Production method of olefin polymer

Abstract

To provide a production method of an olefin polymer with which an olefin polymer having excellent melt flow rate and high stiffness can be produced by using a solid catalyst component for olefin polymerization containing an inner electron-donating compound other than a phthalic acid ester in olefin polymerization.SOLUTION: A production method of an olefin polymer has a polymer mixing step to mix an olefin polymer (A) which is obtained by conducting olefin polymerization by using a succinic diester-based solid catalyst component (1) for olefin polymerization as a solid catalyst component, and an olefin polymer (B) which is obtained by conducting olefin polymerization by using a malonic diester-based solid catalyst component (2) for olefin polymerization as a solid catalyst component with each other in a mixing ratio of 5.0-80.0 mass% of the olefin polymer (A) to the sum total of the olefin polymer (A) and the olefin polymer (B) so as to obtain an olefin polymer (C1).SELECTED DRAWING: None

Description

Technical Field

[0001] The present invention relates to a method for producing an olefin polymer.

Background Art

[0002] In recent years, olefin polymers such as polypropylene (PP) have been used in various applications such as containers and films in addition to molded products for automotive parts or household appliances.

[0003] Polypropylene-based resin compositions are lightweight, excellent in moldability, excellent in chemical stability such as heat resistance and chemical resistance of the molded body, and very excellent in cost performance, and thus are used in many fields as one of the most important plastic materials.

[0004] In order to further expand the applications, polypropylene having a high melt flowability (melt flow rate (MFR)), excellent moldability, and high rigidity, which can be used as an alternative to polystyrene and ABS resins, has been desired.

[0005] In the polymerization of olefins such as propylene, a polymerization method using a solid catalyst component containing a magnesium atom, a titanium atom, a halogen atom, and an internal electron-donating compound as essential components is known, and a method of polymerizing or copolymerizing olefins in the presence of a catalyst for olefin polymerization composed of the above solid catalyst component, an organoaluminum compound, and an organosilicon compound has been proposed in many cases.

[0006] For example, Patent Document 1 proposes a method of polymerizing propylene using a solid titanium catalyst component supporting an internal electron-donating compound such as a phthalic acid ester, an organoaluminum compound as a co-catalyst component, and an organosilicon compound having at least one Si—O—C bond. In many documents including Patent Document 1, a method of using a phthalic acid ester as an internal electron-donating compound to obtain a highly stereoregular polymer under high polymerization activity has been proposed.

[0007] However, di-n-butyl phthalate and benzyl butyl phthalate, which are types of phthalic acid esters, have been specified as Substances of Very High Concern (SVHC) in the European Registration, Evaluation, Authorization and Restriction of Chemicals (REACH) regulations. From the perspective of reducing the environmental impact, the demand for converting to a catalyst system that does not use SVHC substances is increasing.

[0008] Therefore, as a method for producing an olefin polymer excellent in melt flowability (melt flow rate (MFR)) using a solid catalyst component for olefin polymerization containing an internal electron-donating compound other than phthalic acid ester, for example, Patent Document 2 discloses that a polymer having high hydrogen activity and polymerization activity, a high MFR with a smaller amount of hydrogen, and high stereoregularity can be obtained in good yield. Further, as a solid catalyst component for olefin polymerization having high copolymerization activity, good copolymerization characteristics such as block ratio, and consideration for the environment, (a) a magnesium compound, (b) the following general formula (I): R 1 2C(COOCH3)2 (I) (In the formula, R1 is any one selected from a branched alkyl group having 3 to 20 carbon atoms, a halogen atom, a linear or branched halogen-substituted alkyl group having 2 to 20 carbon atoms, a linear alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, a vinyl group, and an allyl group.) An internal electron donor represented by the formula, and (c) a tetravalent halogen compound are brought into contact in an inert organic solvent, and a solid catalyst component for olefin polymerization is disclosed.

[0009] In addition, Patent Document 3 discloses a method for polymerizing propylene and ethylene using a catalyst comprising: (A) a solid catalyst containing, as an essential component, an electron donor compound selected from magnesium, titanium, halogen, and succinate compounds; (B) an organoaluminum compound; and (C) an external electron donor compound, to produce a biaxially stretched polypropylene sheet excellent in transparency, rigidity, heat resistance, uniform stretchability, and impact resistance at low temperatures, and further having excellent thermoformability.

[0010] Further, Patent Document 4 discloses a solid catalyst component for olefin polymerization that can be well balanced while satisfying a practically sufficient level with respect to the stereoregularity and molecular weight distribution breadth of the resulting polymer, copolymerization activity, and block ratio of the resulting copolymer, although it contains an electron donating compound other than a phthalic acid ester. The solid catalyst component for olefin polymerization contains magnesium, titanium, halogen, an ether carbonate compound (A), and a succinic acid diester compound (B), and is characterized in that the molar ratio represented by the following formula (content of ether carbonate compound (A) / content of succinic acid diester compound (B)) is 0.01 to 1.00.

Prior Art Documents

Patent Documents

[0011]

Patent Document 1

Patent Document 2

Patent Document 3

Patent Document 4

Summary of the Invention

Problems to be Solved by the Invention

[0012] However, in the method for producing an olefin polymer disclosed in Patent Document 2, although an olefin polymer with excellent melt fluidity can be obtained to a certain extent, there is still a need to further increase the melt fluidity and rigidity. Also, although Patent Documents 3 and 4 address various required properties of olefin polymers, they are insufficient to meet the requirement for an olefin polymer with even better melt fluidity and high rigidity as described above.

[0013] For a solid catalyst for olefin polymerization using a phthalate ester-based electron-donating compound, it is possible to produce an olefin polymer with a relatively high melt flow rate and a certain degree of high rigidity. On the other hand, it is difficult to produce a polymer with high rigidity and a high melt flow rate using a solid catalyst for olefin polymerization that uses a non-phthalate-based electron-donating compound.

[0014] Also, it is known that a solid catalyst component for olefin polymerization containing a succinic acid diester is effective for increasing the rigidity of an olefin polymer. However, in order to industrially produce an olefin polymer with a high melt flow rate using a solid catalyst component for olefin polymerization containing a succinic acid diester, it is necessary to use an even higher amount of hydrogen.

[0015] Therefore, an object of the present invention is to provide a method for producing an olefin polymer that can industrially and advantageously produce an olefin polymer with excellent melt fluidity and high rigidity by using a solid catalyst component for olefin polymerization containing an internal electron-donating compound other than a phthalate ester in the polymerization of olefins.

Means for Solving the Problems

[0016] As a result of intensive studies by the present inventors to solve the above technical problems, (I) Using the solid catalyst component (1) for polymerizing succinic acid diester-based olefins as a solid catalyst component to carry out the polymerization of olefins, an olefin polymer (A) can be obtained. Mixing the olefin polymer (A) with an olefin polymer (B) obtained by using the solid catalyst component (2) for polymerizing malonic acid diester-based olefins as a solid catalyst component to carry out the polymerization of olefins at a predetermined mixing ratio can obtain an olefin polymer (C1) with excellent melt flowability and high rigidity. (II) Coexisting the solid catalyst component (1) for polymerizing succinic acid diester-based olefins and the solid catalyst component (2) for polymerizing malonic acid diester-based olefins at a predetermined coexistence ratio and using them as solid catalyst components to carry out the polymerization of olefins can industrially advantageously obtain an olefin polymer (C2) with excellent melt flowability and high rigidity. Based on the above findings and others, the present invention has been completed.

[0017] That is, the present invention provides: (1) An olefin polymer (A) obtained by using a solid catalyst component (1) for polymerizing succinic acid diester-based olefins, which contains magnesium, titanium, halogen, and a succinic acid diester compound, and when converted to solid content, the content of the succinic acid diester compound in the total content of all components is 8.0 to 24.0% by mass, as a solid catalyst component to carry out the polymerization of olefins, An olefin polymer (B) obtained by using a solid catalyst component (2) for polymerizing malonic acid diester-based olefins, which contains magnesium, titanium, halogen, and a malonic acid diester compound, and when converted to solid content, the content of the malonic acid diester compound in the total content of all components is 10.0 to 20.0% by mass, as a solid catalyst component to carry out the polymerization of olefins, and A polymer mixing step of mixing the olefin polymer (A) and the olefin polymer (B) at a mixing ratio such that the ratio of the olefin polymer (A) to the total of the olefin polymer (A) and the olefin polymer (B) is 5 to 80% by mass to obtain an olefin polymer (C1). A method for producing an olefin polymer, characterized by the above. (2) The olefin polymer (A) is an olefin polymer obtained by using (I) the solid catalyst component for olefin polymerization of the succinic acid diester type (1) and (II) an organoaluminum compound, or (I) the solid catalyst component for olefin polymerization of the succinic acid diester type (1), (II) an organoaluminum compound, and (III) an external electron donor compound, and supplying hydrogen at a volume ratio (hydrogen / olefins) of 1.0 to 6.0 with respect to the gas supply amount of the olefins, The olefin polymer (B) is an olefin polymer obtained by using (I) the solid catalyst component for olefin polymerization of the malonic acid diester type (2) and (II) an organoaluminum compound, or (I) the solid catalyst component for olefin polymerization of the malonic acid diester type (2), (II) an organoaluminum compound, and (III) an external electron donor compound, and supplying hydrogen at a volume ratio (hydrogen / olefins) of 1.0 to 6.0 with respect to the gas supply amount of the olefins, A method for producing the olefin polymer according to (1), characterized in that (3) The melt flow rate (a1) of the olefin polymer (A) is 1 to 100 g / 10 minutes, and the flexural modulus (b1) is 2200 to 2500 MPa. The melt flow rate (a2) of the olefin polymer (B) is 200 to 1000 g / 10 minutes, and the flexural modulus (b2) is 1500 to 2200 MPa. A method for producing the olefin polymer according to (1) or (2), characterized in that (4) In the polymer mixing step, the olefin polymer (A) and the olefin polymer (B) are mixed at a mixing ratio such that the mixing ratio of the olefin polymer (A) with respect to the total of the olefin polymer (A) and the olefin polymer (B) is 10.0 to 50.0% by mass. A method for producing the olefin polymer according to any one of (1) to (3), characterized in that (5) The (α) melt flow rate of the olefin polymer (C1) is 100 to 200 g / 10 minutes, (β) the flexural modulus is 1900 to 2300 MPa, and (γ) the ratio of the oriented layer in the cross-section of the injection-molded plate made of the olefin polymer (C1) is 10% or more. The method for producing an olefin polymer according to any one of (1) to (4), (6) A succinic acid diester-based solid catalyst component (1) for olefin polymerization, which contains magnesium, titanium, halogen, and a succinic acid diester compound, and when converted to solid content, the content of the succinic acid diester compound in the total content of all components is 8.0 to 24.0% by mass, and A malonic acid diester-based solid catalyst component (2) for olefin polymerization, which contains magnesium, titanium, halogen, and a malonic acid diester compound, and when converted to solid content, the content of the malonic acid diester compound in the total content of all components is 10.0 to 20.0% by mass, and The succinic acid diester-based solid catalyst component (1) for olefin polymerization and the malonic acid diester-based solid catalyst component (2) for olefin polymerization coexist at an existing ratio such that the existing ratio of the succinic acid diester-based solid catalyst component (1) to the total of the succinic acid diester-based solid catalyst component (1) and the malonic acid diester-based solid catalyst component (2) is 10 to 50% by mass. (I) The succinic acid diester-based solid catalyst component (1) for olefin polymerization and the malonic acid diester-based solid catalyst component (2) for olefin polymerization, and (II) an organoaluminum compound, or (I) the succinic acid diester-based solid catalyst component (1) for olefin polymerization and the malonic acid diester-based solid catalyst component (2) for olefin polymerization, (II) an organoaluminum compound, and (III) an external electron donor compound are used to carry out the polymerization of olefins to obtain an olefin polymer (C2). The method for producing an olefin polymer is characterized by having a polymerization step. (7) In the polymerization step, the volume ratio of the hydrogen gas supply amount to the olefin gas supply amount (hydrogen / olefins) is 1.0 to 6.0. The method for producing an olefin polymer according to (6). (8) The (α) melt flow rate of the olefin polymer (C2) is 100 to 200 g / 10 minutes, (β) the flexural modulus is 1900 to 2300 MPa, and (γ) the ratio of the oriented layer in the cross-section of the injection-molded plate made of the olefin polymer (C2) is 10% or more. The method for producing an olefin polymer according to (6) or (7) is characterized in that, is provided.

Effects of the Invention

[0018] According to the present invention, there is provided a method for producing an olefin polymer, which can industrially advantageously produce an olefin polymer having excellent melt fluidity and high rigidity by using a solid catalyst component for olefin polymerization containing an internal electron donor compound other than a phthalic acid ester in the polymerization of olefins.

Brief Description of the Drawings

[0019]

Figure 1

Figure 2

Figure 3

Embodiments for Carrying Out the Invention

[0020] The method for producing an olefin polymer according to the first embodiment of the present invention includes a succinic acid diester-based solid catalyst component (1) containing magnesium, titanium, halogen, and a succinic acid diester compound, and when converted to solid content, the content of the succinic acid diester compound in the total content of all components is 8.0 to 24.0% by mass. Using this as a solid catalyst component, an olefin polymer (A) obtained by polymerizing olefins, A solid catalyst component (2) for polymerizing malonic diester-based olefins, which contains magnesium, titanium, a halogen, and a malonic diester compound and has a content of the malonic diester compound of 10.0 to 20.0% by mass in terms of solid content in the total content of all components, is used as a solid catalyst component to carry out the polymerization of olefins, and an olefin polymer (B) obtained thereby, A polymer mixing step of mixing at a mixing ratio such that the mixing ratio of the olefin polymer (A) to the total of the olefin polymer (A) and the olefin polymer (B) is 5.0 to 80.0% by mass to obtain an olefin polymer (C1), characterized in that it is a method for producing an olefin polymer.

[0021] The solid catalyst component (1) for polymerizing succinic diester-based olefins contains magnesium, titanium, a halogen, and a succinic diester compound, and when converted to solid content, the content of the succinic diester compound in the total content of all components is 8.0 to 24.0% by mass.

[0022] Examples of the solid catalyst component (1) for polymerizing succinic diester-based olefins include contact reaction products obtained by bringing a raw material component serving as a source of magnesium, a raw material component serving as a source of titanium and a halogen, and a succinic diester compound which is an internal electron donor compound into contact with each other and reacting them in an organic solvent. Specifically, dialkoxy magnesium is used as the raw material component serving as a source of magnesium, and a tetravalent titanium halogen compound is used as the raw material component serving as a source of titanium and a halogen, and examples thereof include contact reaction products obtained by bringing these raw materials into contact with an internal electron donor compound containing a succinic diester compound.

[0023] In the solid catalyst component (1) for polymerizing succinic diester-based olefins, examples of the dialkoxymagnesium as the raw material component serving as the magnesium source include one or more selected from magnesium dihalides, dialkylmagnesiums, alkylmagnesium halides, dialkoxymagnesiums, diaryloxymagnesiums, alkoxymagnesium halides, magnesium fatty acids, and the like. Among these magnesium compounds, magnesium dihalides, a mixture of magnesium dihalide and dialkoxymagnesium, and dialkoxymagnesium are preferred, and dialkoxymagnesium is particularly preferred.

[0024] Examples of the dialkoxymagnesium include dimethoxymagnesium, diethoxymagnesium, dipropoxymagnesium, dibutoxymagnesium, ethoxymethoxymagnesium, ethoxypropoxymagnesium, butoxyethoxymagnesium, and the like. Further, these dialkoxymagnesiums may be those obtained by reacting metallic magnesium with an alcohol in the presence of a halogen or a halogen-containing metal compound, etc. Also, the above dialkoxymagnesiums can be used in combination of one or more.

[0025] The above dialkoxymagnesium is preferably in the form of granules or powder, and irregular or spherical shapes can be used for its shape.

[0026] When a spherical dialkoxymagnesium is used, a polymer powder having a better particle shape (more spherical) and a narrow particle size distribution can be obtained, the handling operability of the polymer powder generated during the polymerization operation is improved, and the occurrence of blockage etc. caused by the fine powder contained in the generated polymer powder can be suppressed.

[0027] The above spherical dialkoxymagnesium does not necessarily have to be a perfect sphere, and an elliptical or potato-shaped one can also be used. Substantially, the shape of its particles has a ratio (l / w) of the major axis diameter l to the minor axis diameter w of 3 or less, preferably 1 to 2, more preferably 1 to 1.5.

[0028] Further, the average particle diameter (average particle diameter D50) of the dialkoxymagnesium is preferably 1.0 to 200.0 μm, more preferably 5.0 to 150.0 μm. Here, the average particle diameter D50 means the particle diameter at 50% of the integrated particle size in the volume integrated particle size distribution when measured using a laser light scattering diffraction particle size analyzer. When the dialkoxymagnesium is spherical, the average particle diameter 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.

[0029] Further, regarding the particle size distribution of the dialkoxymagnesium, it is preferably one with less fine powder and coarse powder and a narrow particle size distribution. Specifically, when the dialkoxymagnesium is measured using a laser light scattering diffraction particle size analyzer, the particles with a particle diameter of 5.0 μm or less are preferably 20% or less, more preferably 10% or less. On the other hand, when measured using a laser light scattering diffraction particle size analyzer, the particles with a particle diameter of 100.0 μm or more are preferably 20% or less, more preferably 10% or less. Furthermore, when the particle size distribution is represented by ln(D90 / D10), it is preferably 3 or less, more preferably 2 or less. Here, D90 means the particle diameter at 90% of the integrated particle size in the volume integrated particle size distribution when measured using a laser light scattering diffraction particle size analyzer. Also, D10 means the particle diameter at 10% of the integrated particle size in the volume integrated particle size distribution when measured using a laser light scattering diffraction particle size analyzer.

[0030] The method for producing the spherical dialkoxymagnesium is exemplified in, for example, JP-A-62-51633, JP-A-3-74341, JP-A-4-368391, JP-A-8-73388, etc.

[0031] In the solid catalyst component (1) for polymerizing succinic diester-based olefins, as the dialkoxymagnesium, those having a specific surface area of 5 m 2 / g or more are preferred, those having a specific surface area of 5 to 50 m 2 / g are more preferred, and those having a specific surface area of 10 to 40 m 2 / g are even more preferred. By using dialkoxymagnesium having a specific surface area within the above range, a solid catalyst component for polymerizing olefins having a desired specific surface area can be easily prepared.

[0032] In the present application documents, the specific surface area of dialkoxymagnesium means the value measured by the BET method. Specifically, the specific surface area of dialkoxymagnesium means the value measured by the BET method (automatic measurement) in the presence of a mixed gas of nitrogen and helium after preliminarily vacuum-drying the measurement sample at 50 °C for 2 hours and using the Automatic Surface Area Analyzer HM model-1230 manufactured by Mountech.

[0033] The above dialkoxymagnesium is preferably in a solution state or a suspension state during the reaction, and the reaction can proceed favorably by being in a solution state or a suspension state.

[0034] When the above dialkoxymagnesium is solid, it can be made into a solution-state dialkoxymagnesium by dissolving it in a solvent having solubilizing ability for dialkoxymagnesium, or a dialkoxymagnesium suspension can be made by suspending it in a solvent having no solubilizing ability for dialkoxymagnesium. When the dialkoxymagnesium is liquid, it may be used as it is as a solution-state dialkoxymagnesium, or it may be further dissolved in a solvent having solubilizing ability for dialkoxymagnesium and used as a solution-state dialkoxymagnesium.

[0035] Examples of the compound capable of solubilizing solid dialkoxymagnesium include at least one compound selected from the group consisting of alcohols, ethers, and esters. Alcohols such as ethanol, propanol, butanol, and 2-ethylhexanol are preferred, and 2-ethylhexanol is particularly preferred. On the other hand, examples of the medium that does not have the ability to solubilize solid dialkoxymagnesium include one or more selected from saturated hydrocarbon solvents and unsaturated hydrocarbon solvents that do not dissolve dialkoxymagnesium.

[0036] In the solid catalyst component (1) for polymerizing succinic diester-based olefins, the tetravalent titanium halogen compound, which is a raw material component serving as a source of titanium and halogen, is not particularly limited, but the following general formula (1): Ti(OR 1 ) p X 4-p (1) (In the formula, R 1 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 satisfies 0 ≦ r ≦ 3.) It is preferred that the compound is one or more selected from the group of titanium halides or alkoxytitanium halides represented by the formula.

[0037] In the above general formula (1), p satisfies 0 ≦ p ≦ 3, and specifically, p can be 0, 1, 2, or 3.

[0038] Examples of the titanium halide represented by the above general formula (1) include one or more titanium tetrahalides selected from titanium tetrachloride, titanium tetrabromide, titanium tetraiodide, etc. In addition, examples of the alkoxytitanium halide represented by the general formula (1) include one or more selected from methoxytitanium trichloride, ethoxytitanium trichloride, propoxytitanium trichloride, n-butoxytitanium trichloride, dimethoxytitanium dichloride, diethoxytitanium dichloride, dipropoxytitanium dichloride, di-n-butoxytitanium dichloride, trimethoxytitanium chloride, triethoxytitanium chloride, tripropoxytitanium chloride, tri-n-butoxytitanium chloride, and the like. As the tetravalent titanium halogen compound, titanium tetrahalide is preferable, and titanium tetrachloride is more preferable. These titanium compounds may be used alone or in combination of two or more.

[0039] In the succinic acid diester-based solid catalyst component (1) for olefin polymerization, examples of the succinic acid diester compound include the following general formula (2): R 2 -O-C(=O)-CHR 3 CHR 4 -C(=O)-O-R 5 (2) (R 3 and R 4 are each a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, which may be the same or different from each other, and R 2 and R 5 are each a linear alkyl group or a branched alkyl group having 2 to 4 carbon atoms, which may be the same or different from each other.) One or more selected from the compounds represented by the formula can be mentioned.

[0040] In the compound represented by the general formula (2), R 2 and R 5 are each a linear alkyl group or a branched alkyl group having 2 to 4 carbon atoms, which may be the same or different from each other. R 2 and R 5When it is a linear or branched alkyl group having 2 to 4 carbon atoms, specifically, ethyl, n-propyl group, isopropyl group, n-butyl group or isobutyl group can be mentioned. In the compound represented by the general formula (2), R 3 and R 4 are a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and may be the same as or different from each other. R 3 and R 4 When they are alkyl groups having 1 to 4 carbon atoms, specifically, methyl group, ethyl, n-propyl group, isopropyl group, n-butyl group or isobutyl group can be mentioned.

[0041] In the solid catalyst component (1) for polymerizing succinic acid diester-based olefins, the succinic acid diester compound is not particularly limited, and examples thereof include the compound represented by the general formula (2). As the compound represented by the general formula (2), for example, diethyl succinate, 2,3-dimethyl diethyl succinate, 2,3-diethyl diethyl succinate, 2,3-di-n-propyl diethyl succinate, 2,3-diisopropyl diethyl succinate, 2,3-di-n-butyl diethyl succinate, 2,3-diisobutyl diethyl succinate; di-n-propyl succinate, 2,3-dimethyl di-n-propyl succinate, 2,3-diethyl di-n-propyl succinate, 2,3-di-n-propyl di-n-propyl succinate, 2,3-diisopropyl di-n-propyl succinate, 2,3-di-n-butyl di-n-propyl succinate, 2,3-diisobutyl di-n-propyl succinate; diisopropyl succinate, 2,3-dimethyl diisopropyl succinate, 2,3-diethyl diisopropyl succinate, 2,3-di-n-propyl diisopropyl succinate, 2,3-diisopropyl diisopropyl succinate, 2,3-di-n-butyl diisopropyl succinate, 2,3-diisobutyl diisopropyl succinate; Di-n-butyl succinate, di-n-butyl 2,3-dimethyl succinate, di-n-butyl 2,3-diethyl succinate, di-n-butyl 2,3-di-n-propyl succinate, di-n-butyl 2,3-diisopropyl succinate, di-n-butyl 2,3-di-n-butyl succinate, di-n-butyl 2,3-diisobutyl succinate; Diisobutyl succinate, diisobutyl 2,3-dimethyl succinate, diisobutyl 2,3-diethyl succinate, diisobutyl 2,3-di-n-propyl succinate, diisobutyl 2,3-diisopropyl succinate, diisobutyl 2,3-di-n-butyl succinate, diisobutyl 2,3-diisobutyl succinate; One or more selected from the above can be mentioned. Among these succinic acid diesters, diethyl succinate, di-n-propyl succinate, di-n-butyl succinate, diisobutyl succinate, diethyl 2,3-di-n-propyl succinate, diethyl 2,3-diisopropyl succinate, di-n-propyl 2,3-di-n-propyl succinate, di-n-propyl 2,3-diisopropyl succinate, diisopropyl 2,3-di-n-propyl succinate, diisopropyl 2,3-diisopropyl succinate, di-n-butyl 2,3-di-n-propyl succinate, di-n-butyl 2,3-diisopropyl succinate, diisobutyl 2,3-di-n-propyl succinate, diisobutyl 2,3-diisopropyl succinate are preferably used.

[0042] Further, the compound represented by the above general formula (2) may be used alone or in combination of two or more.

[0043] The solid catalyst component (1) for polymerizing succinic acid diester-based olefins contains a succinic acid diester compound as an essential component as an internal electron donor compound, but as an internal electron donor compound other than the succinic acid diester compound, it may further contain other internal electron donor compounds (hereinafter, appropriately referred to as "other internal electron donor compounds").

[0044] Examples of such other internal electron donating compounds include one or more selected from carbonates, acid halides, acid amides, nitriles, acid anhydrides, diether compounds, carboxylic acid esters, and the like.

[0045] Specific examples of such other internal electron donating compounds include one or more selected from ether carbonate compounds, carboxylic acid diesters such as cycloalkane dicarboxylic acid diesters, cycloalkene dicarboxylic acid diesters, alkyl-substituted malonic acid diesters, and maleic acid diesters, and diether compounds. More specifically, one or more selected from ether carbonate compounds such as (2-ethoxyethyl) methyl carbonate, (2-ethoxyethyl) ethyl carbonate, and (2-ethoxyethyl) phenyl carbonate, cycloalkane dicarboxylic acid diesters such as dimethyl cyclohexane-1,2-dicarboxylate, and 1,3-diether such as (isopropyl)(isopentyl)-1,3-dimethoxypropane and 9,9-bis(methoxymethyl)fluorene are more preferred.

[0046] On the other hand, for the solid catalyst component (1) for polymerizing succinic acid diester-based olefins, the phthalic acid ester content is preferably 0.2% by mass or less (0.0 to 0.2% by mass), more preferably 0.1% by mass or less (0.0 to 0.1% by mass), and still more preferably 0.0% by mass (substantially free of phthalic acid ester (below the detection limit)).

[0047] In the solid catalyst component (1) for the polymerization of succinic diester-based olefins, when converted to solid content, the content of the succinic diester compound in the total content components is 8.0 to 24.0% by mass, preferably 12.0 to 22.0% by mass, more preferably 14.0 to 20.0% by mass. When the content of the succinic diester compound in the total content components when converted to solid content is within the above range, in the polymerization of olefins, the molecular weight distribution of the olefin polymer can be broadened and the rigidity can be increased. On the other hand, when the content of the succinic diester compound in the total content components when converted to solid content is less than the above range, the molecular weight distribution will not be sufficiently broad, and when it exceeds the above range, the polymerization activity will decrease.

[0048] In the solid catalyst component (1) for the polymerization of succinic diester-based olefins, when converted to solid content, the content of titanium atoms in the total content components is 2.0 to 6.0% by mass, preferably 2.5 to 5.0% by mass, more preferably 3.0 to 4.5% by mass.

[0049] In the solid catalyst component (1) for the polymerization of succinic diester-based olefins, when converted to solid content, the content of halogen atoms in the total content components is 50.0 to 70.0% by mass, preferably 55.0 to 68.0% by mass, more preferably 58.0 to 67.0% by mass.

[0050] In the solid catalyst component (1) for the polymerization of succinic diester-based olefins, when converted to solid content, the content of magnesium atoms in the total content components is 15.0 to 25.0% by mass, preferably 16.0 to 23.0% by mass, more preferably 16.0 to 22.0% by mass.

[0051] The solid catalyst component (1) for the polymerization of succinic diester-based olefins may contain polysiloxane.

[0052] Since the solid catalyst component (1) for polymerizing succinic diester-based olefins contains polysiloxane, when olefins are polymerized, the stereoregularity or crystallinity of the resulting polymer can be easily improved, and furthermore, the fine powder of the produced polymer can be easily reduced. Polysiloxane is a polymer having a siloxane bond (-Si-O-bond) in the main chain, and is also called silicone oil, and has a viscosity at 25 °C of 0.02 to 100.00 cm 2 / s (2 to 10,000 centistokes), more preferably 0.03 to 5.00 cm 2 / s (3 to 500 centistokes), and is a chain-like, partially hydrogenated, cyclic or modified polysiloxane that is liquid or viscous at room temperature.

[0053] Examples of the chain-like polysiloxane include dimethylpolysiloxane and methylphenylpolysiloxane. Examples of the partially hydrogenated polysiloxane include methylhydrogenpolysiloxane having a hydrogenation rate of 10 to 80%. Examples of the cyclic polysiloxane include one or more selected from hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, 2,4,6-trimethylcyclotrisiloxane, and 2,4,6,8-tetramethylcyclotetrasiloxane.

[0054] The solid catalyst component (1) for polymerizing succinic diester-based olefins is preferably prepared by bringing the above dialkoxymagnesium, titanium halogen compound, and succinic diester compound into contact with each other in the presence of an inert organic solvent.

[0055] In the present invention, as the inert organic solvent, those that can dissolve the titanium halogen compound but cannot dissolve dialkoxymagnesium are preferred. Specifically, examples include one or more selected from saturated hydrocarbon compounds such as pentane, hexane, heptane, octane, nonane, decane, cyclohexane, methylcyclohexane, ethylcyclohexane, 1,2 - diethylcyclohexane, methylcyclohexene, decalin, mineral oil, etc.; aromatic hydrocarbon compounds such as benzene, toluene, xylene, ethylbenzene, etc.; and halogenated hydrocarbon compounds such as orthodichlorobenzene, methylene chloride, 1,2 - dichlorobenzene, carbon tetrachloride, dichloroethane, etc. As the inert organic solvent, saturated hydrocarbon compounds or aromatic hydrocarbon compounds having a boiling point of about 50 to 200 °C and being liquid at room temperature are preferably used. Among them, one or more selected from hexane, heptane, octane, ethylcyclohexane, mineral oil, toluene, xylene, and ethylbenzene are preferred, and any one or more selected from hexane, heptane, ethylcyclohexane, and toluene are particularly preferred.

[0056] In the solid catalyst component for olefin polymerization according to the present invention, magnesium, titanium, halogen, and the succinic acid diester compound can each be contained in a desired amount as long as they satisfy the content of the succinic acid diester compound described above.

[0057] In the present application documents, the content of titanium contained in the solid catalyst component for olefin polymerization means the value measured according to the method (oxidation - reduction titration) described in JIS 8311 - 1997 "Method for Determination of Titanium in Titanium Ore".

[0058] Also, in the present application documents, the content of magnesium in the solid catalyst component for olefin polymerization means 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.

[0059] In addition, in this application document, the content of the halogen contained in the solid catalyst component for olefin polymerization means the value measured by the silver nitrate titration method in which the solid catalyst component is treated with a mixed solution of sulfuric acid and pure water to form an aqueous solution, a predetermined amount is separated, and the halogen is titrated with a silver nitrate standard solution.

[0060] Furthermore, in this application document, the content ratio of the succinic acid diester compound contained in the solid catalyst component for olefin polymerization and the content of other internal electron donor compounds added as necessary mean the values measured by gas chromatography FID (Flame Ionization Detector) method after hydrolyzing the solid catalyst component for olefin polymerization and extracting the succinic acid diester compound and other internal electron donor compounds added as necessary using an aromatic solvent.

[0061] The solid catalyst component (1) for olefin polymerization based on succinic acid diester can be preferably produced by the production method of the solid catalyst component (1) for olefin polymerization based on succinic acid diester described below.

[0062] Next, the production method of the solid catalyst component (1) for olefin polymerization based on succinic acid diester will be described.

[0063] As a production method of the solid catalyst component (1) for olefin polymerization based on succinic acid diester, a method of obtaining the solid catalyst component (1) for olefin polymerization based on succinic acid diester by bringing a raw material component serving as a source of magnesium, a raw material component serving as a source of titanium and halogen, and a succinic acid diester compound which is an internal electron donor compound into contact with each other and reacting them in an organic solvent can be mentioned. Specifically, a method of obtaining the solid catalyst component (1) for olefin polymerization based on succinic acid diester by using dialkoxymagnesium as a raw material component serving as a source of magnesium and a tetravalent titanium halogen compound as a raw material component serving as a source of titanium and halogen and bringing these raw materials into contact with an internal electron donor compound containing a succinic acid diester compound can be mentioned.

[0064] The contact of each of the above components is preferably carried out while stirring in a container equipped with a stirrer under a situation where moisture and the like are removed in an inert gas atmosphere. When simply bringing the above components into contact and stirring and mixing them, or when dispersing or suspending them for modification treatment, the temperature for bringing the above components into contact may be around room temperature without any particular problem, but it is preferably in a relatively low temperature range, and a temperature range of -20 to 30 °C is preferred. Also, when reacting at a high temperature in the contacted state to obtain a solid product, it is preferably at a relatively high temperature, and a temperature range of 40 to 130 °C is preferred. When the temperature during the reaction is less than 40 °C, the reaction does not proceed sufficiently, and as a result, the performance of the prepared solid catalyst component becomes insufficient. When it exceeds 130 °C, the evaporation of the solvent used becomes remarkable, etc., and it becomes difficult to control the reaction. In addition, the reaction time after the above contact is preferably 1 minute or more, more preferably 10 minutes or more, and even more preferably 30 minutes or more.

[0065] The order of bringing each component into contact when producing the solid catalyst component (1) for polymerizing succinic diester-based olefins is more specifically exemplified below. (1) Magnesium compound → Internal electron donor compound → Inert organic solvent → Tetravalent titanium halogen compound → 《Intermediate washing → Inert organic solvent → Tetravalent halogen compound》 → Final washing (2) Magnesium compound → Inert organic solvent → Internal electron donor compound → Tetravalent halogen compound → 《Intermediate washing → Inert organic solvent → Tetravalent titanium halogen compound》 → Final washing (3) Magnesium compound → Tetravalent halogen compound → Inert organic solvent → Internal electron donor compound → 《Intermediate washing → Inert organic solvent → Internal electron donor compound → Tetravalent titanium halogen compound》 → Final washing (4) Magnesium compound → Tetravalent titanium halogen compound → Inert organic solvent → Internal electron donor compound → 《Intermediate washing → Inert organic solvent → Tetravalent titanium halogen compound → Internal electron donor compound》 → Final washing (5) Magnesium compound → tetravalent halogen compound → inert organic solvent → internal electron donor compound → 《Intermediate washing → inert organic solvent → internal electron donor compound → tetravalent titanium halogen compound》 → final washing (6) Magnesium compound → inert organic solvent → tetravalent titanium halogen compound → internal electron donor compound → 《Intermediate washing → inert organic solvent → tetravalent titanium halogen compound → internal electron donor compound》 → final washing (7) Magnesium compound → inert organic solvent → internal electron donor compound → tetravalent titanium halogen compound → 《Intermediate washing → internal electron donor compound → inert organic solvent → tetravalent titanium halogen compound》 → final washing (8) Magnesium compound → inert organic solvent → internal electron donor compound → tetravalent titanium halogen compound → 《Intermediate washing → internal electron donor compound → inert organic solvent → tetravalent titanium halogen compound》 → final washing

[0066] In the above contact examples (1) to (8), "→" means the contact order. For example, "magnesium compound → internal electron donor compound" means that the magnesium compound and the internal electron donor compound are contacted in this order. Also, in the above contact examples (1) to (8), the processes within the double parentheses (《 》) mean processes that are repeated a plurality of times as necessary. By repeating the processes within the double parentheses, the activity is further improved. Also, the tetravalent halogen compound and the inert organic solvent used in the processes within the double parentheses may be newly added or may be the residues from the previous process. Also, when adding a tetravalent titanium halogen compound, the tetravalent titanium halogen compound used in the processes within the double parentheses may be newly added or may be the residue of the tetravalent halogen compound in the previous process. In the above contact examples (1) to (8), the washing in the intermediate washing and the final washing, etc. is preferably carried out using a liquid hydrocarbon compound at room temperature. In the processes other than the intermediate washing process and the final washing process shown in the above contact examples (1) to (8), it is preferable to wash the product obtained at each contact stage.

[0067] As a particularly preferred preparation method for producing the solid catalyst component (1) for polymerizing succinic diester-based olefins, methods such as the above (2), (4), (6), etc. can be mentioned. That is, dialkoxymagnesium, which is a magnesium compound, is suspended in toluene, heptane, cyclohexane, etc., which are inert organic solvents, and then titanium tetrachloride, which is a tetravalent titanium halogen compound, is added to and contacted with the obtained suspension. Before or after the contact of the tetravalent titanium halogen compound with the suspension, one or more succinic diester compounds, which are internal electron donor compounds, are contacted and reacted with the suspension at -20 to 130 °C. In this case, it is desirable to carry out an aging reaction at a low temperature before or after the contact of the internal electron donor compound with the suspension.

[0068] The solid obtained in this way is, if necessary, washed (pre-washed) with a liquid hydrocarbon compound at room temperature, and then a tetravalent titanium halogen compound is contacted in the presence of a hydrocarbon compound, and a reaction treatment is carried out at 40 to 130 °C. The obtained reaction product may be washed (post-washed) with a liquid hydrocarbon compound at room temperature to obtain the target solid catalyst component for olefin polymerization. The above pre-washing and the reaction of the pre-washed product with the tetravalent titanium halogen compound may be repeated a plurality of times.

[0069] The preferred conditions for the above treatment or washing are as follows. <Aging reaction conditions at low temperature before or after contact of the electron donor> 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.

[0070] <Reaction conditions in the step before intermediate washing> In the process before intermediate washing, the reaction temperature of the magnesium compound, internal electron donor 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.

[0071] <Washing conditions during intermediate washing and final washing> The washing temperature is preferably 0 to 110 °C, more preferably 30 to 100 °C, and even more preferably 30 to 90 °C. The number of washing times is preferably 1 to 20 times, more preferably 1 to 15 times, and even more preferably 1 to 10 times. In addition, the hydrocarbon compound that is liquid at room temperature used during intermediate washing and final washing is preferably an aromatic hydrocarbon compound or a saturated hydrocarbon compound that is liquid at room temperature (20 °C). Specifically, examples of aromatic hydrocarbon compounds include toluene, xylene, ethylbenzene, etc., and examples of saturated hydrocarbon compounds include hexane, heptane, cyclohexane, methylcyclohexane, etc. Preferably, an aromatic hydrocarbon compound is used for intermediate washing and a saturated hydrocarbon compound is used for final washing.

[0072] The usage ratio of each component during the production of the solid catalyst component (1) for polymerizing succinic acid diester-based olefins cannot be generally specified because it varies depending on the preparation method. For example, per mole of the magnesium compound, the succinic acid diester 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.

[0073] In addition, in the above preparation method, in addition to the succinic acid diester compound, other internal electron donating compounds may be used in combination. Further, the above contact may be carried out, for example, in the presence of other reaction reagents such as silicon, phosphorus, aluminum, etc. or a surfactant.

[0074] In the method for producing the solid catalyst component (1) for polymerizing succinic acid diester olefins, a preferred embodiment of the obtained solid catalyst component (1) for polymerizing succinic acid diester olefins is as detailed in the description of the solid catalyst component (1) for polymerizing succinic acid diester olefins.

[0075] The solid catalyst component (2) for polymerizing malonic acid diester olefins contains magnesium, titanium, halogen, and a malonic acid diester compound, and when converted to solid content, the content of the malonic acid diester compound in the total content of all components is 10.0 to 20.0% by mass.

[0076] Examples of the solid catalyst component (2) for polymerizing malonic acid diester olefins include contact reaction products obtained by bringing a raw material component serving as a source of magnesium, a raw material component serving as a source of titanium and halogen, and a malonic acid diester compound which is an internal electron donating compound into contact with each other and reacting them in an organic solvent. Specifically, dialkoxy magnesium is used as the raw material component serving as a source of magnesium, and a tetravalent titanium halogen compound is used as the raw material component serving as a source of titanium and halogen, and examples thereof include contact reaction products obtained by bringing these raw materials into contact with an internal electron donating compound containing a malonic acid diester compound.

[0077] In the solid catalyst component (2) for polymerizing malonic acid diester olefins, the dialkoxy magnesium which is the raw material component serving as a source of magnesium is the same as the dialkoxy magnesium which is the raw material component serving as a source of magnesium in the solid catalyst component (1) for polymerizing succinic acid diester olefins.

[0078] In the solid catalyst component (2) for polymerizing malonic acid diester-based olefins, the tetravalent titanium halogen compound, which is a raw material component serving as a source of titanium and halogen, is the same as the tetravalent titanium halogen compound, which is a raw material component serving as a source of titanium and halogen, in the solid catalyst component (1) for polymerizing succinic acid diester-based olefins.

[0079] In the solid catalyst component (2) for polymerizing malonic acid diester-based olefins, as the malonic acid diester compound, the following general formula (3): R 6 -O-C(=O)-C(R 7 )(R 8 )-C(=O)-O-R 9 (3) (R 6 and R 9 are alkyl groups having 1 to 4 carbon atoms and may be the same as or different from each other, and R 7 and R 8 are linear or branched alkyl groups having 2 to 4 carbon atoms and may be the same as or different from each other.) One or more compounds selected from the compounds represented by the formula can be mentioned. It is preferable that the malonic acid diester compound is a compound represented by the following general formula (3) in terms of obtaining an olefin polymer having a high melt flow rate.

[0080] In the compound represented by the general formula (3), R 6 and R 9 are linear or branched alkyl groups having 1 to 4 carbon atoms and may be the same as or different from each other. R 6 and R 9 When they are linear or branched alkyl groups having 1 to 4 carbon atoms, specifically, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, a t-butyl group or an isobutyl group can be mentioned. In the compound represented by the general formula (3), R 7 and R 8is a linear or branched alkyl group having 2 to 4 carbon atoms, which may be the same or different from each other. R 7 and R 8 When they are linear or branched alkyl groups having 2 to 4 carbon atoms, specifically, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, a t-butyl group or an isobutyl group can be mentioned.

[0081] In the solid catalyst component (2) for polymerizing malonic diester-based olefins, the malonic diester compound is not particularly limited, and examples thereof include the compounds represented by the general formula (3). As the compounds represented by the general formula (3), for example, diethyl di-n-propylmalonate, di-n-propyl di-n-propylmalonate, di-n-propyl di-n-butylmalonate, di-n-propyl diisobutylmalonate, di-n-propyl dimethylmalonate, diisopropyl dimethylmalonate, diisobutyl dimethylmalonate, di-t-butyl dimethylmalonate, di-sec-butyl dimethylmalonate, diisopropyl diethylmalonate, diisopropyl dipropylmalonate, diisopropyl diisopropylmalonate, diisopropyl dibutylmalonate, diisopropyl diisobutylmalonate, diisobutyl diethylmalonate, diisobutyl dipropylmalonate, diisobutyl diisopropylmalonate, diisobutyl dibutylmalonate, diisobutyl diisobutylmalonate, isopropyl isobutyl diethylmalonate, isopropyl isobutyl dipropylmalonate, isopropyl isobutyl diisopropylmalonate, isopropyl isobutyl dibutylmalonate, isopropyl isobutyl diisobutylmalonate and the like can be mentioned. Preferred are dimethyl diisopropylmalonate, dimethyl diisobutylmalonate, dimethyl di-t-butylmalonate, dimethyl di-sec-butylmalonate, dimethyl diisopentylmalonate, dimethyl dineopentylmalonate, and particularly preferred are dimethyl diisopropylmalonate and dimethyl diisobutylmalonate.

[0082] The compound represented by the general formula (3) may be used alone or in combination of two or more thereof.

[0083] The solid catalyst component (2) for polymerizing malonic acid diester-based olefins contains a malonic acid diester compound as an essential component as an internal electron donor compound, but as an internal electron donor compound other than the malonic acid diester compound, it may further contain other internal electron donor compounds (hereinafter, appropriately referred to as "other internal electron donor compounds").

[0084] Such other internal electron donor compounds related to the solid catalyst component (2) for polymerizing malonic acid diester-based olefins are the same as the other internal electron donor compounds related to the solid catalyst component (1) for polymerizing succinic acid diester-based olefins.

[0085] On the other hand, for the solid catalyst component (2) for polymerizing malonic acid diester-based olefins, the content of phthalic acid ester is suitably 0.2% by mass or less (0.0 to 0.2% by mass), more suitably 0.1% by mass or less (0.0 to 0.1% by mass), and even more suitably 0.0% by mass (substantially free of phthalic acid ester (below the detection limit)).

[0086] In the solid catalyst component (2) for polymerizing malonic acid diester-based olefins, when converted to solid content, the content of the malonic acid diester compound in the total content of all components 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 the content of the malonic acid diester compound in the total content of all components when converted to solid content being within the above range, an olefin polymer with a very high melt flow rate can be obtained.

[0087] In the solid catalyst component (2) for polymerizing malonic acid diester-based olefins, when converted to solid content, the content of titanium atoms in the total content of all components is 3.0 to 6.0% by mass, preferably 3.5 to 6.0% by mass, and more preferably 4.0 to 6.0% by mass.

[0088] In the solid catalyst component (2) for polymerizing diester malonate olefins, when converted to solid content, the content of halogen atoms in the total content of all components is 50.0 to 70.0% by mass, preferably 55.0 to 68.0% by mass, more preferably 58.0 to 67.0% by mass.

[0089] In the solid catalyst component (2) for polymerizing diester malonate olefins, when converted to solid content, the content of magnesium atoms in the total content of all components is 15.0 to 25.0% by mass, preferably 16.0 to 23.0% by mass, more preferably 16.0 to 22.0% by mass.

[0090] The solid catalyst component (2) for polymerizing diester malonate olefins may contain polysiloxane. The polysiloxane related to the solid catalyst component (2) for polymerizing diester malonate olefins is the same as the polysiloxane related to the solid catalyst component (1) for polymerizing diester succinate olefins.

[0091] The solid catalyst component (2) for polymerizing diester malonate olefins is preferably prepared by bringing the above dialkoxymagnesium, titanium halogen compound and diester malonate compound into contact in the presence of an inert organic solvent.

[0092] The inert organic solvent related to the solid catalyst component (2) for polymerizing diester malonate olefins is the same as the inert organic solvent related to the solid catalyst component (1) for polymerizing diester succinate olefins.

[0093] The solid catalyst component (2) for polymerizing diester malonate olefins can be preferably produced by the production method of the solid catalyst component (1) for polymerizing diester malonate olefins described below.

[0094] Next, the production method of the solid catalyst component (2) for polymerizing diester malonate olefins will be described.

[0095] As a method for producing the solid catalyst component (2) for polymerizing malonic diester-based olefins, there is a method of obtaining the solid catalyst component (2) for polymerizing malonic diester-based olefins by bringing into mutual contact and reacting a raw material component serving as a source of magnesium, a raw material component serving as a source of titanium and halogen, and a malonic diester compound which is an internal electron donor compound in an organic solvent. Specifically, there is a method of using dialkoxymagnesium as the raw material component serving as a source of magnesium and a tetravalent titanium halogen compound as the raw material component serving as a source of titanium and halogen, and bringing these raw materials into mutual contact with an internal electron donor compound containing a malonic diester compound to obtain the solid catalyst component (2) for polymerizing malonic diester-based olefins.

[0096] The method for producing the solid catalyst component (2) for polymerizing malonic diester-based olefins is the same as the method for producing the solid catalyst component (1) for polymerizing succinic diester-based olefins, except that in the method for producing the solid catalyst component (1) for polymerizing succinic diester-based olefins, the internal electron donor compound used is a malonic diester compound instead of a succinic diester compound.

[0097] The usage ratio of each component in the production of the solid catalyst component (2) for polymerizing malonic diester-based olefins cannot be generally specified because it varies depending on the preparation method. For example, per 1 mol of the magnesium compound, the malonic diester compound is preferably 0.01 to 10 mol, more preferably 0.01 to 1 mol, even more preferably 0.02 to 0.6 mol; the tetravalent titanium halogen compound is preferably 0.5 to 100 mol, more preferably 0.5 to 50 mol, even more preferably 1 to 10 mol; the inert organic solvent is preferably 0.001 to 500 mol, more preferably 0.001 to 100 mol, particularly preferably 0.005 to 10 mol.

[0098] The olefin polymer (A) is a polymer obtained by polymerizing olefins using the succinic acid diester-based solid catalyst component (1) for olefin polymerization as a solid catalyst component. That is, the olefin polymer (A) is a catalyst (A) for olefin polymerization containing (I) the succinic acid diester-based solid catalyst component (1) for olefin polymerization and (II) an organoaluminum compound, or (I) the succinic acid diester-based solid catalyst component (1) for olefin polymerization, (II) an organoaluminum compound, and (III) an external electron donor compound. Preferably, the olefin polymer (A) is a polymer obtained by polymerizing olefins using the catalyst (A) for olefin polymerization obtained by bringing (I) the succinic acid diester-based solid catalyst component (1) for olefin polymerization, (II) an organoaluminum compound, and (III) an external electron donor compound into contact with each other as a catalyst for olefin polymerization.

[0099] The catalyst (A) for olefin polymerization preferably comprises at least (I) the succinic acid diester-based solid catalyst component (1) for olefin polymerization, and (II) the following general formula (4): R 10 q AlQ 3-q (4) (In the formula, R 10 is an alkyl group having 1 to 6 carbon atoms, Q is a hydrogen atom or a halogen, q satisfies 0 < q ≦ 3, and when a plurality of R 10 are present, each R 10 may be the same as or different from each other, and when a plurality of Q are present, each Q may be the same as or different from each other.) and is characterized by containing an organoaluminum compound represented by the formula. As the catalyst (A) for olefin polymerization, (I) the succinic acid diester-based solid catalyst component (1) for olefin polymerization, (II) the following 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 satisfies 0 < q ≦ 3, and when a plurality of R 5 are present, each R 10 may be the same as or different from each other, and when a plurality of Q are present, each Q may be the same as or different from each other.). The organoaluminum compound represented by, and (III) an external electron donor compound is preferably included.

[0100] The details of the solid catalyst component (1) for olefin polymerization of the (I) succinic diester type for constituting the olefin polymerization catalyst (A) are as described above.

[0101] In the olefin polymerization catalyst (A), the (II) organoaluminum compound has the 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, p satisfies 0 < p ≦ 3, and when a plurality of R 10 are present, each R 5 may be the same as or different from each other, and when a plurality of Q are present, each Q may be the same as or different from each other.). It is represented by

[0102] In the compound represented by the general formula (4), p satisfies 0 < p ≦ 3, and specifically, examples of p include 1, 2, or 3.

[0103] Specific examples of such (II) organoaluminum compounds include one or more selected from trialkylaluminums such as triethylaluminum, triisopropylaluminum, tri-n-butylaluminum, tri-n-hexylaluminum, triisobutylaluminum, etc., alkylaluminum halides such as diethylaluminum chloride, diethylaluminum bromide, etc., and diethylaluminum hydride. One or more selected from alkylaluminum halides such as diethylaluminum chloride, and trialkylaluminums such as triethylaluminum, tri-n-butylaluminum, and triisobutylaluminum are preferred, and one or more selected from triethylaluminum and triisobutylaluminum are more preferred.

[0104] As the (III) external electron donor compound constituting the olefin polymerization catalyst (A), For example, the following general formula (5): R 11 r Si(NR 12 R 13 ) s (OR 14 ) 4-(r+s) (5) (In the formula, r is 0 or 1 to 2, s is 0 or 1 to 2, r + s is 0 or 1 to 4, R 11 , R 12 or R 13 is any group selected from a hydrogen atom or a linear or branched alkyl group having 1 to 12 carbon atoms, a substituted or unsubstituted cycloalkyl group, a phenyl group, an allyl group, and an aralkyl group, which may contain a heteroatom and may be the same or different from each other. R 12 and R 13 may be bonded to form a cyclic shape, and R 11 , R 12 and R 13 may be the same or different. Also, R 14 is any group selected from an alkyl group having 1 to 4 carbon atoms, a cycloalkyl group, a phenyl group, a vinyl group, an allyl group, and an aralkyl group, which may contain a heteroatom.) Compounds represented by the formula are included.

[0105] In the compound represented by the general formula (5) above, R 11 is any group selected from a hydrogen atom, a linear or branched alkyl group having 1 to 12 carbon atoms, a substituted or unsubstituted cycloalkyl group, a phenyl group, an allyl group, and an aralkyl group, and may contain a hetero atom. R 11 is preferably a linear or branched alkyl group having 1 to 10 carbon atoms or a cycloalkyl group having 5 to 8 carbon atoms, and particularly preferably a linear or branched alkyl group having 1 to 8 carbon atoms or a cycloalkyl group having 5 to 8 carbon atoms.

[0106] In the compound represented by the general formula (5) above, R 12 or R 13 is any group selected from a hydrogen atom, a linear or branched alkyl group having 1 to 12 carbon atoms, a substituted or unsubstituted cycloalkyl group, a phenyl group, an allyl group, and an aralkyl group, and may contain a hetero atom. R 12 or R 13 is preferably a linear or branched alkyl group having 1 to 10 carbon atoms or a cycloalkyl group having 5 to 8 carbon atoms, and particularly preferably a linear or branched alkyl group having 1 to 8 carbon atoms or a cycloalkyl group having 5 to 8 carbon atoms. Also, R 12 and R 13 may combine to form a cyclic shape. In this case, the (NR 12 R 13 ) forming the cyclic shape is preferably a perhydroquinolino group or a perhydroisoquinolino group.

[0107] In the compound represented by the general formula (5) above, R 11 , R 12 and R 13 may be the same or different.

[0108] In the compound represented by the general formula (5) above, R 14is any group selected from an alkyl group having 1 to 4 carbon atoms, a cycloalkyl group, a phenyl group, an allyl group, and an aralkyl group, which may contain a heteroatom. R 14 is preferably a linear or branched alkyl group having 1 to 4 carbon atoms.

[0109] In the compound represented by the general formula (5) above, r is 0 or 1 to 2, and specifically, examples of r include 0, 1, or 2. In the compound represented by the general formula (5) above, s is 0 or 1 to 2, and specifically, examples of s include 0, 1, or 2. In the compound represented by the general formula (5) above, r + s is 0 or 1 to 4, and specifically, examples of r + s include 0, 1, 2, 3, or 4.

[0110] Specific examples of the compound represented by the general formula (5) above include one or more organosilicon compounds selected from phenylalkoxysilane, alkylalkoxysilane, phenylalkylalkoxysilane, cycloalkylalkoxysilane, cycloalkylalkylalkoxysilane, (alkylamino)alkoxysilane, alkyl(alkylamino)alkoxysilane, alkyl(alkylamino)silane, alkylaminosilane, and the like.

[0111] As the compound in which s is 0 in the general formula (5) above, particularly preferably, one or more organosilicon compounds selected from di-n-propyldimethoxysilane, diisopropyldimethoxysilane, di-n-butyldimethoxysilane, diisobutyldimethoxysilane, di-t-butyldimethoxysilane, t-butylmethyldimethoxysilane, t-butylethyldimethoxysilane, di-n-butyldiethoxysilane, t-butyltrimethoxysilane, t-butyltriethoxysilane, dicyclohexyldimethoxysilane, dicyclohexyldiethoxysilane, cyclohexylmethyldimethoxysilane, cyclohexylmethyldiethoxysilane, cyclohexylethyldimethoxysilane, cyclohexylethyldiethoxysilane, dicyclopentyldimethoxysilane, dicyclopentyldiethoxysilane, cyclopentylmethyldimethoxysilane, cyclopentylmethyldiethoxysilane, cyclopentylethyldiethoxysilane, cyclohexylcyclopentyldimethoxysilane, cyclohexylcyclopentyldiethoxysilane, 3-methylcyclohexylcyclopentyldimethoxysilane, 4-methylcyclohexylcyclopentyldimethoxysilane, 3,5-dimethylcyclohexylcyclopentyldimethoxysilane are mentioned.

[0112] Examples of the compound in which s is 1 or 2 in the general formula (5) include one or more organosilicon compounds selected from di(alkylamino)dialkoxysilanes, (alkylamino)(cycloalkylamino)dialkoxysilanes, (alkylamino)(alkyl)dialkoxysilanes, di(cycloalkylamino)dialkoxysilanes, vinyl(alkylamino)dialkoxysilanes, allyl(alkylamino)dialkoxysilanes, (alkoxyamino)trialkoxysilanes, (alkylamino)trialkoxysilanes, (cycloalkylamino)trialkoxysilanes, etc. Particularly preferred are ethyl(t-butylamino)dimethoxysilane, cyclohexyl(cyclohexylamino)dimethoxysilane, ethyl(t-butylamino)dimethoxysilane, bis(cyclohexylamino)dimethoxysilane, bis(perhydroisoquinolino)dimethoxysilane, bis(perhydroquinolino)dimethoxysilane, ethyl(isoquinolino)dimethoxysilane, diethylaminotrimethoxysilane, diethylaminotriethoxysilane, etc. Among them, one or more organosilicon compounds selected from bis(perhydroisoquinolino)dimethoxysilane, diethylaminotrimethoxysilane, or diethylaminotriethoxysilane are used.

[0113] In addition, the compounds represented by the general formula (5) may be used in combination of two or more.

[0114] The catalyst (A) for olefin polymerization contains (I) a solid catalyst component (1) for olefin polymerization based on a succinic acid diester, and (II) an organoaluminum compound, or contains (I) a solid catalyst component (1) for olefin polymerization based on a succinic acid diester, (II) an organoaluminum compound and (III) an external electron donor compound, that is, these contact substances. The catalyst (A) for olefin polymerization may be prepared by contacting (I) a solid catalyst component (1) for olefin polymerization based on a succinic acid diester and (II) an organoaluminum compound, or further (III) an external electron donor compound in the absence of olefins, or may be prepared by contacting them in the presence of olefins (in the polymerization system) as described below.

[0115] In the catalyst (A) for olefin polymerization, the content ratio of each component is arbitrary as long as it does not affect the effects of the present invention and is not particularly limited. Usually, per mole of titanium atom in the above-mentioned (I) solid catalyst component (1) for olefin polymerization based on a succinic acid diester, it preferably contains 1 to 2000 moles, more preferably 50 to 1000 moles of the above-mentioned (II) organoaluminum compound. Further, the catalyst (A) for olefin polymerization preferably contains 0.002 to 10.000 moles, more preferably 0.010 to 2.000 moles, still more preferably 0.010 to 0.500 moles of the above-mentioned (III) external electron donor compound per mole of the above-mentioned (II) organoaluminum compound.

[0116] The olefin polymer (B) is a polymer obtained by polymerizing olefins using the solid catalyst component (2) for polymerizing malonic acid diester-based olefins as a solid catalyst component. That is, the olefin polymer (B) is a catalyst (B) for olefin polymerization containing the solid catalyst component (2) for polymerizing malonic acid diester-based olefins and (II) an organoaluminum compound, or (I) the solid catalyst component (2) for polymerizing malonic acid diester-based olefins, (II) an organoaluminum compound, and (III) an external electron donor compound. Preferably, the olefin polymer (B) is a polymer obtained by polymerizing olefins using the catalyst (B) for olefin polymerization obtained by bringing the solid catalyst component (2) for polymerizing malonic acid diester-based olefins and (II) an organoaluminum compound, or (I) the solid catalyst component (2) for polymerizing malonic acid diester-based olefins, (II) an organoaluminum compound, and (III) an external electron donor compound into contact with each other as a catalyst for olefin polymerization.

[0117] The catalyst (B) for olefin polymerization is the same as the catalyst (A) for olefin polymerization, except that in the catalyst (A) for olefin polymerization, the solid catalyst component for polymerizing olefins used is the solid catalyst component (2) for polymerizing malonic acid diester-based olefins instead of the solid catalyst component (1) for polymerizing succinic acid diester-based olefins.

[0118] The olefin polymer (A) is a polymer obtained by polymerizing olefins in the presence of the catalyst (A) for olefin polymerization.

[0119] The production method of the olefin polymer (A) will be described. In the production method of the olefin polymer (A), the polymerization of olefins may be homopolymerization or copolymerization. In the method for producing an olefin polymer (A), examples of the olefins to be polymerized include one or more selected from ethylene, propylene, 1-butene, 1-pentene, 4-methyl-1-pentene, vinylcyclohexane, etc. Among them, one or more selected from ethylene, propylene and 1-butene are preferred, and propylene is more preferred. When the above olefins are propylene, it may be a homopolymerization of propylene or a copolymerization with other α-olefins. Examples of the olefins copolymerized with propylene include one or more selected from ethylene, 1-butene, 1-pentene, 4-methyl-1-pentene, vinylcyclohexane, etc.

[0120] When the olefin polymerization catalyst (A) is prepared in the presence of olefins (in the polymerization system), the usage ratio of each component is arbitrary as long as it does not affect the effects of the present invention and is not particularly limited. Usually, the above-mentioned (II) organoaluminum compound is preferably brought into contact with 1 to 2000 moles, more preferably 50 to 1000 moles, per mole of titanium atom in the above-mentioned (I) solid catalyst component for olefin polymerization of the succinic acid diester type (1). Also, the above-mentioned (III) external electron donor compound is preferably brought into contact with 0.002 to 10.000 moles, more preferably 0.010 to 2.000 moles, and even more preferably 0.010 to 0.500 moles, per mole of the above-mentioned (II) organoaluminum compound.

[0121] The contact order of the components constituting the above olefin polymerization catalyst (A) is arbitrary. However, when the above (II) organoaluminum compound is first charged into the polymerization system and the above (III) external electron donor compound is used, then the above (III) external electron donor compound is charged and contacted, and then the above-mentioned (I) solid catalyst component for olefin polymerization of the succinic acid diester type (1) is charged and contacted, which is desirable.

[0122] The method for producing the olefin polymer (A) may be carried out in the presence or absence of an organic solvent. Also, olefin monomers such as propylene can be used in either gaseous or liquid state. The polymerization temperature is preferably 200 °C or lower, more preferably 100 °C or lower, the polymerization pressure is preferably 10 MPa or lower, more preferably 5 MPa or lower. Further, the polymerization of olefins can be carried out by either a continuous polymerization method or a batch polymerization method. Furthermore, the polymerization reaction may be carried out in one stage or in two or more stages.

[0123] In addition, when polymerizing olefins using the olefin polymerization catalyst (A) (also referred to as main polymerization), it is preferable to carry out prepolymerization prior to the main polymerization in order to further improve the catalyst activity, stereoregularity, particle properties of the resulting polymer, etc. When carrying out prepolymerization, the same olefins as in the main polymerization or monomers such as styrene can be used.

[0124] When carrying out prepolymerization, the contact order of each component and monomer (olefins) constituting the above-mentioned olefin polymerization catalyst (A) is arbitrary, but preferably, first, (II) an organoaluminum compound is charged into a prepolymerization system set in an inert gas atmosphere or an olefin gas atmosphere, and then (I) a solid catalyst component for olefin polymerization based on a succinic acid diester (1) is charged and contacted, and then olefins such as propylene are contacted alone or a mixture of olefins such as propylene and one or more other olefins is contacted. In the above prepolymerization, when further charging (III) an external electron donor compound into the prepolymerization system, first, (II) an organoaluminum compound is charged into a prepolymerization system set in an inert gas atmosphere or an olefin gas atmosphere, then (III) the external electron donor compound is charged and contacted, and then (I) the solid catalyst component for olefin polymerization based on a succinic acid diester (1) is contacted, and then olefins such as propylene are contacted alone or a mixture of olefins such as propylene and one or more other olefins is contacted.

[0125] In the method for producing the olefin polymer (A), examples of the polymerization method include a slurry polymerization method using a solvent of an inert hydrocarbon compound such as cyclohexane or heptane, a bulk polymerization method using a solvent such as liquefied propylene, and a gas phase polymerization method that substantially does not use a solvent. The bulk polymerization method or the gas phase polymerization method is preferred.

[0126] When copolymerizing propylene with monomers of other α-olefins, examples include random copolymerization in which propylene and a small amount of ethylene are used as comonomers and polymerized in one stage, and so-called propylene-ethylene block copolymerization in which propylene is homopolymerized in the first stage (first polymerization tank) and copolymerization of propylene with other α-olefins such as ethylene is carried out in the second stage (second polymerization tank) or in two or more stages (multi-stage polymerization tanks). Block copolymerization of propylene with other α-olefins is preferred.

[0127] The block copolymer obtained by block copolymerization is a polymer containing segments in which two or more monomer compositions change continuously, and refers to a form in which polymer chains (segments) having different primary structures of the polymer such as monomer species, comonomer species, comonomer composition, comonomer content, comonomer sequence, and stereoregularity are connected in one molecular chain in two or more types.

[0128] In the method for producing the olefin polymer (A), the block copolymerization reaction of propylene with other α-olefins is usually carried out by contacting propylene alone or propylene with a small amount of α-olefin (such as ethylene) in the previous stage in the presence of the olefin polymerization catalyst (A), and then contacting propylene with α-olefin (such as ethylene) in the subsequent stage. The polymerization reaction in the previous stage may be repeated a plurality of times, or the polymerization reaction in the subsequent stage may be repeated a plurality of times and carried out by a multi-stage reaction.

[0129] The block copolymerization reaction of propylene and other α-olefins is specifically carried out by adjusting the polymerization temperature and time in the first stage so that the proportion of the polypropylene part (in the finally obtained copolymer) is 20 to 90% by mass, and then in the second stage, propylene and ethylene or other α-olefins are introduced, and polymerization is preferably carried out so that the proportion of the rubber part such as ethylene-propylene rubber (EPR) (in the finally obtained copolymer) is 10 to 80% by mass. The polymerization temperature in both the first stage and the second stage is preferably 200°C or lower, more preferably 100°C or lower, further preferably 65°C to 80°C, and still more preferably 75 to 80°C. The polymerization pressure is preferably 10 MPa or lower, more preferably 6 MPa or lower, and further preferably 5 MPa or lower. In the above copolymerization reaction, either a continuous polymerization method or a batch polymerization method can be adopted, and the polymerization reaction may be carried out in one stage or in two or more stages. Also, the polymerization time (residence time in the reactor) is preferably 1 minute to 5 hours in each polymerization stage of the first stage or the second stage, or also in the case of continuous polymerization. Examples of the polymerization method include a slurry polymerization method using a solvent of an inert hydrocarbon compound such as cyclohexane or heptane, a bulk polymerization method using a solvent such as liquefied propylene, and a gas-phase polymerization method that substantially does not use a solvent. The bulk polymerization method or the gas-phase polymerization method is preferred.

[0130] The olefin polymer (A) is an olefin polymer obtained by supplying hydrogen gas and olefins in a volume ratio of hydrogen gas supply amount to olefin gas supply amount (hydrogen / olefins) of 1.0 to 6.0, preferably 2.0 to 5.8, more preferably 2.0 to 4.3 with respect to the olefin gas supply amount. That is, in the method for producing the olefin polymer (A), hydrogen gas and olefins are supplied in a volume ratio of hydrogen gas supply amount to olefin gas supply amount (hydrogen / olefins) of 1.0 to 6.0, preferably 2.0 to 5.8, more preferably 2.0 to 4.3. By the volume ratio of hydrogen gas supply amount to olefin gas supply amount (hydrogen / olefins) being within the above range, an olefin polymer with an appropriate melt flow rate can be obtained.

[0131] The olefin polymer (B) is a polymer obtained by polymerizing olefins in the presence of an olefin polymerization catalyst (B).

[0132] The method for producing the olefin polymer (B) is the same as the method for producing the olefin polymer (A) except that the olefin polymerization catalyst (A) is replaced with the olefin polymerization catalyst (B) in the method for producing the olefin polymer (A).

[0133] The olefin polymer (B) is an olefin polymer obtained by supplying hydrogen gas and olefins in a volume ratio of hydrogen gas supply amount to olefin gas supply amount (hydrogen / olefins) of 1.0 to 6.0, preferably 2.0 to 5.8, more preferably 2.0 to 4.3. That is, in the method for producing the olefin polymer (B), hydrogen gas and olefins are supplied in a volume ratio of hydrogen gas supply amount to olefin gas supply amount (hydrogen / olefins) of 1.0 to 6.0, preferably 2.0 to 5.8, more preferably 2.0 to 4.3. In the present invention, by using the olefin polymer (B) obtained by using the diester malonate-based solid catalyst component for olefin polymerization (2) as the solid catalyst component for olefin polymerization in the olefin polymer to be mixed with the olefin polymer (A), the volume ratio of the hydrogen gas supply amount to the olefin gas supply amount (hydrogen / olefins) is 1.0 to 6.0, preferably 2.0 to 5.8, more preferably 2.0 to 4.3, and even if the amount of hydrogen used is small, the rigidity of the olefin polymer (C1) can be increased and the melt flow rate can be increased. On the other hand, when a phthalate diester-based solid catalyst component for olefin polymerization is used as the solid catalyst component for olefin polymerization in the olefin polymer to be mixed with the olefin polymer (A), the volume ratio of the hydrogen gas supply amount to the olefin gas supply amount (hydrogen / olefins) is 4.3 to 8.0, and the melt flow rate of the mixed polymer cannot be increased unless the amount of hydrogen used is very large.

[0134] The olefin polymer (A) has (a1) a melt flow rate of 1 to 100 g / 10 minutes and (b1) a flexural modulus of 2200 to 2500 MPa.

[0135] In the olefin polymer (A), the melt flow rate (MFR) indicating the melt fluidity of the olefin polymer is 1 to 100 g / 10 minutes, preferably 10 to 100 g / 10 minutes, more preferably 10 to 80 g / 10 minutes.

[0136] The olefin polymer (A) has a flexural modulus (FM) of 2,200 to 2,500 MPa, preferably 2,300 to 2,500 MPa.

[0137] The olefin polymer (B) has a melt flow rate (a2) of 200 to 1,000 g / 10 min and a flexural modulus (b2) of 1,500 to 2,200 MPa.

[0138] In the olefin polymer (B), the melt flow rate (MFR) indicating the melt fluidity of the olefin polymer is 200 to 1,000 g / 10 min, preferably 300 to 1,000 g / 10 min, more preferably 400 to 1,000 g / 10 min.

[0139] The flexural modulus (FM) of the olefin polymer (B) is 1,500 to 2,200 MPa, preferably 1,600 to 2,100 MPa, more preferably 1,700 to 2,000 MPa.

[0140] In this application document, the melt flow rate (MFR) means a value measured based on ASTM D 1238 and JIS K 7210.

[0141] Also, in this application document, the flexural modulus (FM) of the olefin polymer means a value measured at a measurement ambient temperature of 23°C (unit: MPa) based on JIS K7171 using an injection molding test piece with a thickness of 4.0 mm, a width of 10.0 mm, and a length of 80.0 mm, which was prepared under the conditions of a molding temperature of 200°C and a mold temperature of 40°C after mixing a nucleating agent (sodium benzoate: 1,000 ppm) using NEX30III3EG manufactured by Nissei Plastic Industrial Co., Ltd.

[0142] And the manufacturing method of the olefin polymer of the first form of the present invention has a polymer mixing step of mixing at a mixing ratio such that the mixing ratio of the olefin polymer (A) to the total of the olefin polymer (A) and the olefin polymer (B) is 5 to 80 mass% to obtain the olefin polymer (C1).

[0143] The polymer mixing step is a step of mixing an olefin polymer (A) and an olefin polymer (B) to obtain an olefin polymer (C1).

[0144] In the polymer mixing step, the mixing ratio of the olefin polymer (A) and the olefin polymer (B) is the ratio of the olefin polymer (A) to the total of the olefin polymer (A) and the olefin polymer (B), and is 5.0 to 80.0% by mass, preferably 10.0 to 50.0% by mass, more preferably 14.0 to 48.0% by mass. When the mixing ratio of the olefin polymer (A) to the total of the olefin polymer (A) and the olefin polymer (B) is within the above range, an olefin polymer having high rigidity of the olefin polymer (C1) and a high melt flow rate can be produced with a small amount of hydrogen used.

[0145] In the polymer mixing step, the method of mixing the olefin polymer (A) and the olefin polymer (B) is not particularly limited, and examples thereof include a method of mixing in a powder state and kneading together, a method of kneading, pelletizing, mixing, and kneading again, and the like.

[0146] The (α) melt flow rate of the olefin polymer (C1) obtained by performing the method for producing an olefin polymer according to the first embodiment of the present invention is 100 to 200 g / 10 minutes, preferably 120 to 200 g / 10 minutes, more preferably 120 to 180 g / 10 minutes.

[0147] The (β) flexural modulus of the olefin polymer (C1) is 1900 to 2300 MPa, preferably 2000 to 2300 MPa.

[0148] In the olefin polymer (C1), the ratio of the oriented layer in the cross section of the injection molded plate made of the (γ) olefin polymer (C1) is preferably 10% or more, more preferably 10 to 35%, still more preferably 15 to 30%.

[0149] When the olefin polymer of the present invention is molded into an injection-molded plate, the proportion of the oriented layer in the cross section of the injection-molded plate satisfies the above-mentioned specification, so that the thickness of the oriented layer becomes thick, and it is easy to provide a plate with excellent bending elastic modulus.

[0150] In the present application, the proportion of an oriented layer in a cross section of an injection-molded plate of an olefin polymer means a value measured by the following method. 1. Formation of molded products According to JIS K 7152-1 and JIS K 6921-2, an olefin polymer is injection molded under the following conditions to obtain a molded article having the external shape shown in FIG. Equipment: NEX-III-3EG manufactured by Nissei Plastics Co., Ltd. Type of test piece: Multipurpose test piece type A1 as specified in JIS K 7139 Resin melting temperature: 200℃ Mold temperature: 40℃ Injection speed: 180mm / sec Holding pressure: 50MPa - 40 seconds 2. Preparation of measurement samples (thin sections for polarizing microscope observation) (1) As shown in FIG. 1, the obtained molded product is cut in a direction perpendicular to the resin traveling direction MD at a position c1 1 cm in front and behind the center of the MD length to obtain a cut product S1 shown in FIG. 2(a). (2) As shown in FIG. 2(a), the cut product S1 obtained in (1) is cut in the center (position c2) parallel to the resin traveling direction MD to obtain a cut product S2 shown in FIG. 2(b). (3) As shown in FIG. 2(b), using a rotary microtome device (RX-860 manufactured by Yamato Kogyo Co., Ltd.), the cut piece S2 is cut out at position c3 parallel to the resin traveling direction MD to a thickness of 30 μm to obtain a thin-section measurement sample S3 shown in FIG. 2(c). (4) Figure 2(d) is a schematic diagram showing the obtained flake-shaped measurement sample S3, in which the left side of Figure 2(d) is a side view of the thin flake-shaped measurement sample S3 corresponding to Figure 2(c), and the right side of Figure 2(d) is a front view of the thin flake-shaped measurement sample S4. 3. Polarizing Microscope Observation Figure 3 is an enlarged front view of the flaky measurement sample S3 shown on the right side of Fig. 2(d). The above measurement sample S3 is observed with a polarized light microscope (EPCLIPSE LV-100NDA manufactured by NIKON CORPORATION), the core layer c and the alignment layers h1 and h2 are specified, the thickness of the core layer is Tc, the thicknesses of the alignment layers are Th1 and Th2, and the ratio F (%) of the alignment layer to the thickness of the molding layer is calculated by the following formula (5). F(%) = ((Th1 + Th2) / (Th1 + Tc + Th2)) × 100 (5) Note that as the thickness Tc of the core layer and the thicknesses Th1 and Th2 of the alignment layers, the arithmetic mean values when the thickness of the core layer c and the thicknesses of the alignment layers h1 and h2 are measured at any 10 locations are adopted.

[0151] When the olefin polymer according to the present invention is a crystalline polymer, when the polymer melted for injection molding flows into a mold, the polymer flows into the mold under a high shear stress, and in order to cool it, orientation crystallization occurs near the surface of the obtained injection molded product. When this injection molded product is thinly cut with a microtome or the like and the cross section is observed under a polarized light microscope, it can be confirmed that the highly birefringent alignment layer formed near the surface and the internal core layer are clearly separated from each other. Therefore, the thickness Tc of the core layer and the thicknesses Th1 and Th2 of the alignment layer can be easily specified.

[0152] The method for producing an olefin polymer according to the second embodiment of the present invention includes a succinic acid diester-based solid catalyst component (1) containing magnesium, titanium, a halogen, and a succinic acid diester compound, and when converted to solid content, the content of the succinic acid diester compound in the total content of all components is 8.0 to 24.0% by mass, and a malonic acid diester-based solid catalyst component (2) containing magnesium, titanium, a halogen, and a malonic acid diester compound, and when converted to solid content, the content of the malonic acid diester compound in the total content of all components is 10.0 to 20.0% by mass. The succinic diester-based solid catalyst component for olefin polymerization (1) and the malonic diester-based solid catalyst component for olefin polymerization (2) are coexisted at a proportion such that the proportion of the succinic diester-based solid catalyst component for olefin polymerization (1) relative to the total of the two is 10.0 to 50.0% by mass. A method for producing an olefin polymer, comprising a polymerization step of using (I) the succinic diester-based solid catalyst component for olefin polymerization (1) and the malonic diester-based solid catalyst component for olefin polymerization (2), and (II) an organoaluminum compound, or (I) the succinic diester-based solid catalyst component for olefin polymerization (1), the malonic diester-based solid catalyst component for olefin polymerization (2), (II) an organoaluminum compound and (III) an external electron donor compound to carry out the polymerization of olefins to obtain an olefin polymer (C2).

[0153] The polymerization step in the method for producing an olefin polymer according to the second embodiment of the present invention is a step of coexisting the succinic diester-based solid catalyst component for olefin polymerization (1) and the malonic diester-based solid catalyst component for olefin polymerization (2) in the polymerization reaction system to carry out the polymerization of olefins to obtain an olefin polymer (C2).

[0154] The succinic diester-based solid catalyst component for olefin polymerization (1) and the malonic diester-based solid catalyst component for olefin polymerization (2) in the method for producing an olefin polymer according to the second embodiment of the present invention are the same as the succinic diester-based solid catalyst component for olefin polymerization (1) and the malonic diester-based solid catalyst component for olefin polymerization (2) in the method for producing an olefin polymer according to the first embodiment of the present invention.

[0155] In the polymerization step according to the method for producing an olefin polymer of the second form of the present invention, the proportion of the succinic acid diester-based solid catalyst component (1) for olefin polymerization and the malonic acid diester-based solid catalyst component (2) for olefin polymerization present in the polymerization reaction system is such that the proportion of the succinic acid diester-based solid catalyst component (1) for olefin polymerization with respect to the total of the succinic acid diester-based solid catalyst component (1) for olefin polymerization and the malonic acid diester-based solid catalyst component (2) for olefin polymerization is 10.0 to 50.0% by mass, preferably 15.0 to 50.0% by mass, more preferably 20.0 to 50.0% by mass. In the polymerization step, when the proportions of the succinic acid diester-based solid catalyst component (1) for olefin polymerization and the malonic acid diester-based solid catalyst component (2) for olefin polymerization in the polymerization reaction system are within the above ranges, an olefin polymer (C2) having high rigidity and a high melt flow rate can be produced with a small amount of hydrogen used.

[0156] In the polymerization step according to the method for producing an olefin polymer of the second form of the present invention, the method of coexisting the succinic acid diester-based solid catalyst component (1) for olefin polymerization and the malonic acid diester-based solid catalyst component (2) for olefin polymerization in the polymerization reaction system is not particularly limited, and examples thereof include a method of previously mixing the solid catalyst components at the above-mentioned proportions, a method of charging each solid catalyst component so as to have the above-mentioned proportions during polymerization, and the like.

[0157] And in the polymerization step according to the method for producing an olefin polymer of the second form of the present invention, in the polymerization reaction system, as a solid catalyst component for olefin polymerization, a solid catalyst component (1) for olefin polymerization using a succinic acid diester and a solid catalyst component (2) for olefin polymerization using a malonic acid diester are coexisted in the above-mentioned predetermined proportion, and (I) the solid catalyst component (1) for olefin polymerization using a succinic acid diester and the solid catalyst component (2) for olefin polymerization using a malonic acid diester, and (II) an organoaluminum compound, or (I) the solid catalyst component (1) for olefin polymerization using a succinic acid diester and the solid catalyst component (2) for olefin polymerization using a malonic acid diester, (II) an organoaluminum compound and (III) an external electron donor compound are used to polymerize olefins to obtain an olefin polymer (C2). Preferably, the polymerization step according to the method for producing an olefin polymer of the second form of the present invention is a polymerization step in which olefins are polymerized using an olefin polymerization catalyst (C) obtained by bringing (I) the solid catalyst component (1) for olefin polymerization using a succinic acid diester and the solid catalyst component (2) for olefin polymerization using a malonic acid diester, and (II) an organoaluminum compound, or (I) the solid catalyst component (1) for olefin polymerization using a succinic acid diester and the solid catalyst component (2) for olefin polymerization using a malonic acid diester, (II) an organoaluminum compound and (III) an external electron donor compound into contact with each other to obtain an olefin polymer (C2).

[0158] The olefin polymerization catalyst (C) contains (I) the solid catalyst component (1) for olefin polymerization using a succinic acid diester and the solid catalyst component (2) for olefin polymerization using a malonic acid diester, and (II) an organoaluminum compound, or contains (I) the solid catalyst component (1) for olefin polymerization using a succinic acid diester and the solid catalyst component (2) for olefin polymerization using a malonic acid diester, (II) an organoaluminum compound and (III) an external electron donor compound, that is, a contact product of these. The catalyst (C) for olefin polymerization may be prepared by contacting (I) a solid catalyst component (1) for olefin polymerization based on a succinic acid diester, a solid catalyst component (2) for olefin polymerization based on a malonic acid diester, and (II) an organoaluminum compound, or further (III) an external electron donor compound in the absence of olefins, or may be prepared by contacting them in the presence of olefins (in the polymerization system).

[0159] In the polymerization step according to the method for producing an olefin polymer of the second embodiment of the present invention, the (II) organoaluminum compound and the (III) external electron donor compound are the same as the (II) organoaluminum compound and the (III) external electron donor compound in the method for producing the olefin polymer (A).

[0160] In the catalyst (C) for olefin polymerization, the content ratio of each component is arbitrary as long as it does not affect the effects of the present invention and is not particularly limited. Usually, per mole of the total titanium atoms in the above (I) solid catalyst component (1) for olefin polymerization based on a succinic acid diester and the solid catalyst component (2) for olefin polymerization based on a malonic acid diester, it is preferable that the above (II) organoaluminum compound contains 1 to 2000 moles, and more preferably 50 to 1000 moles. Further, the catalyst (C) for olefin polymerization preferably contains 0.002 to 10.000 moles, more preferably 0.010 to 2.000 moles, and even more preferably 0.010 to 0.500 moles of the above (III) external electron donor compound per mole of the above (II) organoaluminum compound.

[0161] In the polymerization step according to the method for producing an olefin polymer of the second form of the present invention, hydrogen gas and olefins are supplied at a volume ratio of hydrogen gas supply amount to olefin gas supply amount (hydrogen / olefins) of 1.0 to 6.0, preferably 2.0 to 5.8, more preferably 2.0 to 4.3. That is, in the polymerization step, hydrogen gas and olefins are supplied at a volume ratio of hydrogen gas supply amount to olefin gas supply amount (hydrogen / olefins) of 1.0 to 6.0, preferably 2.0 to 5.8, more preferably 2.0 to 4.3. In the present invention, as the solid catalyst component for olefin polymerization, the succinic acid diester-based solid catalyst component for olefin polymerization (1) and the malonic acid diester-based solid catalyst component for olefin polymerization (2) are used in a predetermined proportion, so that the volume ratio of hydrogen gas supply amount to olefin gas supply amount (hydrogen / olefins) is 1.0 to 6.0, preferably 2.0 to 5.8, more preferably 2.0 to 4.3. Even when the amount of hydrogen used is small, the rigidity of the olefin polymer (C2) can be increased and the melt flow rate can be increased. On the other hand, when a phthalic acid diester-based solid catalyst component for olefin polymerization is used as the solid catalyst component for olefin polymerization, the volume ratio of hydrogen gas supply amount to olefin gas supply amount (hydrogen / olefins) is 4.3 to 8.0, and the melt flow rate of the polymer cannot be increased unless the amount of hydrogen used is very large.

[0162] The (α) melt flow rate of the olefin polymer (C2) obtained by performing the method for producing an olefin polymer of the second form of the present invention is 100 to 200 g / 10 minutes, preferably 120 to 200 g / 10 minutes, more preferably 120 to 180 g / 10 minutes.

[0163] The (β) flexural modulus of the olefin polymer (C2) is 1900 to 2300 MPa, preferably 2000 to 2300 MPa.

[0164] In the olefin polymer (C2), the ratio of the oriented layer in the cross-section of the injection-molded plate made of the (γ) olefin polymer (C2) is preferably 10% or more, more preferably 20 to 50%, and still more preferably 25 to 40%.

Examples

[0165] Next, the present invention will be described more specifically with reference to examples, which are merely illustrative and do not limit the present invention.

[0166] (Example 1) (I) Production of olefin polymer (A) 1. Synthesis of solid catalyst component (1) for olefin polymerization using succinic diester As the internal electron donor compound, diethyl diisopropyl succinate, which is a succinic diester compound, was employed, and a solid catalyst component for olefin polymerization was prepared by the following method. (i) 60 ml (545.8 mmol) of titanium tetrachloride and 75 ml of toluene were charged into a 500-ml flask equipped with a stirrer and having an internal volume fully replaced with nitrogen gas 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 diethyl diisopropyl succinate was added to the above mixed solution maintained at a liquid temperature of -6°C. (iii) The temperature of the above initial contact product-containing liquid was raised, and 4.5 mL (16.8 mmol) of diethyl diisopropyl succinate was added at 60°C during the temperature rise. The temperature was further raised to 100°C and the reaction was carried out for 90 minutes while maintaining this temperature. After the reaction was completed, the supernatant was withdrawn, and the first contact product, which is the reaction product, was washed 4 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 above first contact product, the temperature was raised to 115°C, and the reaction was carried out for 60 minutes. After the reaction was completed, the operation of withdrawing the supernatant was carried out 3 times to obtain a final contact product. Next, the obtained final contact product was washed six times with 225 mL of n-heptane at 40°C, and the solid-liquid separation was carried out to obtain a solid catalyst component (solid catalyst component (1a) for polymerizing diester-based olefins). The solid-liquid of the obtained solid catalyst component was separated, and the titanium content and the content of the succinic acid diester compound (ID) in the obtained solid were measured. As a result, they were 3.5% by mass and 19.8% by mass, respectively. The properties of the obtained solid catalyst component (1a) are shown in Table 1.

[0167] In addition, the titanium content in the solid catalyst component, the content of diisopropyl succinate corresponding to the succinic acid diester compound which is an internal electron donor compound, and the physical properties were measured by the following methods.

[0168] <Titanium content in solid catalyst component> The titanium content in the solid catalyst component was measured based on the method of JIS 8311-1997.

[0169] <Content of internal electron donor compound> The content of the internal electron donor compound was determined by measuring under the following conditions using gas chromatography (GC-2014, manufactured by Shimadzu Corporation). Also, the number of moles of the internal electron donor compound was determined using a calibration curve measured in advance at a known concentration from the measurement results of gas chromatography. <Measurement conditions> Column: Capillary column (φ0.32 mm, film thickness 1.0 μm, Rxi-1ms, manufactured by GL Sciences Inc.) Detector: FID (Flame Ionization Detector, hydrogen flame ionization detector) Carrier gas: Helium, flow rate 7.0 ml / min Measurement temperature: Vaporization chamber 280°C, column 170°C, detector 280°C

[0170] 2. Formation of polymerization catalyst and polymerization reaction Into an autoclave with a capacity of 2.0 liters equipped with a stirrer and replaced with nitrogen gas, 1.32 mmol of triethylaluminum, 0.262 mmol of dicyclopentylbis(ethylamino)silane, and 0.00264 mmol of the above solid catalyst component (1a) for polymerizing succinic diester-based olefins in terms of titanium atoms were charged to form a polymerization catalyst. Then, 6.0 liters of hydrogen gas and 1.4 liters of liquefied propylene were charged, and prepolymerization was carried out at 20 °C for 5 minutes, followed by heating the temperature, and a polymerization reaction was carried out at 70 °C for 1 hour to obtain an olefin polymer (A-1). At this time, the supply volume ratio of "hydrogen gas / olefin gas" was 2.1. Next, the polymerization activity per 1 g of the solid catalyst component, the melt flowability (melt flow rate (MFR)) of the polymer, the flexural modulus (FM) of the polymer, and the molecular weight distribution (Mw / Mn and Mz / Mw) of the polymer were measured by the following methods. The results are shown in Table 1.

[0171] <Polymerization activity per 1 g of the solid catalyst component> Regarding the polymerization activity per 1 g of the solid catalyst component, it was determined by the following formula (6). Polymerization activity (g / g-cat) = mass of polymer (g) / mass of solid catalyst component (g) (6)

[0172] <Melt flowability (MFR) of the polymer> The melt flow rate (MFR) (g / 10 minutes) indicating the melt flowability of the polymer was measured in accordance with ASTM D 1238 and JIS K 7210.

[0173] <Flexural modulus (FM) of the polymer> Using an injection molding test piece with a thickness of 4.0 mm, a width of 10.0 mm, and a length of 80 mm, prepared under the conditions of a molding temperature of 200 °C and a mold temperature of 40 °C using NEX30III3EG manufactured by Nissei Plastic Industrial Co., Ltd., and measured based on JIS K7171 at a measurement ambient temperature of 23 °C.

[0174] <Molecular weight distribution of the polymer> The molecular weight distribution of the polymer was evaluated by the ratio Mw / Mn of the weight-average molecular weight Mw and the number-average molecular weight Mn, and the ratio Mz / Mw of the Z-average molecular weight Mz and the weight-average molecular weight Mw, which were determined by measuring with gel permeation chromatography (GPC) (HLC-8321GPC / HT manufactured by Tosoh Corporation) under the following conditions. · Solvent: o-dichlorobenzene (ODCB) · Temperature: 140 °C · Column: TSKgel GMHHR-H(S)HT, G2000HHR(20)HT2 · Sample concentration: 0.5 g / liter-ODCB · Injection volume: 0.5 mL · Flow rate: 1.0 mL / min · Calibration curve: Universal Calibration

[0175] (II) Production of olefin polymer (B) 1. Synthesis of solid catalyst component (2) for polymerization of malonic acid diester-based olefins Dimethyl diisobutyl malonate, which is a malonic acid diester compound, was employed as the internal electron donor compound, and a solid catalyst component for olefin polymerization was prepared by the following method. (i) 10 g (87.4 mmol) of diethoxymagnesium, 30.0 mL of heptane, and 1.0 mL (4.1 mmol) of dimethyl diisobutyl malonate were charged into a 500 mL flask equipped with a stirrer and purged with nitrogen gas to form a suspension. (ii) Then, 10.0 mL (91.0 mmol) of titanium tetrachloride was added to obtain an initial contact product-containing liquid. (iii) The above initial contact product-containing liquid was heated, held at 30 °C for 60 minutes, and 35.0 mL (318.4 mmol) of titanium tetrachloride and 2.0 mL (8.2 mmol) of dimethyl diisobutyl malonate were added. The temperature was further raised, and 1.3 mL (5.3 mmol) of diethyl diisobutyl malonate was added at 90 °C during the temperature increase. The temperature was further raised to 110 °C and reacted for 180 minutes while maintaining the same temperature. After the reaction was completed, the supernatant was withdrawn, and the first contact product, which is the reaction product, was washed 4 times with 75 mL of heptane at 90 °C. (iv) Next, to the above first contact product, 30 mL of heptane and 30 mL (547 mmol) of titanium tetrachloride were added, the temperature was raised to 100 °C, and the reaction was carried out for 15 minutes. After the reaction was completed, the supernatant was drawn out 4 times to obtain the final contact product. Subsequently, the obtained final contact product was washed 6 times with 75 mL of n-heptane at 40 °C, and the solid and liquid were separated to obtain a solid catalyst component (solid catalyst component (2a) for the polymerization of diester malonate olefins). The solid and liquid of the obtained solid catalyst component were separated, and the titanium content and the content of the diester malonate compound (ID) in the obtained solid were measured. As a result, they were 5.3% by mass and 17.6% by mass, respectively. The properties of the obtained solid catalyst component (2a) are shown in Table 1.

[0176] 2. Formation of Polymerization Catalyst and Polymerization Reaction Into an autoclave with a capacity of 2.0 liters equipped with a stirrer and replaced with nitrogen gas, 1.32 mmol of triethylaluminum, 0.262 mmol of dicyclopentylbis(ethylamino)silane, and 0.00264 mmol of the above solid catalyst component (2a) for the polymerization of diester malonate olefins in terms of titanium atoms were charged to form a polymerization catalyst. Then, 6.0 liters of hydrogen gas and 1.4 liters of liquefied propylene were charged, and prepolymerization was carried out at 20 °C for 5 minutes, followed by heating, and a polymerization reaction was carried out at 70 °C for 1 hour to obtain an olefin polymer (B-1). At this time, the supply volume ratio of "hydrogen gas / olefin gas" was 3.6. Subsequently, the polymerization activity per 1 g of the solid catalyst component, the melt flowability (melt flow rate (MFR)) of the polymer, and the molecular weight distribution (Mw / Mn and Mz / Mw) of the polymer were measured by the same method as above. The results are shown in Table 1.

[0177] (III) Production of Olefin Polymer (C1) (Polymer Mixing Step) 30.0 parts by mass of the olefin polymer (A-1) obtained above and 70.0 parts by mass of the olefin polymer (B-1) obtained above were mixed in a powder state and then kneaded with a twin-screw kneader to obtain a pelletized mixed polymer (olefin polymer (C1)). At this time, the mixing ratio of the olefin polymer (A-1) and the olefin polymer (B-1) was 30.0% by mass based on the ratio of the olefin polymer (A-1) to the total of the olefin polymer (A-1) and the olefin polymer (B-1). Next, the melt flowability (melt flow rate (MFR)) of the obtained mixed polymer (olefin polymer (C1)), the flexural modulus (FM) of the polymer, and the molecular weight distribution (Mw / Mn and Mz / Mw) of the polymer were measured by the same method as above. In addition, the ratio of the oriented layer in the cross-section of the injection-molded plate of the obtained mixed polymer (olefin polymer (C1)) was measured by the following method. The results are shown in Table 2.

[0178] <Ratio of oriented layer in cross-section of injection-molded plate made of polymer> 1. Formation of molded product In accordance with JIS K 7152-1 and JIS K 6921-2, injection molding of the olefin polymer was carried out under the following conditions to obtain a molded product having the external shape shown in Fig. 1. Apparatus: NEX-III-3EG manufactured by Nissei Plastic Industrial Co., Ltd. Type of test piece: Multi-purpose test piece type A1 described in JIS K 7139 Melt temperature of resin: 200 °C Mold temperature: 40 °C Injection speed: 180 mm / second Packing pressure: 50 MPa - 40 seconds 2. Preparation of measurement sample (thin slice for polarized light microscope observation) (1) As shown in Fig. 1, a cut product S1 shown in Fig. 2(a) was obtained by cutting the obtained molded product at a position c1 about 2 cm in the resin flow direction MD from the gate G 1 cm before and after the center of the molded product in a direction perpendicular to the resin flow direction MD. (2) As shown in Fig. 2(a), at the central part (position c2) of the cut product S1 obtained in (1), it was cut parallel to the resin advancing direction MD to obtain a cut product S2 shown in Fig. 2(b). (3) As shown in Fig. 2(b), using a rotary microtome apparatus (RX-860 manufactured by Yamato Koki Co., Ltd.), the cut product S2 was cut out at position c3 to a thickness of 30 μm parallel to the resin advancing direction MD to obtain a flaky measurement sample S3 shown in Fig. 2(c). (4) Fig. 2(d) is a schematic view showing the obtained flaky measurement sample S3. The left figure in Fig. 2(d) is a side view of the flaky measurement sample S3 corresponding to Fig. 2(c), and the right figure in Fig. 2(d) is a front view of the flaky measurement sample S3. 3. Polarizing microscope observation Fig. 3 is an enlarged view of the front view of the flaky measurement sample S3 shown in the right figure of Fig. 2(d). The above measurement sample S3 was observed with a polarizing microscope apparatus (EPCLIPSE LV-100NDA manufactured by NIKON Corporation) to identify the core layer c and the oriented layers h1, h2. Taking the thickness of the core layer as Tc, and the thicknesses of the oriented layers as Th1, Th2, the ratio F (%) of the oriented layer to the thickness of the molding layer was calculated by the following formula (5). F (%) = ((Th1 + Th2) / (Th1 + Tc + Th2)) × 100 (5) Note that for the thickness Tc of the core layer and the thicknesses Th1, Th2 of the oriented layers, the arithmetic mean values when measuring the thickness of the core layer c and the thicknesses of the oriented layers h1, h2 at any 10 locations of the measurement sample S3 were adopted.

[0179] (Examples 2 and 3) (I) Production of olefin polymer (A) The olefin polymer (A) was produced in the same manner as in Example 1 to obtain an olefin polymer (A-1).

[0180] (II) Production of olefin polymer (B) 1. Solid catalyst component for olefin polymerization based on malonic acid diester (2) In the same manner as the solid catalyst component (2) for polymerizing malonic acid diester-based olefins in Example 1, solid catalyst components (2b) and (2c) for polymerizing malonic acid diester-based olefins were obtained. The titanium content and the content of the malonic acid diester compound in the obtained solid catalyst component were measured by the same method as above. The results are shown in Table 1. 2. Formation of Polymerization Catalyst and Polymerization Reaction Using the solid catalyst component for polymerizing malonic acid diester-based olefins shown in Table 1 and under the conditions shown in Table 1, the formation of the polymerization catalyst and the polymerization reaction in Example 1 were carried out in the same manner to obtain olefin polymers (B-2) and (B-3). The polymerization activity per 1 g of the solid catalyst component, the melt flowability (melt flow rate (MFR)) of the polymer, the flexural modulus (FM) of the polymer, and the molecular weight distribution (Mw / Mn and Mz / Mw) of the polymer were measured by the same method as above. The results are shown in Table 1.

[0181] (III) Production of Olefin Polymer (C1) (Polymer Mixing Step) The mixed polymer (olefin polymer (C1)) was obtained in the same manner as in Example 1 except that the mixing amount of the polymer was as shown in Table 2. The melt flowability (melt flow rate (MFR)) of the obtained mixed polymer (olefin polymer (C1)), the flexural modulus (FM) of the polymer, and the molecular weight distribution (Mw / Mn and Mz / Mw) of the polymer were measured by the same method as above. Also, the ratio of the oriented layer in the cross-section of the injection-molded plate of the obtained mixed polymer (olefin polymer (C1)) was measured by the same method as above. The results are shown in Table 2.

[0182] (Comparative Example 1) (I) Production of Olefin Polymer (Using Solid Catalyst Component for Polymerizing Phthalic Acid Diester-Based Olefins) 1. Synthesis of Solid Catalyst Component for Polymerizing Phthalic Acid Diester-Based Olefins As the internal electron donor compound, dibutyl phthalate, which is a phthalic acid diester compound, was employed, and a solid catalyst component for polymerizing olefins was prepared by the following method. (i) A 500 ml flask equipped with a stirring device and fully replaced with nitrogen gas inside was charged with 20 ml (545.8 mmol) of titanium tetrachloride and 39 ml of toluene to form a mixed solution. (ii) Next, a suspension formed using 10.0 g (181.9 mmol) of diethoxymagnesium, 46 ml of toluene, and 2.4 ml (9.0 mmol) of dibutyl phthalate was added to the above mixed solution maintained at a liquid temperature of 4°C. (iii) After holding the above initial contact product-containing liquid at 4°C for 60 minutes, the temperature was raised. During the temperature rise, 1.2 mL (4.5 mmol) of dibutyl phthalate was added at 60°C, and the temperature was further raised to 109°C and the reaction was carried out for 120 minutes while maintaining this temperature. After the reaction was completed, the supernatant was withdrawn, and the first contact product, which is the reaction product, was washed 4 times with 85 mL of toluene at 105°C. (iv) Next, 84 mL of toluene and 16 mL (145.6 mmol) of titanium tetrachloride were added to the above first contact product, the temperature was raised to 110°C, and the reaction was carried out for 120 minutes to obtain a final contact product. Next, the obtained final contact product was washed 8 times with 70 mL of n-heptane at 40°C, and the solid catalyst component (solid catalyst component p1 for polymerizing phthalic acid diester-based olefins) was obtained by separating the solid and liquid. The solid and liquid of the obtained solid catalyst component were separated, and the titanium content and the content of the phthalic acid diester compound in the obtained solid were measured. As a result, they were 1.92% by mass and 10.5% by mass, respectively. The characteristics of the obtained solid catalyst component (p1) are shown in Table 1.

[0183] 2. Formation of Polymerization Catalyst and Polymerization Reaction Into an autoclave with a capacity of 2.0 liters equipped with a stirrer and replaced with nitrogen gas, 1.32 mmol of triethylaluminum, 0.262 mmol of dicyclopentylbis(ethylamino)silane, and 0.00264 mmol of the above-mentioned solid catalyst component for polymerizing phthalic acid diester-based olefins in terms of titanium atoms were charged to form a polymerization catalyst. Then, 6.0 liters of hydrogen gas and 1.4 liters of liquefied propylene were charged, and prepolymerization was carried out at 20°C for 5 minutes, followed by heating, and a polymerization reaction was carried out at 70°C for 1 hour to obtain an olefin polymer (P-1) (using the solid catalyst component for polymerizing phthalic acid diester-based olefins). At this time, the supply volume ratio of "hydrogen gas / olefin gas" was 4.3. Next, the polymerization activity per 1 g of the solid catalyst component, the melt fluidity (melt flow rate (MFR)) of the polymer, the flexural modulus (FM) of the polymer, and the molecular weight distribution (Mw / Mn and Mz / Mw) of the polymer were measured in the same manner as above. The results are shown in Table 1.

[0184] (Reference Example 1) (I) Production of olefin polymer (using the solid catalyst component for polymerizing phthalic acid diester-based olefins) 1. Solid catalyst component for polymerizing phthalic acid diester-based olefins In the same manner as in Comparative Example 1, a solid catalyst component for polymerizing phthalic acid diester-based olefins was obtained. The titanium content and the phthalic acid diester compound content in the obtained solid catalyst component were measured in the same manner as above. The results are shown in Table 1. 2. Formation of polymerization catalyst and polymerization reaction Except for setting the conditions shown in Table 1, the same procedure as in Example 1 was carried out to obtain an olefin polymer (P-2) (using the solid catalyst component for polymerizing phthalic acid diester-based olefins). The polymerization activity per 1 g of the solid catalyst component, the melt fluidity (melt flow rate (MFR)) of the polymer, the flexural modulus (FM) of the polymer, and the molecular weight distribution (Mw / Mn and Mz / Mw) of the polymer were measured in the same manner as above. The results are shown in Table 1.

[0185]

Table 1

[0186] In Table 1, the "-" in the FM column means unmeasured.

[0187] [Table 2]

[0188] In Table 2, the "proportion of polymer A" is the mixing ratio of the olefin polymer (A) to the total of the olefin polymer (A) and the olefin polymer (B).

[0189] (Example 4) (I) Polymerization step Into an autoclave with a volume of 2.0 liters equipped with a stirrer and replaced with nitrogen gas, 1.32 mmol of triethylaluminum, 0.262 mmol of dicyclopentylbis(ethylamino)silane, 2.63 mg (0.00264 mmol in terms of titanium atoms) of the succinic acid diester-based solid catalyst component for olefin polymerization (1) obtained in the same manner as the synthesis of the succinic acid diester-based solid catalyst component for olefin polymerization (1a) in Example 1, and 3.28 mg (0.00264 mmol in terms of titanium atoms) of the malonic acid diester-based solid catalyst component for olefin polymerization (2) obtained in the same manner as the synthesis of the malonic acid diester-based solid catalyst component for olefin polymerization (2a) in Example 1 were charged to form a polymerization catalyst. At this time, the presence ratio of the succinic acid diester-based solid catalyst component for olefin polymerization (1a) and the malonic acid diester-based solid catalyst component for olefin polymerization (2a) was 44.5% by mass based on the ratio of the succinic acid diester-based solid catalyst component for olefin polymerization (1a) to the total of the succinic acid diester-based solid catalyst component for olefin polymerization (1a) and the malonic acid diester-based solid catalyst component for olefin polymerization (2a). Thereafter, 6.0 liters of hydrogen gas and 1.4 liters of liquefied propylene were charged, and prepolymerization was carried out at 20°C for 5 minutes, followed by heating the temperature, and a polymerization reaction was carried out at 70°C for 1 hour to obtain an olefin polymer (C2). At this time, the supply volume ratio of "hydrogen gas / olefin gas" was 3.6. Next, the polymerization activity per 1 g of the solid catalyst component, the melt fluidity (melt flow rate (MFR)) of the obtained olefin polymer (C2), and the flexural modulus (FM) of the polymer were measured in the same manner as above. Also, the ratio of the oriented layer in the cross-section of the injection molded plate of the obtained olefin polymer (C2) was measured in the same manner as above. The results are shown in Table 3.

[0190]

Table 3

Industrial Applicability

[0191] According to the present invention, an olefin polymer excellent in melt fluidity and high in rigidity can be produced under general polymerization conditions using a solid catalyst component for olefin polymerization containing an internal electron donating compound other than phthalic acid ester.

Claims

1. A solid catalyst component (1) for olefin polymerization of a succinic diester system, which contains magnesium, titanium, a halogen, and a succinic diester compound, and when converted to solid content, the content of the succinic diester compound in the total content of all components is 8.0 to 24.0% by mass. Using this as a solid catalyst component, an olefin polymer (A) obtained by polymerizing olefins, and A solid catalyst component (2) for olefin polymerization of a malonic diester system, which contains magnesium, titanium, a halogen, and a malonic diester compound, and when converted to solid content, the content of the malonic diester compound in the total content of all components is 10.0 to 20.0% by mass. Using this as a solid catalyst component, an olefin polymer (B) obtained by polymerizing olefins, and A polymer mixing step of mixing them at a mixing ratio such that the ratio of the olefin polymer (A) to the total of the olefin polymer (A) and the olefin polymer (B) is 5.0 to 80.0% by mass to obtain an olefin polymer (C1). A method for producing an olefin polymer, characterized by the above.

2. The olefin polymer (A) is an olefin polymer obtained by using (I) the solid catalyst component (1) for olefin polymerization of the succinic diester system and (II) an organoaluminum compound, or (I) the solid catalyst component (1) for olefin polymerization of the succinic diester system, (II) an organoaluminum compound, and (III) an external electron donor compound, and supplying hydrogen at a volume ratio (hydrogen / olefins) of 1.0 to 6.0 with respect to the gas supply amount of the olefins. The olefin polymer (B) is an olefin polymer obtained by using (I) the solid catalyst component (2) for olefin polymerization of the malonic diester system and (II) an organoaluminum compound, or (I) the solid catalyst component (2) for olefin polymerization of the malonic diester system, (II) an organoaluminum compound, and (III) an external electron donor compound, and supplying hydrogen at a volume ratio (hydrogen / olefins) of 1.0 to 6.0 with respect to the gas supply amount of the olefins. The method for producing an olefin polymer according to Claim 1, characterized by the above.

3. The melt flow rate (a1) of the olefin polymer (A) is 1 to 100 g / 10 minutes, the flexural modulus (b1) is 2200 to 2500 MPa, the melt flow rate (a2) of the olefin polymer (B) is 200 to 1000 g / 10 minutes, and the flexural modulus (b2) is 1500 to 2200 MPa. The method for producing an olefin polymer according to claim 1, characterized in that.

4. In the polymer mixing step, the olefin polymer (A) and the olefin polymer (B) are mixed at a mixing ratio such that the mixing ratio of the olefin polymer (A) to the total of the olefin polymer (A) and the olefin polymer (B) is 10.0 to 50.0% by mass. The method for producing an olefin polymer according to claim 1, characterized in that.

5. The melt flow rate (α) of the olefin polymer (C1) is 100 to 200 g / 10 minutes, the flexural modulus (β) is 1900 to 2300 MPa, and the ratio of the oriented layer in the cross-section of the injection-molded plate made of the olefin polymer (C1) is 10% or more. The method for producing an olefin polymer according to claim 1, characterized in that.

6. A succinic acid diester-based solid catalyst component (1) for olefin polymerization, which contains magnesium, titanium, a halogen, and a succinic acid diester compound, and when converted to solid content, the content of the succinic acid diester compound in the total content of all components is 8.0 to 24.0% by mass, and A malonic acid diester-based solid catalyst component (2) for olefin polymerization, which contains magnesium, titanium, a halogen, and a malonic acid diester compound, and when converted to solid content, the content of the malonic acid diester compound in the total content of all components is 10.0 to 20.0% by mass, and The succinic acid diester-based solid catalyst component (1) for olefin polymerization and the malonic acid diester-based solid catalyst component (2) for olefin polymerization coexist at a ratio such that the ratio of the succinic acid diester-based solid catalyst component (1) to the total of the succinic acid diester-based solid catalyst component (1) and the malonic acid diester-based solid catalyst component (2) is 10.0 to 50.0% by mass. (I) The solid catalyst component (1) for the polymerization of succinic diester olefins, the solid catalyst component (2) for the polymerization of malonic diester olefins, and (II) an organoaluminum compound, or (I) the solid catalyst component (1) for the polymerization of succinic diester olefins, the solid catalyst component (2) for the polymerization of malonic diester olefins, (II) an organoaluminum compound, and (III) an external electron donor compound are used to carry out the polymerization of olefins to obtain an olefin polymer (C2). A method for producing an olefin polymer, characterized by comprising a polymerization step.

7. The method for producing an olefin polymer according to claim 6, characterized in that, in the polymerization step, the volume ratio (hydrogen / olefins) of the gas supply amount of hydrogen to the gas supply amount of olefins is 1.0 to 6.

0.

8. The method for producing an olefin polymer according to claim 6, characterized in that (α) the melt flow rate of the olefin polymer (C2) is 100 to 200 g / 10 minutes, (β) the flexural modulus is 1900 to 2300 MPa, and (γ) the ratio of the oriented layer in the cross section of the injection molded plate made of the olefin polymer (C2) is 10% or more.

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