2-isobutyloxyethyl-p-methylphenyl carbonate, 2-benzyloxyethyl-p-methylphenyl carbonate, 2-(2-ethoxyethyloxy)ethyl-p-methylphenyl carbonate, 2-methoxyethyl-o-methylphenyl carbonate, 2-ethoxyethyl-o-methylphenyl carbonate, 2-propoxyethyl 2---methylphenyl carbonate, 2-butoxyethyl-o-methylphenyl carbonate, 2-isobutyloxyethyl-o-methylphenyl carbonate, 2-benzyloxyethyl-o-methylphenyl carbonate, 2-(2-ethoxyethyloxy)ethyl-o-methylphenyl carbonate, 2-methoxyethyl-o,p-dimethylphenyl carbonate, 2-ethoxyethyl-o,p-dimethylphenyl carbonate, 2-propoxyethyl-o,p-dimethylphenyl carbonate, 2-butoxyethyl-o,p-dimethylphenyl carbonate - phenyl carbonate, 2-isobutyloxyethyl-o,p-dimethylphenyl carbonate, 2-benzyloxyethyl-o,p-dimethylphenyl carbonate, 2-(2-ethoxyethyloxy)ethyl-o,p-dimethylphenyl carbonate, 2-methoxypropylphenyl carbonate, 2-ethoxypropylphenyl carbonate, 2-propoxypropylphenyl carbonate, 2-butoxypropylphenyl carbonate, 2-isobutyloxypropylphenyl carbonate, 2-(2-ethoxyethyloxy)propylphenyl carbonate,2-phenyl(2-methoxy)ethylphenyl carbonate, 2-phenyl(2-ethoxy)ethylphenyl carbonate, 2-phenyl(2-propoxy)ethylphenyl carbonate, 2-phenyl(2-butoxy)ethylphenyl carbonate, 2-phenyl(2-isobutyloxy)ethylphenyl carbonate, 2-phenyl(2-(2-ethoxyethyloxy))ethylphenyl carbonate, 1-phenyl(2-methoxy)propylphenyl carbonate, 1-phenyl(2-ethoxy)propylphenyl carbonate , 1-phenyl(2-propoxy)propylphenyl carbonate, 1-phenyl(2-isobutyloxy)propylphenyl carbonate, 1-phenyl(2-methoxy)ethylphenyl carbonate, 1-phenyl(2-ethoxy)ethylphenyl carbonate, 1-phenyl(2-propoxy)ethylphenyl carbonate, 1-phenyl(2-butoxy)ethylphenyl carbonate, 1-phenyl(2-isobutyloxy)ethylphenyl carbonate, 1-phenyl(2-(2-ethoxyethyloxy))ethylphenyl Carbonate, 1-methyl-1-phenyl(2-methoxy)ethylphenyl carbonate, 1-methyl-1-phenyl(2-ethoxy)ethylphenyl carbonate, 1-methyl-1-phenyl(2-propoxy)ethylphenyl carbonate, 1-methyl-1-phenyl(2-butoxy)ethylphenyl carbonate, 1-methyl-1-phenyl(2-isobutyloxy)ethylphenyl carbonate, 1-methyl-1-phenyl(2-benzyloxy)ethylphenyl carbonate, 1-methyl-1-phenyl(2-(2-ethoxy Examples include (2-ethoxyethyl)ethylphenyl carbonate, and particularly preferably one or more selected from (2-ethoxyethyl)methyl carbonate, (2-ethoxyethyl)ethyl carbonate, (2-propoxyethyl)propyl carbonate, (2-butoxyethyl)butyl carbonate, (2-butoxyethyl)ethyl carbonate, (2-ethoxyethyl)propyl carbonate, (2-ethoxyethyl)phenyl carbonate, and (2-ethoxyethyl)-p-methylphenyl carbonate. Among the above, (2-ethoxyethyl)methyl carbonate,(2-ethoxyethyl)ethyl carbonate and (2-ethoxyethyl)phenyl carbonate are particularly preferred.

[0112] Furthermore, ether carbonate compounds may be used alone or in combination of two or more types.

[0113] Examples of polyol ester compounds include the following general formula (11):

[0114]

[0115] (In the formula, R ３１ and R ３２ R can be selected from the group consisting of hydrogen atoms, halogen atoms, and substituted or unsubstituted hydrocarbon groups having 1 to 20 carbon atoms, and may be the same or different from each other. ３１ ~R ３６ The group optionally contains one or more heteroatoms substituting a carbon atom, a hydrogen atom, or both, wherein the heteroatoms are selected from the group consisting of nitrogen atoms, oxygen atoms, sulfur atoms, silicon atoms, phosphorus atoms, and halogen atoms, R ３３ , R ３４ , R ３５ and R ３６ It is not the case that all of them are hydrogen at the same time. R' is a hydrogen atom, a halogen atom, a linear or branched alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an alkaryl group having 7 to 20 carbon atoms, or an aralkyl group having 7 to 20 carbon atoms, and they may be the same or different from each other.) Examples of polyol ester compounds represented by )

[0116] As for the polyol ester compound of formula (11), R ３１ and R ３２ However, selected from the group consisting of a benzene ring-containing group in which a carbon atom on the benzene ring is optionally substituted by a heteroatom consisting of an oxygen atom and / or a nitrogen atom, or substituted by an alkyl group, alkoxy group or halogen atom; a substituted alkenyl group such as a vinyl group, propenyl group or styryl group or a phenyl group; and alkyl groups such as a methyl group, ethyl group or propyl group, and R ３３ and R３４ , R ３５ and R ３６ Preferably, at least one of the compounds is selected from the group consisting of halogen-substituted or unsubstituted linear or branched alkyl groups having 1 to 10 carbon atoms, cycloalkyl groups having 3 to 10 carbon atoms, aryl groups having 6 to 10 carbon atoms, alkaryl groups having 7 to 10 carbon atoms, and aralkyl groups having 7 to 10 carbon atoms. Particularly preferred are polyol ester compounds such as 9,9-bis(benzoyloxymethyl)fluorene, 9,9-bis((m-methoxybenzoyloxy)methyl)fluorene, 9,9-bis((m-chlorobenzoyloxy)methyl)fluorene, 9,9-bis((p-chlorobenzoyloxy)methyl)fluorene, 9,9-bis(cinnamoyloxymethyl)fluorene, 9-(benzoyloxymethyl)-9-(propionyloxymethyl)fluorene, 9,9-bis(propionyloxymethyl)fluorene, 9,9-bis(acryloyloxymethyl)fluorene, 9,9-bis(pivalyloxymethyl)fluorene, and 9,9-fluorenylmethanoldibenzoate.

[0117] The solid catalyst component (a2) for polymerization of olefins containing a second internal electron-donating compound contains a second internal electron-donating compound as an essential component, but may also contain other internal electron-donating compounds (hereinafter referred to as "other internal electron-donating compounds" as appropriate) as internal electron-donating compounds other than the second internal electron-donating compound.

[0118] Other internal electron-donating compounds related to the solid catalyst component for olefin polymerization containing the second internal electron-donating compound (a2) are the same as other internal electron-donating compounds related to the solid catalyst component for olefin polymerization containing the first internal electron-donating compound (a1).

[0119] In the solid catalyst component (a2) for olefin polymerization containing a second internal electron-donating compound, the content of the second internal electron-donating compound in the total amount of components, when calculated on a solid content basis, is 10.0 to 20.0% by mass, preferably 12.0 to 20.0% by mass, and more preferably 13.0 to 18.0% by mass. By having the content of the second internal electron-donating compound in the total amount of components, when calculated on a solid content basis, a catalyst exhibiting good polymerization performance, including polymer stereoregularity and fluidity such as MFR, can be obtained.

[0120] In the solid catalyst component (a2) for polymerization of olefins containing a second internal electron-donating compound, the content of titanium atoms in the total amount of components, when calculated on a solid content basis, is 1.0 to 6.0% by mass, preferably 1.5 to 5.5% by mass, and more preferably 2.0 to 5.0% by mass.

[0121] In the solid catalyst component (a2) for polymerization of olefins containing a second internal electron-donating compound, the halogen atom content in the total amount of components, when calculated on a solid content basis, is 50.0 to 70.0% by mass, preferably 55.0 to 68.0% by mass, and more preferably 58.0 to 67.0% by mass.

[0122] In the second internal electron-donating compound-containing solid catalyst component for olefin polymerization (a2), the magnesium atom content in the total amount of components, when calculated on a solid content basis, is 15.0 to 25.0% by mass, preferably 16.0 to 23.0% by mass, and more preferably 16.0 to 22.0% by mass.

[0123] The solid catalyst component (a2) for polymerization of olefins containing a second internal electron-donating compound is preferably prepared by contacting the above-mentioned dialkoxymagnesium, titanium halogen compound, and second internal electron-donating compound in the presence of an inert organic solvent.

[0124] The inert organic solvent for the solid catalyst component (a2) containing the second internally electron-donating compound for olefin polymerization is the same as the inert organic solvent for the solid catalyst component (a1) containing the first internally electron-donating compound for olefin polymerization.

[0125] The solid catalyst component (a2) for polymerization of olefins containing a second internal electron-donating compound can be suitably produced by the method for producing the solid catalyst component (a2) for polymerization of olefins containing a second internal electron-donating compound described below.

[0126] Next, a method for producing a solid catalyst component (a2) for polymerization of olefins containing a second internal electron-donating compound will be described.

[0127] A method for producing a solid catalyst component (a2) for olefin polymerization containing a second internal electron-donating compound is to bring together and react a raw material component that serves as a source of magnesium, a raw material component that serves as a source of titanium and halogen, and a second internal electron-donating compound, which is an internal electron-donating compound, in an organic solvent. Specifically, a method is to use dialkoxymagnesium as the raw material component that serves as the source of magnesium, and a tetravalent titanium-halogen compound as the raw material component that serves as the source of titanium and halogen, and bring together these raw materials and an internal electron-donating compound containing a second internal electron-donating compound to obtain a solid catalyst component (a2) for olefin polymerization containing a second internal electron-donating compound.

[0128] The method for producing the solid catalyst component (a2) for polymerization of olefins containing a second internal electron-donating compound is the same as the method for producing the solid catalyst component (a1) for polymerization of olefins containing a first internal electron-donating compound, except that the second internal electron-donating compound is used instead of the first internal electron-donating compound.

[0129] The ratio of each component used in the production of the solid catalyst component (a2) for polymerization of olefins containing a second internal electron-donating compound cannot be specified in general terms as it varies depending on the preparation method. However, for example, it is preferable that the amount of the second internal electron-donating compound per mole of magnesium compound be 0.01 to 10 moles, more preferably 0.01 to 1 mole, and even more preferably 0.02 to 0.6 moles. It is preferable that the amount of the tetravalent titanium halogen compound be 0.5 to 100 moles, more preferably 0.5 to 50 moles, and even more preferably 1 to 10 moles. It is preferable that the amount of the inert organic solvent be 0.001 to 500 moles, more preferably 0.001 to 100 moles, and particularly preferable 0.005 to 10 moles.

[0130] Furthermore, in the above preparation method, other internal electron-donating compounds may be used in combination with the second internal electron-donating compound. In addition, the above contact may be carried out in the presence of other reaction reagents or surfactants, such as silicon, phosphorus, or aluminum.

[0131] In the method for producing a solid catalyst component (a2) for polymerization of olefins containing a second internal electron-donating compound, preferred embodiments of the obtained solid catalyst component (a2) for polymerization of olefins containing a second internal electron-donating compound are as described in detail in the description of the solid catalyst component (a2) for polymerization of olefins containing a second internal electron-donating compound.

[0132] In the first embodiment of the olefin polymerization catalyst of the present invention, the molar ratio (A / B) expressed by the content of the first internal electron-donating compound in the first internal electron-donating compound-containing solid catalyst component (a1) to the content of the second internal electron-donating compound (B) in the second internal electron-donating compound-containing solid catalyst component (a2) for olefin polymerization (a2) is preferably 1 / 99 to 50 / 50, more preferably 5 / 95 to 15 / 85. By having the molar ratio (A / B) within the above range, a polymer with excellent rigidity and impact resistance can be obtained.

[0133] The catalyst for olefin polymerization in the first embodiment of the present invention contains (II) an organoaluminum compound.

[0134] In the first embodiment of the present invention, a catalyst for olefin polymerization, (II) an organoaluminum compound is of general formula (4): R １０ ｑ AlQ ３－ｑ (4) (wherein, R １０ is an alkyl group having 1 to 6 carbon atoms, Q is a hydrogen atom or a halogen atom, q is 0 < q ≤ 3, and R １０ If multiple R １０ The elements Q may be identical or different from each other, and if there are multiple Qs, each Q may be identical or different from each other. ) This is an organoaluminum compound represented by .

[0135] In the organoaluminum compound represented by general formula (4), q is 0 < q ≤ 3, and specifically, q can be 1, 2, or 3.

[0136] Specific examples of such (II) organoaluminum compounds include one or more compounds selected from trialkylaluminum such as triethylaluminum, triisopropylaluminum, tri-n-butylaluminum, tri-n-hexylaluminum, and triisobutylaluminum; alkylaluminum halides such as diethylaluminum chloride and diethylaluminum bromide; and diethylaluminum hydrides. Preferably, one or more compounds selected from alkylaluminum halides such as diethylaluminum chloride, trialkylaluminum such as triethylaluminum, tri-n-butylaluminum, and triisobutylaluminum are preferred, and more preferably, one or more compounds selected from triethylaluminum and triisobutylaluminum are preferred.

[0137] The catalyst for olefin polymerization according to the first embodiment of the present invention contains, as (III) an external electron-donating compound, at least an alkoxysilane compound represented by general formula (1) and an (alkylamino)alkylsilane compound represented by general formula (2).

[0138] The catalyst for olefin polymerization in the first embodiment of the present invention is an external electron-donating compound, comprising the following general formula (1): Si(OR １ ) ( OR２ ) ( OR ３ ) ( OR ４ ) (1) (wherein, R １ , R ２ , R ３ and R ４ It contains one or more compounds selected from alkoxysilane compounds represented by (where (1 to 8) is a linear alkyl group or a branched alkyl group having 3 to 8 carbon atoms, and they may be the same or different from each other).

[0139] In an alkoxysilane compound represented by general formula (1), R １ , R ２ , R ３ and R ４ R is a linear alkyl group or branched alkyl group having 1 to 8 carbon atoms, preferably 1 to 4 carbon atoms, and may be the same or different from each other. １ , R ２ , R ３ and R ４ When the group is a linear alkyl group having 1 to 4 carbon atoms or a branched alkyl group, specific examples include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, or an isobutyl group.

[0140] The alkoxysilane compound represented by general formula (1) is not particularly limited, and examples include tetramethoxysilane, tetraethoxysilane, tetra-n-propoxysilane, tetraisopropoxysilane, tetra-n-butoxysilane, and tetraisobutoxysilane, among which tetraethoxysilane and tetra-n-propoxysilane are preferred.

[0141] The catalyst for olefin polymerization in the first embodiment of the present invention is an external electron-donating compound of the following general formula (2): R ５ R ６ Si (NHR ７ ) (NHR ８ ) (2) (wherein, R ５ and R ６R 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 may be the same as or different from each other. ７ and R ８ It contains one or more compounds selected from (alkylamino)alkylsilane compounds represented by 1 to 8 linear alkyl groups, which may be the same or different from each other.

[0142] In an (alkylamino)alkylsilane compound represented by general formula (2), R ５ and R ６ 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, 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. ５ and R ６ Examples include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group or isobutyl group, neopentyl group, cyclopentyl group, n-hexyl group, cyclohexyl group, and 2-ethylhexyl group. In the (alkylamino)alkylsilane compound represented by general formula (2), R ７ and R ８ 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. 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.

[0143] Examples of (alkylamino)alkylsilane compounds represented by general formula (2) include diisopropylbis(ethylamino)silane, dicyclopentylbis(ethylamino)silane, dicyclohexylbis(ethylamino)silane, cyclohexylmethylbis(ethylamino)silane, and cyclohexylcyclopentylbis(ethylamino)silane.

[0144] In the first embodiment of the olefin polymerization catalyst of the present invention, the molar ratio (Y / X) of the content (Y) of the (alkylamino)alkylsilane compound represented by general formula (2) to the content (X) of the alkoxysilane compound represented by general formula (1) is preferably 1 / 99 to 50 / 50, more preferably 10 / 90 to 30 / 70. Having the mass ratio (Y / X) within the above range results in an external donor mixture that exhibits high activity and high copolymerizability.

[0145] The first embodiment of the olefin polymerization catalyst of the present invention comprises (I) a solid catalyst component for olefin polymerization containing a first internal electron-donating compound (a1) and a solid catalyst component for olefin polymerization containing a second internal electron-donating compound (a2), (II) an organoaluminum compound, and (III) an external electron-donating compound comprising at least an alkoxysilane compound represented by general formula (1) and an (alkylamino)alkylsilane compound represented by general formula (2), i.e., a contact thereof. The catalyst for olefin polymerization in the first embodiment of the present invention may be prepared by contacting (I) a solid catalyst component for olefin polymerization containing a first internal electron-donating compound (a1) and a solid catalyst component for olefin polymerization containing a second internal electron-donating compound (a2), (II) an organoaluminum compound, and (III) an external electron-donating compound, at least an alkoxysilane compound represented by general formula (1) and an (alkylamino)alkylsilane compound represented by general formula (2), in the absence of olefins, or, as described later, by contacting them in the presence of olefins (within the polymerization system).

[0146] In the first embodiment of the catalyst for olefin polymerization of the present invention, the content ratio of each component is arbitrary and not particularly limited as long as it does not affect the effects of the present invention. However, it is generally preferable that the amount of (II) organoaluminum compound is 1 to 2000 moles, and more preferably 50 to 1000 moles, per total mole of titanium atoms in the first internal electron-donating compound-containing solid catalyst component for olefin polymerization (a1) and the second internal electron-donating compound-containing solid catalyst component for olefin polymerization (a2). Furthermore, the catalyst for olefin polymerization according to the first embodiment of the present invention preferably contains, in total, 0.002 to 10.000 moles, of the above (III) external electron-donating compounds, an alkoxysilane compound represented by general formula (1) and an (alkylamino)alkylsilane compound represented by general formula (2), per mole of the above (II) organoaluminum compound, more preferably 0.010 to 2.000 moles, and even more preferably 0.010 to 0.500 moles.

[0147] The second embodiment of the olefin polymerization catalyst of the present invention contains (I) a solid catalyst component for olefin polymerization (b) containing at least a first internal electron-donating compound and a second internal electron-donating compound.

[0148] The solid catalyst component (b) for olefin polymerization containing a first internal electron-donating compound and a second internal electron-donating compound according to the second embodiment of the present invention is a solid catalyst component for olefin polymerization that contains at least magnesium, titanium, halogen, and, as internal electron-donating compounds, at least a first internal electron-donating compound and a second internal electron-donating compound. The solid catalyst component (b) for olefin polymerization containing a first internal electron-donating compound and a second internal electron-donating compound is a solid catalyst component in which both the first internal electron-donating compound and the second internal electron-donating compound are supported in the solid catalyst component.

[0149] As a solid catalyst component (b) for olefin polymerization containing a first internal electron-donating compound and a second internal electron-donating compound, a catalytic reaction product can be obtained by bringing a raw material component that serves as a source of magnesium, a raw material component that serves as a source of titanium and halogen, and the first internal electron-donating compound and the second internal electron-donating compound, which are internal electron-donating compounds, into contact with each other in an organic solvent and reacting them. Specifically, a catalytic reaction product can be obtained by using dialkoxymagnesium as the raw material component that serves as the source of magnesium and a tetravalent titanium-halogen compound as the raw material component that serves as the source of titanium and halogen, and bringing these raw materials into contact with the internal electron-donating compound containing the first internal electron-donating compound and the internal electron-donating compound containing the second internal electron-donating compound.

[0150] In the solid catalyst component (b) for polymerization of olefins containing a first internal electron-donating compound and a second internal electron-donating compound, the dialkoxymagnesium, which is a raw material component that serves as a source of magnesium, is the same as the dialkoxymagnesium, which is a raw material component that serves as a source of magnesium, in the solid catalyst component (a1) for polymerization of olefins containing a first internal electron-donating compound.

[0151] In the solid catalyst component (b) for polymerization of olefins containing the first internal electron-donating compound and the second internal electron-donating compound, the tetravalent titanium halogen compound, which is a raw material component that serves as a source of titanium and halogen, is the same as the tetravalent titanium halogen compound, which is a raw material component that serves as a source of titanium and halogen, in the solid catalyst component (a1) for polymerization of olefins containing the first internal electron-donating compound.

[0152] The first internal electron-donating compound in the solid catalyst component (b) for olefin polymerization containing the first internal electron-donating compound and the second internal electron-donating compound is the same as the first internal electron-donating compound in the solid catalyst component (a1) for olefin polymerization containing the first internal electron-donating compound. The second internal electron-donating compound in the solid catalyst component (b) for olefin polymerization containing the first internal electron-donating compound and the second internal electron-donating compound is the same as the second internal electron-donating compound in the solid catalyst component (a2) for olefin polymerization containing the second internal electron-donating compound.

[0153] Furthermore, the first internal electron-donating compound and the second internal electron-donating compound may be used individually or in combination of two or more.

[0154] Solid catalyst component (b) for olefin polymerization containing a first internal electron-donating compound and a second internal electron-donating compound contains the first internal electron-donating compound and the second internal electron-donating compound as essential components, but may also contain other internal electron-donating compounds (hereinafter referred to as "other internal electron-donating compounds" as appropriate) as internal electron-donating compounds other than the first internal electron-donating compound and the second internal electron-donating compound.

[0155] Other internal electron-donating compounds related to the solid catalyst component (b) for olefin polymerization containing the first internal electron-donating compound and the second internal electron-donating compound are the same as other internal electron-donating compounds related to the solid catalyst component (a1) for olefin polymerization containing the first internal electron-donating compound.

[0156] In the solid catalyst component (b) for olefin polymerization containing a first internal electron-donating compound and a second internal electron-donating compound, the content of the first internal electron-donating compound in the total amount of components, when calculated on a solid content basis, is 10.0 to 20.0% by mass, preferably 12.0 to 20.0% by mass, and more preferably 13.0 to 18.0% by mass. By having the content of the first internal electron-donating compound in the total amount of components, when calculated on a solid content basis, a large amount of high molecular weight polymer can be generated during polymerization, thereby achieving high rigidity.

[0157] In the solid catalyst component (b) for olefin polymerization containing a first internal electron-donating compound and a second internal electron-donating compound, the content of the second internal electron-donating compound in the total amount of components, when calculated on a solid content basis, is 10.0 to 20.0% by mass, preferably 12.0 to 20.0% by mass, and more preferably 13.0 to 18.0% by mass. Having the content of the second internal electron-donating compound in the total amount of components, when calculated on a solid content basis, within the above range allows for obtaining a high MFR with a relatively low hydrogen content during polymerization, resulting in a highly fluid polymer.

[0158] In the solid catalyst component (b) for polymerization of olefins containing a first internal electron-donating compound and a second internal electron-donating compound, the content of titanium atoms in the total amount of components, when calculated on a solid content basis, is 1.0 to 6.0% by mass, preferably 1.5 to 5.5% by mass, and more preferably 2.0 to 5.0% by mass.

[0159] In the solid catalyst component (b) for polymerization of olefins containing a first internal electron-donating compound and a second internal electron-donating compound, the halogen atom content in the total amount of components, when calculated on a solid content basis, is 50.0 to 70.0% by mass, preferably 55.0 to 68.0% by mass, and more preferably 58.0 to 67.0% by mass.

[0160] In the solid catalyst component (b) for polymerization of olefins containing a first internal electron-donating compound and a second internal electron-donating compound, the magnesium atom content in the total amount of components, when calculated on a solid content basis, is 15.0 to 25.0% by mass, preferably 16.0 to 23.0% by mass, and more preferably 16.0 to 22.0% by mass.

[0161] The solid catalyst component (b) for olefin polymerization containing the first internal electron-donating compound and the second internal electron-donating compound is preferably prepared by contacting the above-mentioned dialkoxymagnesium, titanium halogen compound, first internal electron-donating compound, and second internal electron-donating compound in the presence of an inert organic solvent.

[0162] The inert organic solvent for the solid catalyst component (b) for polymerization of olefins containing the first internal electron-donating compound and the second internal electron-donating compound is the same as the inert organic solvent for the solid catalyst component (a1) for polymerization of olefins containing the first internal electron-donating compound.

[0163] The solid catalyst component (b) for olefin polymerization containing the first internal electron-donating compound and the second internal electron-donating compound can be suitably produced by the method for producing the solid catalyst component (b) for olefin polymerization containing the first internal electron-donating compound and the second internal electron-donating compound described below.

[0164] Next, a method for producing a solid catalyst component (b) for olefin polymerization containing a first internal electron-donating compound and a second internal electron-donating compound will be described.

[0165] A method for producing the solid catalyst component (b) for olefin polymerization containing the first internal electron-donating compound and the second internal electron-donating compound is to bring together and react a raw material component that serves as a source of magnesium, a raw material component that serves as a source of titanium and halogen, and the first internal electron-donating compound and the second internal electron-donating compound, which are internal electron-donating compounds, in an organic solvent to obtain the solid catalyst component (b) for olefin polymerization containing the first internal electron-donating compound and the second internal electron-donating compound. Specifically, a method is to use dialkoxymagnesium as the raw material component that serves as the source of magnesium, and a tetravalent titanium-halogen compound as the raw material component that serves as the source of titanium and halogen, and bring together these raw materials and the internal electron-donating compound containing the first internal electron-donating compound and the internal electron-donating compound containing the second internal electron-donating compound to obtain the solid catalyst component (b) for olefin polymerization containing the first internal electron-donating compound and the second internal electron-donating compound.

[0166] The method for producing the solid catalyst component (b) for olefin polymerization containing the first internal electron-donating compound and the second internal electron-donating compound is the same as the method for producing the solid catalyst component (a1) for olefin polymerization containing the first internal electron-donating compound, except that the first internal electron-donating compound and the second internal electron-donating compound are used as the internal electron-donating compound, and the first internal electron-donating compound and the second internal electron-donating compound are brought into contact with raw materials such as dialkoxymagnesium as a source of magnesium and a tetravalent titanium halogen compound as a source of titanium and halogen. In the method for producing the solid catalyst component (b) for olefin polymerization containing the first internal electron-donating compound and the second internal electron-donating compound, the order in which the first internal electron-donating compound and the second internal electron-donating compound are contacted is not particularly limited. The first internal electron-donating compound may be contacted first, the second internal electron-donating compound may be contacted first, or both may be contacted simultaneously. However, as the conversion of dialkoxymagnesium to magnesium chloride by the titanium halide compound progresses, it becomes more difficult for the first internal electron-donating compound to be supported on the solid catalyst component. Therefore, it is preferable to contact the first internal electron-donating compound first, followed by the second internal electron-donating compound.

[0167] The ratio of each component used in the production of the solid catalyst component (b) for polymerization of olefins containing the first internal electron-donating compound and the second internal electron-donating compound cannot be specified in general terms as it varies depending on the preparation method. However, for example, the total number of moles of the first internal electron-donating compound and the second internal electron-donating compound per mole of magnesium compound is preferably 0.01 to 10 moles, more preferably 0.01 to 1 mole, and even more preferably 0.02 to 0.6 moles. The tetravalent titanium halogen compound is preferably 0.5 to 100 moles, more preferably 0.5 to 50 moles, and even more preferably 1 to 10 moles. The inert organic solvent is preferably 0.001 to 500 moles, more preferably 0.001 to 100 moles, and particularly preferably 0.005 to 10 moles.

[0168] In addition, other internal electron-donating compounds may be used in combination with the first internal electron-donating compound and the second internal electron-donating compound in the above preparation method. Furthermore, the above contact may be carried out in the presence of other reaction reagents or surfactants, such as silicon, phosphorus, or aluminum.

[0169] In the method for producing a solid catalyst component (b) for olefin polymerization containing a first internal electron-donating compound and a second internal electron-donating compound, preferred embodiments of the obtained solid catalyst component (b) for olefin polymerization containing a first internal electron-donating compound and a second internal electron-donating compound are as described in detail in the description of the solid catalyst component (b) for olefin polymerization containing a first internal electron-donating compound and a second internal electron-donating compound.

[0170] In the second embodiment of the present invention, the molar ratio (C / D) of the content of the first internal electron-donating compound (C) to the content of the second internal electron-donating compound (D) in the solid catalyst component (b) for olefin polymerization containing the first internal electron-donating compound and the second internal electron-donating compound is preferably 1 / 99 to 50 / 50, more preferably 5 / 95 to 40 / 60. Having a molar ratio (C / D) within this range results in an olefin polymerization catalyst that exhibits high activity and high rigidity.

[0171] The second embodiment of the olefin polymerization catalyst of the present invention contains (II) an organoaluminum compound.

[0172] The (II) organoaluminum compound according to the second embodiment of the olefin polymerization catalyst of the present invention is the same as the (II) organoaluminum compound according to the first embodiment of the olefin polymerization catalyst of the present invention.

[0173] The second embodiment of the olefin polymerization catalyst of the present invention contains, as (III) an external electron-donating compound, at least an alkoxysilane compound represented by general formula (1) and an (alkylamino)alkylsilane compound represented by general formula (2).

[0174] In the second embodiment of the olefin polymerization catalyst of the present invention, the alkoxysilane compound represented by general formula (1) and the (alkylamino)alkylsilane compound represented by general formula (2) used as (III) external electron-donating compounds are the same as the alkoxysilane compound represented by general formula (1) and the (alkylamino)alkylsilane compound represented by general formula (2) used as (III) external electron-donating compounds in the first embodiment of the olefin polymerization catalyst of the present invention.

[0175] In the second embodiment of the olefin polymerization catalyst of the present invention, the molar ratio (Y / X), represented by the content (Y) of the (alkylamino)alkylsilane compound represented by general formula (2) to the content (X) of the alkoxysilane compound represented by general formula (1), is preferably 1 / 99 to 50 / 50, more preferably 10 / 90 to 30 / 70. Having the molar ratio (Y / X) within this range allows for the generation of a large amount of high molecular weight polymer during polymerization, resulting in a polymer with high rigidity.

[0176] The second embodiment of the olefin polymerization catalyst of the present invention comprises (I) a solid catalyst component (b) for olefin polymerization containing a first internal electron-donating compound and a second internal electron-donating compound, (II) an organoaluminum compound, and (III) an external electron-donating compound, at least an alkoxysilane compound represented by general formula (1) and an (alkylamino)alkylsilane compound represented by general formula (2), i.e., a contact thereof. The second embodiment of the olefin polymerization catalyst of the present invention may be prepared by contacting (I) a solid catalyst component (b) for olefin polymerization containing a first internal electron-donating compound and a second internal electron-donating compound, (II) an organoaluminum compound, and (III) an external electron-donating compound, an alkoxysilane compound represented by general formula (1) and an (alkylamino)alkylsilane compound represented by general formula (2), in the absence of olefins, or, as described later, by contacting them in the presence of olefins (within the polymerization system).

[0177] In the second embodiment of the catalyst for olefin polymerization of the present invention, the content ratio of each component is arbitrary and not particularly limited as long as it does not affect the effects of the present invention. However, it is generally preferable that the solid catalyst component (b) for olefin polymerization containing the (I) first internal electron-donating compound and the second internal electron-donating compound contains 1 to 2,000 moles of the (II) organoaluminum compound per mole of titanium atoms, and more preferably 50 to 1,000 moles. Furthermore, in the second embodiment of the catalyst for olefin polymerization of the present invention, it is preferable that the (III) external electron-donating compound, which is an alkoxysilane compound represented by general formula (1) and a (alkylamino)alkylsilane compound represented by general formula (2), contains a total of 0.002 to 10,000 moles per mole of the (II) organoaluminum compound, more preferably 0.010 to 2,000 moles, and even more preferably 0.010 to 0.500 moles.

[0178] Catalysts for olefin polymerization that use succinate diester alone as an internal electron-donating compound yield polymers with high rigidity (FM), but require a large amount of hydrogen to achieve high melt flow rate (MFR).

[0179] The inventors of the present invention have found that when polymerizing olefins using a solid catalyst component for olefin polymerization that contains a succinate diester compound as an internal electron-donating compound, using an alkoxysilane compound represented by general formula (1) as an external electron-donating compound allows for the acquisition of polymers with high melt flow rate (MFR) even with low hydrogen usage. Based on this finding, the inventors of the present invention have found that in the olefin polymerization catalyst of the present invention, by using a succinate diester compound as the internal electron-donating compound of the solid catalyst component for olefin polymerization, the molecular weight distribution of the olefin polymer can be broadened and polymer components with very large molecular weights can be generated. This increases the rigidity (FM) of the olefin polymer, and by using a second internal electron-donating compound in combination as an internal electron-donating compound, it is possible to improve activity and strengthen the influence of the external donor. Furthermore, in the olefin polymerization catalyst of the present invention, after designing the solid catalyst components for olefin polymerization in this manner, by combining an (alkylamino)alkylsilane compound represented by general formula (2), which exhibits high polymerization activity and high regularity, with an alkoxysilane compound represented by general formula (1) as an external electron-donating compound, it is possible to obtain olefin polymers with high melt flow rate (MFR) even with a reduced amount of hydrogen used.

[0180] The present invention provides a method for producing olefin polymers, characterized by polymerizing olefins using an olefin polymerization catalyst of the present invention, for example, the olefin polymerization catalyst of the first embodiment of the present invention or the olefin polymerization catalyst of the second embodiment of the present invention.

[0181] In the method for producing olefin polymers of the present invention, the polymerization of olefins may be homopolymerization or copolymerization. In the method for producing olefin polymers of the present invention, one or more olefins to be polymerized can be selected from ethylene, propylene, 1-butene, 1-pentene, 4-methyl-1-pentene, vinylcyclohexane, etc., and among these, one or more selected from ethylene, propylene, and 1-butene are preferred, with propylene being more preferred. When the above olefin is propylene, it may be homopolymerization of propylene, or copolymerization with other α-olefins. One or more olefins to be copolymerized with propylene can be selected from ethylene, 1-butene, 1-pentene, 4-methyl-1-pentene, vinylcyclohexane, etc.

[0182] When the olefin polymerization catalyst of the present invention is prepared in the presence of olefins (within the polymerization system), the ratio of each component used is arbitrary and not particularly limited, as long as it does not affect the effects of the present invention. However, it is generally preferable to contact the above-mentioned (II) organoaluminum compound at a rate of 1 to 2,000 moles per mole of titanium atoms in the above-mentioned (I) solid catalyst component for olefin polymerization, and more preferably 50 to 1,000 moles. Furthermore, it is preferable to contact the above-mentioned (III) external electron-donating compound at a rate of 0.002 to 10,000 moles per mole of the above-mentioned (II) organoaluminum compound, more preferably 0.010 to 2,000 moles, and even more preferably 0.010 to 0.500 moles.

[0183] The order in which the components constituting the above-mentioned olefin polymerization catalyst come into contact is arbitrary, but it is desirable to first charge the above-mentioned (II) organoaluminum compound into the polymerization system, and if the above-mentioned (III) external electron-donating compound is used, then charge the above-mentioned (III) external electron-donating compound and bring it into contact, and then charge and bring it into contact with the above-mentioned (I) solid catalyst component for olefin polymerization.

[0184] The method for producing olefin polymers of the present invention may be carried out in or without the presence of an organic solvent. Furthermore, olefin monomers such as propylene can be used in either gaseous or liquid form. The polymerization temperature is preferably 200°C or lower, more preferably 100°C or lower, and the polymerization pressure is preferably 10 MPa or lower, more preferably 5 MPa or lower. In addition, the polymerization of olefins can be carried out by either a continuous polymerization method or a batch polymerization method. Furthermore, the polymerization reaction may be carried out in one step or in two or more steps.

[0185] In addition, when polymerizing olefins using the olefin polymerization catalyst of the present invention (also referred to as the main polymerization), it is preferable to perform prepolymerization prior to the main polymerization in order to further improve the catalytic activity, stereoregularity, and particle properties of the resulting polymer. In prepolymerization, the same olefins or monomers such as styrene as those used in the main polymerization can be used.

[0186] When performing prepolymerization, the order in which the components constituting the olefin polymerization catalyst and the monomers (olefins) are brought into contact is arbitrary, but preferably, in a prepolymerization system set to an inert gas atmosphere or an olefin gas atmosphere, (II) an organoaluminum compound is first charged in, then (I) the solid catalyst component for olefin polymerization according to the present invention is charged in 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. In the above prepolymerization, when (III) an external electron-donating compound is further charged into the prepolymerization system, in a prepolymerization system set to an inert gas atmosphere or an olefin gas atmosphere, (II) an organoaluminum compound is first charged in, then (III) the external electron-donating compound is charged in and brought into contact, and then (I) the solid catalyst component for olefin polymerization according to the present invention 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.

[0187] In the method for producing olefin polymers of the present invention, the polymerization methods include slurry polymerization using an inert hydrocarbon compound solvent such as cyclohexane or heptane, bulk polymerization using a solvent such as liquefied propylene, and gas-phase polymerization using substantially no solvent, with bulk polymerization or gas-phase polymerization being preferred.

[0188] 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.

[0189] 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.

[0190] In the method for producing olefin polymers of the present invention, the block copolymerization reaction between propylene and other α-olefins can usually be carried out in the presence of the olefin polymerization catalyst of the present invention by first contacting propylene alone or propylene with a small amount of α-olefin (such as ethylene) in the preceding step, and then contacting propylene with α-olefin (such as ethylene) in the subsequent step. The polymerization reaction in the preceding step may be repeated multiple times, or the polymerization reaction in the subsequent step may be repeated multiple times to carry out a multi-stage reaction.

[0191] In the block copolymerization reaction between propylene and other α-olefins, it is preferable to perform polymerization in the first stage by adjusting the polymerization temperature and time so that the proportion of the polypropylene portion (in the final copolymer) is 20 to 90% by mass, and then in the second stage, introduce propylene and ethylene or other α-olefins so that the proportion of the rubber portion (such as ethylene-propylene rubber (EPR)) (in the final copolymer) is 10 to 80% by mass. The polymerization temperature in both the first and second stages is preferably 200°C or less, more preferably 100°C or less, even more preferably 65°C to 80°C, and even more preferably 75 to 80°C. The polymerization pressure is preferably 10 MPa or less, more preferably 6 MPa or less, and even more preferably 5 MPa or less. In the above copolymerization reaction, either a continuous polymerization method or a batch polymerization method can be used, and the polymerization reaction may be carried out in one stage or in two or more stages. Furthermore, the polymerization time (residence time in the reactor) is preferably 1 minute to 5 hours at each polymerization stage in the preceding or succeeding stages, or even in continuous polymerization. Examples of polymerization methods include slurry polymerization using inert hydrocarbon compounds such as cyclohexane and heptane as solvents, bulk polymerization using solvents such as liquefied propylene, and gas-phase polymerization using substantially no solvent. Bulk polymerization or gas-phase polymerization is preferred.

[0192] According to the present invention, it is possible to provide a method for producing olefin polymers that have excellent melt flow properties and high rigidity even with low hydrogen usage.

[0193] In the method for producing olefin polymers of the present invention, hydrogen gas and olefins are supplied in a ratio such that the melt flow rate (MFR) of the propylene polymer obtained in homopolymerization is 350 g / 10 min or less. By supplying hydrogen gas and olefins in such a ratio, an olefin polymer with an appropriate melt flow rate (MFR) can be obtained.

[0194] The melt flow rate (MFR) of the olefin homopolymer obtained by the method for producing olefin polymers according to the present invention is 1 to 1000 g / 10 minutes, preferably 10 to 500 g / 10 minutes, and more preferably 50 to 350 g / 10 minutes.

[0195] In this application, the melt flow rate (MFR) refers to the value measured according to ASTM D 1238 and JIS K 7210.

[0196] Furthermore, in this application, the flexural modulus (FM) of the olefin polymer refers to the value measured at a measurement ambient temperature of 23°C in accordance with JIS K7171, using an injection-molded test specimen with a thickness of 4.0 mm, a width of 10.0 mm, and a length of 80.0 mm, prepared using NEX30III3EG manufactured by Nissei Plastic Industrial Co., Ltd., after mixing with a nucleating agent (sodium benzoate: 1000 ppm) under conditions of a molding temperature of 200°C and a mold temperature of 40°C (unit: MPa).

[0197] 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.

[0198] (Production Example 1) Synthesis of Solid Catalyst Component (1) for Polymerization of Olefins Containing Diethyl Succinate As an internal electron-donating compound, 2,3-diisopropylsuccinate diethyl, a diethyl succinate compound, was used, 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 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 diethyl 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 (1) for polymerization of succinic acid diester-containing olefins). 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 3.1% by mass and 19.8% by mass, respectively. The properties of the obtained solid catalyst component (1) are shown in Table 1.

[0199] The titanium content in the solid catalyst component, the content of 2,3-diisopropylsuccinate diethyl (which corresponds to the succinate diester compound, an internally electron-donating compound), and its physical properties were measured using the method described below.

[0200] <Titanium content in solid catalyst components> The titanium content in the solid catalyst components was measured according to the method of JIS 8311-1997.

[0201] <Content of Internally Electron-Donating Compounds> The content of internally electron-donating compounds was determined by measuring using gas chromatography (Shimadzu Corporation, GC-2014) under the following conditions. The number of moles of internally electron-donating compounds was determined from the gas chromatography measurement results using a calibration curve previously measured at known concentrations. <Measurement Conditions> Column: Capillary column (φ0.32 mm, film thickness 1.0 μm, Rxi-1 ms, GL Sciences Co., Ltd.) Detector: FID (Flame Ionization Detector) Carrier gas: Helium, flow rate 7.0 ml / min Measurement temperature: Vaporization chamber 280°C, column 170°C, detector 280°C

[0202] (Production Example 2) Synthesis of Solid Catalyst Component (2) for Polymerization of Olefins Containing 1-Cyclohexene-1,2-Dicarboxylic Acid Diester A non-phthalate diester compound, 1-cyclohexene-1,2-dicarboxylic acid di-n-butyl, was used as the internal electron-donating compound, and a solid catalyst component for polymerization of olefins containing 1-cyclohexene-1,2-dicarboxylic acid diester was prepared by the following method: (i) A 500 ml flask equipped with a stirring device and thoroughly purged with nitrogen gas was filled with 60 ml of titanium tetrachloride (545.8 mmol) and 75 ml of toluene to form a mixed solution. (ii) Next, a suspension formed using 30.0 g (262.2 mmol) of diethoxymagnesium and 90 ml of toluene was added to the mixed solution, which was maintained at a liquid temperature of 0°C. (iii) The initial contact solution was kept at 0°C for 60 minutes, then the temperature was raised. During the heating process, 10.8 ml (39.8 mmol) of 1-cyclohexene-1,2-dicarboxylate di-n-butyl was added, and the mixture was reacted at 100°C for 120 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 150 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 110°C and the mixture was reacted for 60 minutes to obtain the final contact product. Then, the obtained final contact product was washed eight times with 150 mL of n-heptane at 40°C, and the solid and liquid were separated to obtain a solid catalyst component (1-cyclohexene-1,2-dicarboxylate diester-containing solid catalyst component for polymerization of olefins (2)). The solid and liquid components of the obtained solid catalyst component (2) were separated, and the titanium content and 1-cyclohexene-1,2-dicarboxylic acid diester content in the obtained solid were measured to be 3.0% by mass and 13.2% by mass, respectively.

[0203] (Production Example 3) Synthesis of Solid Catalyst Component (3) for Polymerization of Olefins Containing Benzylidenemalonate Diester A solid catalyst component (3) for polymerization of olefins containing benzylidenemalonate diester was prepared in the same manner as in (I) synthesis of solid catalyst component (1) for polymerization of succinic acid diester. The titanium content and benzylidenemalonate diester content in the obtained solid catalyst component (3) were measured to be 3.2% by mass and 8.8% by mass, respectively.

[0204] (Production Example 4) Synthesis of Solid Catalyst Component (4) for Polymerization of Phthalate Diesters A solid catalyst component for polymerization of olefins was prepared by the following method using di-n-propyl phthalate, a phthalate diester compound, as the internal electron-donating compound. (i) A mixed solution was formed by charging 105 ml (952.0 mmol) of titanium tetrachloride and 75 ml of toluene into a 500 ml flask equipped with a stirring device and thoroughly purged with nitrogen gas. (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 initial contact-containing solution was set to 110°C and reacted for 180 minutes while maintaining the same temperature. After the reaction was complete, the supernatant was removed and the first contact product, which was the reaction product, was washed four times with 250 mL of toluene at 100°C. (iv) Next, 185 mL of toluene and 30 mL (272.0 mmol) of titanium tetrachloride were added to the first contact product and the temperature was raised to 110°C and the reaction was carried out for 120 minutes to obtain the final contact product. Then, the obtained final contact product was washed eight times with 188 mL of n-heptane at 40°C and the solid-liquid was separated to obtain solid catalyst component (4) for polymerization of phthalate diester-containing olefins. The solid-liquid of the obtained solid catalyst component (4) was separated and the titanium content and phthalate diester compound content in the obtained solid were measured to be 2.5% by mass and 12.2% by mass, respectively.

[0205] (Example 1) <Preparation of Ethylene-Propylene Copolymerization Catalyst> Solid catalyst component (1) for olefin polymerization containing succinate diester compound and solid catalyst component (2) for olefin polymerization containing 1-cyclohexene-1,2-dicarboxylic acid diester were collected in a heat-resistant glass bottle in a weight ratio of 1:9, and then mixed by shaking to obtain a solid catalyst component mixture. In addition, tetraethoxysilane and dicyclopentylbis(ethylamino)silane were collected in a molar ratio of 70:30 in a heat-resistant glass bottle containing a stirrer tip, and then stirred and mixed with a magnetic stirrer, and diluted with n-heptane to prepare an external donor mixture. Next, 2.2 mmol of triethylaluminum, a total of 0.22 mmol of the external donor mixture (calculated in terms of silicon atoms), and a total of 10.9 mg of the solid catalyst component mixture (calculated in terms of titanium atoms) were charged into a 2.0 liter autoclave with a stirrer, which was completely purged with nitrogen gas, to prepare an ethylene-propylene copolymer catalyst.

[0206] <Ethylene-Propylene Copolymerization> In an autoclave equipped with a stirrer containing the ethylene-propylene copolymerization catalyst prepared above, 15 moles (1.2 liters) of liquefied propylene and hydrogen gas at 0.20 MPa (partial pressure) were charged. Prepolymerization was carried out at 20°C for 5 minutes, then the temperature was increased, and the first stage of propylene homopolymerization (homo-stage polymerization) was carried out at 70°C for 45 minutes. After returning to atmospheric pressure, the inside of the autoclave (reactor) was purged with nitrogen, and the autoclave was weighed. The polymerization activity of the homo-stage (first stage) (homo-activity, g-PP / g-cat) was calculated by subtracting the tare mass of the autoclave. A portion of the generated polymer was separated for evaluation of polymerization performance and polymer properties. Next, ethylene and propylene were added to the autoclave (reactor) in a molar ratio of 1.0 / 1.5, respectively. The temperature was then raised to 70°C, and ethylene, propylene, and hydrogen were introduced at gas supply rates (liters / minute) of 1.6 / 2.4 / 0.09 respectively. The reaction was carried out under conditions of 1.2 MPa and 70°C to obtain an ethylene-propylene copolymer.

[0207] <Polymerization activity per gram of solid catalyst component> The polymerization activity per gram of solid catalyst component was calculated using the following formula (12): Polymerization activity (g / g-cat) = Mass of polymer (g) / Mass of solid catalyst component (g) (12)

[0208] <Melt Flow Rate (MFR)> The melt flow rate (MFR) of olefin polymers was measured according to ASTM D 1238 and JIS K 7210.

[0209] <Blocking rate (mass%)> The blocking rate of the ethylene-propylene copolymer was calculated using the following formula (13): Blocking rate (mass%) = {(I (g) - G (g)) / (I (g) - F (g))} × 100 (13) 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).

[0210] <Flexural Modulus (FM)> Using NEX-III-3EG manufactured by Nissei Plastic Industrial Co., Ltd., an injection-molded test specimen with a thickness of 4.0 mm, a width of 10.0 mm, and a length of 170.0 mm was prepared under the conditions of a molding temperature of 180°C and a mold temperature of 40°C. The flexural modulus (FM) of the olefin polymer was measured according to JIS K7171 at a measurement ambient temperature of 23°C (unit: MPa).

[0211] <Impact Resistance (IZOD)> The impact resistance (IZOD) of olefin polymers was measured in accordance with JIS K 7110 ("Method of Izod Impact Test For Rigid Plastics") (unit: kJ / m2). 0.10 wt% IRGANOX 1010 (BASF) and 0.10 wt% IRGAFOS 168 (BASF) were added to ethylene-propylene copolymer, and this mixture was kneaded in a twin-screw kneader to form granules, obtaining ethylene-propylene copolymer pellets. The ethylene-propylene copolymer pellets were introduced into an injection molding machine (mold temperature: 40°C, cylinder temperature: 180°C) and injection molded to prepare specimens for property measurement. The specimen was cut and processed as described below, conditioned for more than 72 hours in a temperature-controlled chamber maintained at 23°C, and the Izod impact strength of the specimen was measured using an impact testing machine No. 258-L (with low-temperature chamber) manufactured by Yasuda Seiki Seisakusho. • Specimen shape: ISO 180 / 1A, thickness: 4.0 mm, width: 8.0 mm, length: 80.0 mm • Notch shape: A-type notch formed using a die mold with a notch (radius: 0.25 mm) • Temperature: 23°C • Impact velocity: 3.5 m / sec • Nominal pendulum energy: 2.75 J (23°C)

[0212] (Comparative Example 1) Except that the solid catalyst component for polymerization of olefins containing succinic acid diester compound (a) was not used as the solid catalyst component, only 0.0055 mmol of the solid catalyst component for polymerization of olefins containing 1-cyclohexene-1,2-dicarboxylic acid diester (b) was used in the same manner as in Example 1, an ethylene-propylene copolymer was prepared and ethylene-propylene copolymer was obtained.

[0213] (Comparative Example 2) Except that, as the solid catalyst component, only the solid catalyst component for olefin polymerization containing benzylidenemalonate diester (3) was used in the same manner as in Example 2, with 0.0055 mmol in terms of titanium atoms being used instead of the solid catalyst component for olefin polymerization containing succinic acid diester compound (1) and the solid catalyst component for olefin polymerization containing 1-cyclohexene-1,2-dicarboxylic acid diester (2), an ethylene-propylene copolymer was obtained by preparing an ethylene-propylene copolymer catalyst and performing ethylene-propylene copolymerization.

[0214] (Comparative Example 3) Except that, as the solid catalyst component, only the solid catalyst component (4) containing a phthalate diester compound was used in the same manner as in Example 1, with 0.0055 mmol in titanium atoms equivalent, instead of the solid catalyst component (1) containing a succinate diester compound for olefin polymerization and the solid catalyst component (2) containing 1-cyclohexene-1,2-dicarboxylic acid diester for olefin polymerization, an ethylene-propylene copolymer was obtained by preparing an ethylene-propylene copolymer catalyst and performing ethylene-propylene copolymerization.

[0215] (Comparative Example 4) Except that tetraethoxysilane was not used as the external electron-donating compound, and only dicyclopentylbis(ethylamino)silane was used at a rate of 0.22 mmol in terms of silicon 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.

[0216] (Comparative Example 5) Except that tetraethoxysilane was not used as the external electron-donating compound, and only dicyclopentylbis(ethylamino)silane was used at a rate of 0.22 mmol in terms of silicon atoms, the ethylene-propylene copolymer catalyst was prepared and ethylene-propylene copolymerization was carried out in the same manner as in Example 2 to obtain an ethylene-propylene copolymer.

[0217]

[0218]

[0219] According to the present invention, it is possible to produce olefin polymers with excellent melt flow properties and high rigidity using a small amount of hydrogen.

Claims

1. (I) A solid catalyst component for olefin polymerization containing at least magnesium, titanium, a halogen, and an internal electron donor compound; (II) an organoaluminum compound; and (III) an external electron donor compound, a catalyst for olefin polymerization, wherein in the solid catalyst for olefin polymerization, at least a first internal electron donor compound and a second internal electron donor compound are present as the internal electron donor compound, the first internal electron donor compound is one or more compounds selected from succinic acid diester compounds, and the second internal electron donor compound is one or more compounds selected from diester compounds other than phthalic acid diester compounds and succinic acid diester compounds, ether carbonate compounds, and polyol ester compounds, and as the external electron donor compound, at least the following general formula (1): Si(OR １ )(OR ２ )(OR ３ )(OR ４ ) (1) (In the formula, R １ , R ２ , R ３ , and R ４ are linear alkyl groups having 1 to 8 carbon atoms or branched alkyl groups having 3 to 8 carbon atoms, which may be the same as or different from each other.) one or more compounds selected from alkoxysilane compounds represented by, and the following general formula (2): R ５ R ６ Si(NHR ７ )(NHR ８ ) (2) (In the formula, R ５ and R ６ are linear alkyl groups having 1 to 8 carbon atoms, branched alkyl groups having 3 to 12 carbon atoms, cycloalkyl groups having 3 to 12 carbon atoms, cycloalkenyl groups having 3 to 12 carbon atoms, or aromatic hydrocarbon groups having 6 to 20 carbon atoms, which may be the same as or different from each other, and R ７ and R ８ are linear alkyl groups having 1 to 8 carbon atoms or branched alkyl groups having 3 to 8 carbon atoms, which may be the same as or different from each other.) one or more compounds selected from (alkylamino)alkylsilane compounds represented by are present, a catalyst for olefin polymerization, characterized by the above.

2. The catalyst for polymerization of olefins according to claim 1, characterized in that the diester compound other than the phthalate diester compound and succinate diester compound is one or more compounds selected from the group consisting of malonic acid diester compounds, cyclohexanedicarboxylic acid ester compounds, cyclohexenedicarboxylic acid ester compounds, citraconic acid diester compounds, phenylenedibenzoate compounds, ether carbonate compounds, and polyol ester compounds.

3. The catalyst for polymerization of olefins according to claim 1, characterized in that the (I) solid catalyst component for polymerization of olefins contains magnesium, titanium, halogen and the first internal electron-donating compound as an internal electron-donating compound (a1), and the (III) external electron-donating compound contains an alkoxysilane compound represented by general formula (1) and an (alkylamino)alkylsilane compound represented by general formula (2).

4. The catalyst for polymerization of olefins according to claim 1, characterized in that the (I) solid catalyst component for polymerization of olefins contains magnesium, titanium, halogen, and an internal electron-donating compound, the first internal electron-donating compound and the second internal electron-donating compound-containing solid catalyst component (b), and the (III) external electron-donating compound contains an alkoxysilane compound represented by general formula (1) and an (alkylamino)alkylsilane compound represented by general formula (2).

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

6. The catalyst for polymerization of olefins according to claim 1, characterized in that the (alkylamino)alkylsilane compound represented by the general formula (2) is at least one selected from the group consisting of diisopropylbis(ethylamino)silane, dicyclopentylbis(ethylamino)silane, dicyclohexylbis(ethylamino)silane, cyclohexylmethylbis(ethylamino)silane, and cyclohexylcyclopentylbis(ethylamino)silane.

7. The catalyst for polymerization of olefins according to claim 1, characterized in that the molar ratio (Y / X) of the content (Y) of the (alkylamino)alkylsilane compound represented by general formula (2) to the content (X) of the alkoxysilane compound represented by general formula (1) is 1 / 99 to 50 / 50.

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

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