Olefin polymerization catalyst, method for producing olefin polymerization catalyst, and method for producing olefin polymer

Abstract

To provide an olefin polymerization catalyst which, while employing an internal electron-donating compound without a phthalate structure, enables preparation of an olefin polymer that exhibits a practically sufficient broad molecular weight distribution and a high melt flow rate (MFR) when used for olefin polymerization.SOLUTION: An olefin polymerization catalyst comprises (A) a solid catalyst component for olefin polymerization which contains titanium, magnesium, a halogen, and a compound without a phthalate structure, serving as an internal electron-donating compound, (B) an organoaluminum compound, and (C) at least one external electron-donating compound, selected from organosilicon compounds represented by the general formula SiR12(OR2)2 and organosilicon compounds represented by the general formula SiR3R4(OR5)(OR6).SELECTED DRAWING: None

Description

Technical Field

[0001] The present invention relates to a catalyst for olefin polymerization, a method for producing the catalyst for olefin polymerization, and a method for producing an olefin polymer.

Background Art

[0002] Conventionally, as a catalyst for olefin polymerization, a solid catalyst composed of a transition metal catalyst component such as titanium and a typical metal catalyst component such as aluminum has been widely known.

[0003]

[0004] In the polymerization of olefins such as propylene, olefins are polymerized or copolymerized in the presence of a catalyst for olefin polymerization composed of a solid catalyst component containing a magnesium atom, a titanium atom, a halogen atom, and an internal electron-donating compound as essential components, an organoaluminum compound, and an organosilicon compound. Many methods have been proposed.

Prior Art Documents

Patent Documents

[0005]

Patent Document 1

Summary of the Invention

Problems to be Solved by the Invention

[0006] When a solid catalyst component containing a phthalic acid ester compound as an internal electron-donating compound as described in Patent Document 1 is used for the polymerization of olefins, it is known that an olefin polymer having a wide molecular weight distribution can be obtained.​ Olefin polymers containing a high molecular weight polymer component and having a sufficiently wide molecular weight distribution are generally excellent in mechanical properties such as flexural modulus (FM), and thus the above solid catalyst component containing a phthalate ester compound as an internal electron donor compound has been widely studied.

[0007] On the other hand, in recent years, from the perspective of reducing environmental impact, various substances of very high concern (SVHC substances) have been listed as candidates for authorized substances in the European REACH regulation (official name: Registration, Evaluation, Authorisation, Restriction of Chemicals), and compounds having no phthalate structure other than phthalate ester compounds have been studied as internal electron donor compounds.

[0008] However, when a compound other than a phthalate ester compound is used as the internal electron donor compound constituting the solid catalyst component, it has been difficult to obtain an olefin polymer having a molecular weight distribution that is practically sufficiently wide when subjected to the polymerization of olefins.

[0009] In addition, as an olefin polymerization catalyst, one that can obtain an olefin polymer excellent in melt flowability (MFR) and processability when subjected to the polymerization of olefins has been demanded.

[0010] Under such circumstances, the present invention provides an olefin polymerization catalyst capable of preparing an olefin polymer having a practically sufficiently wide molecular weight distribution and a high melt flowability (MFR) when subjected to the polymerization of olefins, although it uses an internal electron donor compound having no phthalate structure, and also provides a method for producing an olefin polymerization catalyst and a method for producing an olefin polymer.

Means for Solving the Problems

[0011] As a result of intensive studies by the present inventors to solve the above technical problems, (A) a solid catalyst component for olefin polymerization containing titanium, magnesium, a halogen, and a compound having no phthalate structure as an internal electron donor compound, (B) an organoaluminum compound, and (C) a general formula SiR 1 2 (OR 2 ) 2 (I) (wherein R 1 is a cycloalkyl group having 6 or more carbon atoms, and R 2 is an alkyl group having 1 to 5 carbon atoms.) and an organosilicon compound represented by the general formula SiR 3 R 4 (OR 5 )(OR 6 ) (II) (wherein R 3 is a cycloalkyl group having 6 or more carbon atoms or a derivative thereof, R 4 is a cycloalkyl group having 5 or more carbon atoms or a derivative thereof, R 5 and R 6 are alkyl groups having 1 to 3 carbon atoms, and R 5 and R 6 may be the same as or different from each other.) It has been found that the above technical problems can be solved by an olefin polymerization catalyst containing one or more external electron donor compounds selected from organosilicon compounds represented by the formula, and the present invention has been completed based on this finding.

[0012] That is, the present invention provides (1) (A) a solid catalyst component for olefin polymerization containing titanium, magnesium, a halogen, and a compound having no phthalate structure as an internal electron donor compound, (B) an organoaluminum compound, (C) the following general formula (I) SiR 1 2 (OR 2 ) 2 (I) (wherein R 1 is a cycloalkyl group having 6 or more carbon atoms, and R 2 is an alkyl group having 1 to 5 carbon atoms.) and an organosilicon compound represented by The following general formula (II) SiR 3 R 4 (OR 5 )(OR 6 ) (II) (wherein R 3 is a cycloalkyl group having 6 or more carbon atoms or a derivative thereof, R 4 is a cycloalkyl group having 5 or more carbon atoms or a derivative thereof, R 5 and R 6 are alkyl groups having 1 to 3 carbon atoms, and R 5 and R 6 may be the same as or different from each other.) An organosilicon compound represented by One or more external electron donating compounds selected from A catalyst for olefin polymerization, characterized by containing (2) The solid catalyst component for olefin polymerization (A) contains an ether carbonate compound as an internal electron donating compound, The ether carbonate compound is contained in an amount of 30 to 100 mol% based on the total content of the internal electron donating compound The catalyst for olefin polymerization according to (1) above, (3) The organoaluminum compound (B) is represented by the following general formula (III) R 7 p AlQ 3-p (III) (In the formula, R 1 is an alkyl group having 1 to 6 carbon atoms, Q is a hydrogen atom or a halogen atom, p is 0 < p ≦ 3, and when there are a plurality of R 7 , each R 7 may be the same as or different from each other, and when there are a plurality of Q, each Q may be the same as or different from each other.) One or more represented by The catalyst for olefin polymerization according to (1) or (2) above, (4) The olefin polymerization catalyst according to any one of (1) to (3) above, wherein the (C) external electron donating compound is at least one selected from dicyclohexyldimethoxysilane and cyclohexylcyclopentyldimethoxysilane. (5) A method for producing an olefin polymerization catalyst, comprising: (A) A solid catalyst component for olefin polymerization containing titanium, magnesium, a halogen, and a compound having no phthalate structure as an internal electron donating compound; (B) an organoaluminum compound; (C) The following general formula (I) SiR 1 2 (OR 2 ) 2 (I) (wherein R 1 is a cycloalkyl group having 6 or more carbon atoms, and R 2 is an alkyl group having 1 to 5 carbon atoms.) an organosilicon compound represented by and the following general formula (II) SiR 3 R 4 (OR 5 )(OR 6 ) (II) (wherein R 3 is a cycloalkyl group having 6 or more carbon atoms or a derivative thereof, R 4 is a cycloalkyl group having 5 or more carbon atoms or a derivative thereof, and R 5 and R 6 are alkyl groups having 1 to 3 carbon atoms, which may be the same or different from each other.) an organosilicon compound represented by at least one external electron donating compound selected from and are brought into contact with each other to obtain an olefin polymerization catalyst A method for producing an olefin polymerization catalyst, characterized in that: (6) A method for producing an olefin polymer, characterized in that olefin polymerization is carried out using the olefin polymerization catalyst according to any one of (1) to (4) above or the olefin polymerization catalyst obtained by the production method according to (5) above. The method for producing an olefin polymer according to the above (6), wherein the resulting olefin polymer is a propylene-based block copolymer, is provided.

Effect of the Invention

[0013] According to the present invention, despite using an internal electron donor compound having no phthalate structure, when used for the polymerization of olefins, an olefin polymerization catalyst capable of preparing an olefin polymer having a practically wide enough molecular weight distribution and a high melt flowability (MFR) can be provided, and a method for producing an olefin polymerization catalyst and a method for producing an olefin polymer can be provided.

Embodiments for Carrying Out the Invention

[0014] <Olefin Polymerization Catalyst> First, the olefin polymerization catalyst according to the present invention will be described. The olefin polymerization catalyst according to the present invention is (A) a solid catalyst component for olefin polymerization containing titanium, magnesium, halogen, and a compound having no phthalate structure as an internal electron donor compound, (B) an organoaluminum compound, and (C) an organosilicon compound represented by the following general formula (I) SiR 1 2 (OR 2 ) 2 (I) (wherein R 1 is a cycloalkyl group having 6 or more carbon atoms, and R 2 is an alkyl group having 1 to 5 carbon atoms.) and an organosilicon compound represented by the following general formula (II) SiR 3 R 4 (OR 5 )(OR 6 ) (II) (wherein R 3 is a cycloalkyl group having 6 or more carbon atoms or a derivative thereof, and R 4is a cycloalkyl group having 5 or more carbon atoms or a derivative thereof, R 5 and R 6 is an alkyl group having 1 to 3 carbon atoms, R 5 and R 6 may be the same as or different from each other. An organosilicon compound represented by one or more external electron-donating compounds selected from and is characterized by containing

[0015] In the olefin polymerization catalyst according to the present invention, as the solid catalyst component for olefin polymerization containing (A) titanium, magnesium, halogen, and a compound having no phthalate structure as an internal electron-donating compound, a contact reactant obtained by bringing a raw material component serving as a source of magnesium, titanium, and halogen into contact with and reacting an internal electron-donating compound composed of a compound having no phthalate structure in an organic solvent can be mentioned. Specifically, as the solid catalyst component for olefin polymerization of (A) above, a contact reactant obtained by bringing a magnesium compound and a tetravalent titanium halogen compound as raw material components serving as sources of magnesium, titanium, and halogen into contact with an internal electron-donating compound composed of these raw materials and a compound having no phthalate structure can be mentioned.

[0016] Examples of the magnesium compound include one or more selected from dialkoxymagnesium, dihalogenated magnesium, alkoxymagnesium halide, and the like. Among the above magnesium compounds, dialkoxymagnesium or magnesium dihalide is preferable. Specifically, dimethoxymagnesium, diethoxymagnesium, dipropoxymagnesium, dibutoxymagnesium, ethoxymethoxymagnesium, ethoxypropoxymagnesium, butoxyethoxymagnesium, magnesium dichloride, magnesium dibromide, magnesium diiodide, etc. can be mentioned, and diethoxymagnesium and magnesium dichloride are particularly preferable.

[0017] Among the above magnesium compounds, the dialkoxymagnesium may be obtained by reacting metallic magnesium with an alcohol in the presence of a halogen or a halogen-containing metal compound or the like.

[0018] The above dialkoxymagnesium is preferably in granular or powder form, and its shape may be irregular or spherical.

[0019] When 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 or the like caused by fine powder contained in the generated polymer powder can be suppressed.

[0020] The above spherical dialkoxymagnesium does not necessarily have to be a perfect sphere, and an elliptical or potato-shaped one can also be used.

[0021] Also, the average particle diameter (average particle diameter D50) of the above 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% in the volume integrated particle size distribution when measured using a laser light scattering diffraction method particle size measuring instrument. When the dialkoxymagnesium is spherical, the above 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.

[0022] Also, 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 method particle size measuring instrument, the particles having a particle diameter of 5.0 μm or less are preferably 20% or less, more preferably 10% or less. On the one hand, when measured using a laser light scattering diffraction particle size analyzer, the particles having a particle diameter of 100.0 μm or more are preferably 20% or less, and more preferably 10% or less. Furthermore, when the particle size distribution is represented by ln(D90 / D10), it is preferably 3 or less, and more preferably 2 or less. Here, D90 means the particle diameter at which the integrated particle size in the volume integrated particle size distribution is 90% when measured using a laser light scattering diffraction particle size analyzer. Also, D10 means the particle diameter at which the integrated particle size in the volume integrated particle size distribution is 10% when measured using a laser light scattering diffraction particle size analyzer.

[0023] The method for producing the above spherical dialkoxymagnesium is exemplified in, for example, JP-A-62-51633, JP-A-3-74341, JP-A-4-368391, JP-A-8-73388, and the like.

[0024] In the solid catalyst component for olefin polymerization that constitutes the catalyst for olefin polymerization according to the present invention, as the magnesium compound, 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 a magnesium compound having a specific surface area within the above range, a solid catalyst component for olefin polymerization having a desired specific surface area can be easily prepared.

[0025] In the present application documents, the specific surface area of the magnesium compound means the value measured by the BET method. Specifically, the specific surface area of the magnesium compound means the value measured by the BET method (automatic measurement) in the presence of a mixed gas of nitrogen and helium using an Automatic Surface Area Analyzer HM model-1230 manufactured by Mountech after preliminarily vacuum-drying the measurement sample at 50 °C for 2 hours.

[0026] The magnesium compound is preferably in a solution state or a suspension state during the reaction, and the reaction can proceed favorably due to being in a solution state or a suspension state.

[0027] When the magnesium compound is solid, it can be made into a solution-state magnesium compound by dissolving it in a solvent having solubilizing ability for the magnesium compound, or a magnesium compound suspension can be made by suspending it in a solvent having no solubilizing ability for the magnesium compound. When the magnesium compound is liquid, it may be used as a solution-state magnesium compound as it is, or may be further dissolved in a solvent having solubilizing ability for the magnesium compound and used as a solution-state magnesium compound.

[0028] Examples of the compound capable of solubilizing the solid magnesium compound 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 preferable, and 2-ethylhexanol is particularly preferable. On the other hand, examples of the medium having no solubilizing ability for the solid magnesium compound include one or more selected from saturated hydrocarbon solvents or unsaturated hydrocarbon solvents that do not dissolve the magnesium compound.

[0029] In the solid catalyst component for olefin polymerization that constitutes the catalyst for olefin polymerization according to the present invention, the tetravalent titanium halogen compound, which is a raw material component serving as a supply source of titanium and halogen, is not particularly limited, but the following general formula (IV) Ti(OR 8 ) r X 4-r (IV) (In the formula, R 8 represents an alkyl group having 1 to 4 carbon atoms, X represents a halogen atom such as a chlorine atom, a bromine atom, or an iodine atom, and r satisfies 0 ≦ r ≦ 3.) It is preferable that it is one or more compounds selected from the group of titanium halides or alkoxytitanium halides represented by the formula.

[0030] In the general formula (IV) above, r satisfies 0 ≦ r ≦ 3. Specifically, examples of r include 0, 1, 2, or 3.

[0031] Examples of the titanium halide represented by the general formula (IV) include one or more titanium tetrahalides selected from titanium tetrachloride, titanium tetrabromide, titanium tetraiodide, and the like. Examples of the alkoxytitanium halide represented by the general formula (IV) 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 preferred, and titanium tetrachloride is more preferred. These titanium compounds may be used alone or in combination of two or more.

[0032] In the olefin polymerization catalyst according to the present invention, the solid catalyst component for olefin polymerization (A) contains a compound having no phthalate structure as an internal electron donor compound. In the olefin polymerization catalyst according to the present invention, examples of the compound having no phthalate structure used as the internal electron donor compound include ether carbonate compounds, 1,3-diether compounds, and as the internal electron donor compound having an ester group, one or more selected from succinic acid diester compounds, malonic acid diester compounds, maleic acid diester compounds, and cyclohexene carboxylic acid diester compounds can be mentioned, and ether carbonate compounds are preferred.

[0033] In the olefin polymerization catalyst according to the present invention, when the solid catalyst component for olefin polymerization (A) contains an ether carbonate compound as an internal electron donor compound, as the ether carbonate compound, the following general formula (V) R 9 -O-C(=O)-O-Z-OR 10 (V) (In the general formula (3), R 9 and R 10 represent a linear alkyl group having 1 to 20 carbon atoms, a branched alkyl group having 3 to 20 carbon atoms, a vinyl group, a linear alkenyl group or a branched alkenyl group having 3 to 20 carbon atoms, a linear halogen-substituted alkyl group having 1 to 20 carbon atoms, a branched halogen-substituted alkyl group having 3 to 20 carbon atoms, a linear halogen-substituted alkenyl group having 2 to 20 carbon atoms, a branched halogen-substituted alkenyl group having 3 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, a cycloalkenyl group having 3 to 20 carbon atoms, a halogen-substituted cycloalkyl group having 3 to 20 carbon atoms, a halogen-substituted cycloalkenyl group having 3 to 20 carbon atoms, an aromatic hydrocarbon group having 6 to 24 carbon atoms, a halogen-substituted aromatic hydrocarbon group having 6 to 24 carbon atoms, a nitrogen atom-containing hydrocarbon group having 2 to 24 carbon atoms whose bonding terminal is a carbon atom (excluding those whose bonding terminal is a C=N group), an oxygen atom-containing hydrocarbon group having 2 to 24 carbon atoms whose bonding terminal is a carbon atom (excluding those whose bonding terminal is a carbonyl group), or a phosphorus atom-containing hydrocarbon group having 2 to 24 carbon atoms whose bonding terminal is a carbon atom (excluding those whose bonding terminal is a C=P group), R 9 and R 10 may be the same or different, and Z represents a bonding group bonded via a carbon atom or a carbon chain.) A compound represented by the formula can be used.

[0034] Specific examples of such ether carbonates include one or more selected from (2-ethoxyethyl) methyl carbonate, (2-ethoxyethyl) ethyl carbonate, (2-propoxyethyl) ethyl carbonate, (2-butoxyethyl) ethyl carbonate, (2-ethoxyethyl) phenyl carbonate, (2-ethoxyethyl) p-methylphenyl carbonate, and the like.

[0035] In the catalyst for olefin polymerization according to the present invention, in the solid catalyst component for olefin polymerization (A), it is preferable that the ether carbonate compound is contained in an amount of 30 to 100 mol%, more preferably 40 to 100 mol%, and even more preferably 49 to 100 mol% based on the total content of the internal electron donor compound (when the total content of the internal electron donor compound is 100 mol%).

[0036] In the catalyst for olefin polymerization according to the present invention, when the solid catalyst component for olefin polymerization (A) contains the ether carbonate compound in the above ratio with respect to the total content of the internal electron donor compound, the ether carbonate compound in the solid catalyst component for olefin polymerization (A) is easily extracted by the organoaluminum compound (B) which is a cocatalyst during the polymerization of olefins, and the organosilicon compound (C) described later can be effectively supported on the solid catalyst component for olefin polymerization (A). Therefore, when the catalyst for olefin polymerization according to the present invention is used in the polymerization reaction of olefins, an olefin polymer having a practically excellent molecular weight distribution and a practically excellent melt flowability (MFR) can be easily prepared, and particularly excellent copolymerization activity can be exhibited when used in a copolymerization reaction.

[0037] In the catalyst for olefin polymerization according to the present invention, the solid catalyst component for olefin polymerization (A) may contain a phthalic acid ester together with a compound having no phthalate structure as the internal electron donor compound. However, when the phthalic acid ester is contained as the internal electron donor compound, it is preferably more than 0 mol% and 15 mol% or less based on the total content of the internal electron donor compound (when the total content of the internal electron donor compound is 100 mol%).

[0038] In the catalyst for olefin polymerization according to the present invention, the solid catalyst component for olefin polymerization (A) may further contain polysiloxane. Polysiloxane is a polymer having a siloxane bond (-Si-O- bond) in the main chain, and is also collectively referred to as silicone oil. It has a viscosity of 0.02 to 100 cm 2 / s (2 to 10,000 centistokes) at 25°C, more preferably 0.03 to 5 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. In the catalyst for olefin polymerization according to the present invention, since the solid catalyst component (A) for olefin polymerization further contains polysiloxane, when used for the polymerization of olefins, an olefin polymer excellent in stereoregularity or crystallinity can be easily produced, and furthermore, the amount of fine powder in the produced olefin polymer can be easily reduced.

[0039] In the catalyst for olefin polymerization according to the present invention, the solid catalyst component (A) for olefin polymerization can be prepared, for example, by bringing dialkoxymagnesium, a tetravalent titanium halogen compound, an internal electron donating compound, and optionally polysiloxane into contact with each other in an inert organic solvent.

[0040] As the above-mentioned inert organic solvent, those that are liquid at room temperature (20°C) and have a boiling point of 50 to 150°C are preferred, and saturated hydrocarbon compounds or aromatic hydrocarbon compounds that are liquid at room temperature and have a boiling point of 50 to 150°C are more preferred.

[0041] Specific examples of the above-mentioned inert organic solvent include one or more selected from linear aliphatic hydrocarbon compounds such as hexane, heptane, and decane, branched aliphatic hydrocarbon compounds such as methylheptane, alicyclic hydrocarbon compounds such as cyclohexane, methylcyclohexane, and ethylcyclohexane, and aromatic hydrocarbon compounds such as toluene, xylene, and ethylbenzene. Among the above-mentioned inert organic solvents, aromatic hydrocarbon compounds that are liquid at room temperature and have a boiling point of 50 to 150 °C are suitable because they can easily improve the activity of the obtained solid catalyst component and easily improve the stereoregularity of the obtained polymer.

[0042] In the catalyst for olefin polymerization according to the present invention, when preparing the solid catalyst component for olefin polymerization (A), each component can be brought into contact with each other in an inert gas atmosphere.

[0043] Specifically, in an inert gas atmosphere and under a situation where moisture and the like are removed, in a container equipped with a stirrer, each component is brought into contact while stirring, and then reacted at a predetermined temperature to obtain the solid catalyst component for olefin polymerization (A).

[0044] When simply bringing the components into contact and stirring and mixing them, or when dispersing or suspending them for modification treatment, the temperature at which the components are brought into contact may be in a relatively low temperature range near room temperature.

[0045] When reacting after bringing the components into contact to obtain a product, a temperature range of 40 to 130 °C is preferable. In this case, it is preferable to hold the reaction at the same temperature after bringing the components into contact.

[0046] When the temperature for obtaining the above product is less than 40 °C, the reaction does not proceed sufficiently, and as a result, it becomes difficult for the obtained solid catalyst component to exhibit sufficient performance. Also, when the temperature exceeds 130 °C, the evaporation of the used solvent becomes significant, making it difficult to control the reaction.

[0047] The reaction time for obtaining the above product is preferably 1 minute or more, more preferably 10 minutes or more, and even more preferably 30 minutes or more.

[0048] Since the usage ratio of each component when preparing the solid catalyst component for olefin polymerization (A) varies depending on the preparation method, it may be appropriately determined.

[0049] When preparing the solid catalyst component for olefin polymerization, it is preferable to contact 0.50 to 100.00 moles of a tetravalent titanium halogen compound per 1.00 mole of the dialkoxymagnesium compound, more preferably 0.50 to 10.00 moles, and even more preferably 1.00 to 5.00 moles.

[0050] Also, when preparing the solid catalyst component for olefin polymerization (A), it is preferable to contact 0.01 to 10.00 moles of an internal electron donor compound per 1.00 mole of dialkoxymagnesium, more preferably 0.01 to 1.00 mole, and even more preferably 0.02 to 0.6 mole.

[0051] Furthermore, when using polysiloxane in the preparation of the solid catalyst component for olefin polymerization (A), it is preferable to contact 0.01 to 100.00 g of polysiloxane per 1.00 mole of dialkoxymagnesium, more preferably 0.05 to 80.00 g, and even more preferably 1.00 to 50.00 g.

[0052] Also, when preparing the solid catalyst component for olefin polymerization (A), the amount of the inert organic solvent used is preferably 0.001 to 500.000 moles, more preferably 0.001 to 70.000 moles, and even more preferably 0.005 to 50.000 moles per 1.000 mole of dialkoxymagnesium.

[0053] As a particularly preferred method for preparing the solid catalyst component for olefin polymerization, the following preparation methods can be mentioned.

[0054] First, dialkoxymagnesium is suspended in an inert organic solvent containing an alicyclic hydrocarbon compound having a boiling point of 50 to 150 °C to obtain a suspension. Next, the obtained suspension is contacted with a tetravalent titanium halogen compound for reaction treatment. Before or after contacting the suspension with a tetravalent titanium halogen compound, one or more selected from internal electron donor compounds are contacted at -20 to 130 °C. Further, if necessary, polysiloxane is contacted for reaction treatment. In the above preparation method, it is desirable to carry out an aging reaction at a low temperature before or after contacting the internal electron donor compound.

[0055] (A) The solid catalyst component for olefin polymerization preferably contains titanium atoms in an amount of 1.0 to 10.0% by mass, more preferably 1.5 to 8.0% by mass, and even more preferably 1.5 to 5.0% by mass.

[0056] (A) The solid catalyst component for olefin polymerization preferably contains magnesium atoms in an amount of 10.0 to 70.0% by mass, more preferably 10.0 to 50.0% by mass, even more preferably 15.0 to 40.0% by mass, and still more preferably 15.0 to 25.0% by mass.

[0057] (A) The solid catalyst component for olefin polymerization preferably contains halogen atoms in an amount of 20.0 to 90.0% by mass, more preferably 30.0 to 85.0% by mass, even more preferably 40.0 to 80.0% by mass, and still more preferably 45.0 to 80.0% by mass.

[0058] (A) The solid catalyst component for olefin polymerization preferably contains internal electron donor compounds in a total amount of 0.5 to 30.0% by mass, more preferably 1.0 to 25.0% by mass, and even more preferably 2.0 to 20.0% by mass.

[0059] In these application documents, the content rate of titanium atoms contained in the solid catalyst component for olefin polymerization means the value measured according to the method (redox titration) described in JIS 8311-1997 "Method for Determination of Titanium in Titanium Ore".

[0060] In addition, in this application document, the content ratio 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.

[0061] In this application document, the content ratio of halogen atoms 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 atoms are titrated with a silver nitrate standard solution. Further, the content ratio of the electron donor compound means the value measured by the gas chromatography FID (Flame Ionization Detector) method in which the internal electron donor is extracted using an aromatic solvent after hydrolyzing the solid catalyst.

[0062] The catalyst for olefin polymerization according to the present invention contains (B) an organoaluminum compound.

[0063] In the catalyst for olefin polymerization according to the present invention, as the (B) organoaluminum compound, the following general formula (III) R 7 p AlQ 3-p (III) (In the formula, R 7 is an alkyl group having 1 to 6 carbon atoms, Q is a hydrogen atom or a halogen atom, p is 0 < p ≤ 3, and when a plurality of R 7 exist, each R 7 may be the same as or different from each other, and when a plurality of Q exist, each Q may be the same as or different from each other.) It is preferably one or more represented by.

[0064] In the organoaluminum compound represented by the general formula (III), R 7 is an alkyl group having 1 to 6 carbon atoms, and specifically, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, etc. can be mentioned.

[0065] In the organoaluminum compound represented by the general formula (III), Q represents a hydrogen atom or a halogen atom, and when Q is a halogen atom, examples thereof include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

[0066] In the organoaluminum compound represented by the general formula (III), p satisfies 0 < p ≤ 3, preferably 2 to 3, more preferably 2, 2.5, or 3.

[0067] Specific examples of the organoaluminum compound represented by the general formula (III) include one or more selected from triethylaluminum, diethylaluminum chloride, triisobutylaluminum, diethylaluminum bromide, and diethylaluminum hydride, and triethylaluminum and triisobutylaluminum are preferred.

[0068] The catalyst for olefin polymerization according to the present invention preferably contains (B) an organoaluminum compound in an amount of 0.1 to 1000.0 moles, more preferably 1.0 to 900.0 moles, and even more preferably 20.0 to 800.0 moles per mole of titanium atom constituting the solid catalyst component for olefin polymerization.

[0069] Since the catalyst for olefin polymerization according to the present invention contains a specific organoaluminum compound represented by the general formula (III), it is considered that the action of the organoaluminum compound on the internal electron-donating compound constituting the solid catalyst component for olefin polymerization can be improved, and the solid catalyst component for olefin polymerization can be optimally activated. And it is considered that excellent catalytic activity can be exhibited during the polymerization process, and an olefin polymer excellent in stereoregularity can be produced.

[0070] The catalyst for olefin polymerization according to the present invention, together with (A) a solid catalyst component for olefin polymerization and (B) an organoaluminum compound, (C) The following general formula (I) SiR 12 (OR 2 ) 2 (I) (wherein R 1 is a cycloalkyl group having 6 or more carbon atoms, and R 2 is an alkyl group having 1 to 5 carbon atoms.) and an organosilicon compound represented by the following general formula (II) SiR 3 R 4 (OR 5 )(OR 6 ) (II) (wherein R 3 is a cycloalkyl group having 6 or more carbon atoms or a derivative thereof, R 4 is a cycloalkyl group having 5 or more carbon atoms or a derivative thereof, R 5 and R 6 are alkyl groups having 1 to 3 carbon atoms, and R 5 and R 6 may be the same as or different from each other.) and contains one or more external electron donating compounds selected from the organosilicon compounds represented by

[0071] In the organosilicon compound represented by the above general formula (I), R 1 is a cycloalkyl group having 6 or more carbon atoms, preferably a cycloalkyl group having 6 to 10 carbon atoms, and more preferably a cycloalkyl group having 6 carbon atoms (cyclohexyl group).

[0072] In the organosilicon compound represented by the above general formula (I), R 2 is an alkyl group having 1 to 5 carbon atoms, preferably an alkyl group having 1 to 3 carbon atoms, and more preferably an alkyl group having 1 to 2 carbon atoms.

[0073] Examples of the organosilicon compound represented by the above general formula (I) include one or more selected from dicyclohexyldimethoxysilane, dicyclohexyldiethoxysilane, dicyclohexylpropoxysilane, dicyclohexyldibutoxysilane, and the like.

[0074] ​In the organosilicon compound represented by the general formula (II) above, R 3 is a cycloalkyl group having 6 or more carbon atoms or a derivative thereof, preferably a cycloalkyl group having 6 to 10 carbon atoms or a derivative thereof, and more preferably a cycloalkyl group having 6 carbon atoms (cyclohexyl group) or a derivative thereof.

[0075] In the organosilicon compound represented by the general formula (II) above, R 3 When it is a derivative of a cycloalkyl group having 6 or more carbon atoms, examples of the derivative include those in which 1 to 3 alkyl groups such as a methyl group or an ethyl group are substituted at the 3-position, 4-position, or 5-position of the cyclohexyl group, and those in which a halogen atom such as a chlorine atom or a bromine atom is substituted on the cyclohexyl group. Note that the number of substituents substituting one carbon constituting the cyclohexyl group is 1 or 2.

[0076] In the organosilicon compound represented by the general formula (II) above, R 4 is a cycloalkyl group having 5 or more carbon atoms or a derivative thereof, preferably a cycloalkyl group having 5 to 10 carbon atoms or a derivative thereof, and more preferably a cycloalkyl group having 5 carbon atoms (cyclopentyl group) or a derivative thereof.

[0077] In the organosilicon compound represented by the general formula (II) above, R 4 When it is a derivative of a cycloalkyl group having 5 or more carbon atoms, examples of the derivative include those in which 1 to 3 alkyl groups such as a methyl group or an ethyl group are substituted at the 2-position, 3-position, or 5-position of the cyclopentyl group, and those in which a halogen atom such as a chlorine atom or a bromine atom is substituted on the cyclopentyl group. Note that the number of substituents substituting one carbon constituting the cyclopentyl group is 1 or 2.

[0078] In the organosilicon compound represented by the general formula (II) above, R 5 and R 6is an alkyl group having 1 to 3 carbon atoms, preferably an alkyl group having 1 to 2 carbon atoms, and more preferably a methyl group having 1 carbon atom. In the organosilicon compound represented by the general formula (II), R 5 and R 6 may be the same as or different from each other.

[0079] Specific examples of the organosilicon compound represented by the general formula (II) include cyclohexylcyclopentyldimethoxysilane, cyclohexylcyclopentyldiethoxysilane, cyclohexylcyclopentyldipropoxysilane, dicyclohexyldimethoxysilane, dicyclohexyldiethoxysilane, dicyclohexyldipropoxysilane and the like.

[0080] The catalyst for olefin polymerization according to the present invention includes (A) a solid catalyst component for olefin polymerization containing a compound having no phthalate structure as an internal electron donor compound, (B) an organoaluminum compound, and (C) one or more external electron donor compounds selected from specific organosilicon compounds represented by the general formula (I) and the general formula (II). Since the catalyst for olefin polymerization according to the present invention contains the above specific components, they exhibit a synergistic effect with each other. Despite using an internal electron donor compound having no phthalate structure, when subjected to the polymerization reaction of olefins, it is possible to easily prepare an olefin polymer having a practically excellent flexural modulus (FM) and molecular weight distribution, and a practically excellent melt flowability (MFR), and particularly, it can exhibit excellent copolymerization activity when subjected to a copolymerization reaction.

[0081] The catalyst for olefin polymerization according to the present invention preferably contains, per 1 mol of the (B) organoaluminum compound, a total of 0.002 to 10.000 mol, more preferably 0.010 to 2.000 mol, and even more preferably 0.010 to 0.500 mol of one or more external electron donor compounds selected from the organosilicon compounds represented by the general formula (I) and the general formula (II).

[0082] The olefin polymerization catalyst according to the present invention contains, per mole of the organoaluminum compound (B), one or more external electron donor compounds selected from organosilicon compounds represented by the general formula (I) and the general formula (II) in the above ratio. When subjected to the polymerization of olefins, particularly copolymerization reaction, an olefin polymer having a practically sufficiently wide molecular weight distribution and excellent melt flowability (MFR) can be easily prepared, and particularly excellent copolymerization activity can be exhibited when subjected to the copolymerization reaction.

[0083] The olefin polymerization catalyst according to the present invention can be preferably produced by the method for producing an olefin polymerization catalyst according to the present invention described later.

[0084] According to the present invention, an olefin polymerization catalyst capable of preparing an olefin polymer having a practically sufficiently wide molecular weight distribution and high melt flowability (MFR) when subjected to the polymerization of olefins can be provided, although an internal electron donor compound having no phthalate structure is used.

[0085] Next, the method for producing an olefin polymerization catalyst according to the present invention will be described.

[0086] The method for producing an olefin polymerization catalyst according to the present invention is a method for producing an olefin polymerization catalyst, comprising: (A) a solid catalyst component for olefin polymerization containing titanium, magnesium, halogen, and a compound having no phthalate structure as an internal electron donor compound; (B) an organoaluminum compound; (C) the following general formula (I) SiR 1 2 (OR 2 ) 2 (I) (wherein R 1 is a cycloalkyl group having 6 or more carbon atoms, R 2is an alkyl group having 1 to 5 carbon atoms. The organosilicon compound represented by ()) and The following general formula (II) SiR 3 R 4 (OR 5 )(OR 6 ) (II) (However, R 3 is a cycloalkyl group having 6 or more carbon atoms and its derivatives, R 4 is a cycloalkyl group having 5 or more carbon atoms and its derivatives, R 5 and R 6 are alkyl groups having 1 to 3 carbon atoms, which may be the same or different from each other.) The organosilicon compound represented by One or more external electron donor compounds selected from are brought into contact with each other to obtain a catalyst for olefin polymerization It is characterized by that.

[0087] In the method for producing a catalyst for olefin polymerization according to the present invention, the details of (A) the solid catalyst component for olefin polymerization, (B) the organoaluminum compound, and (C) the organosilicon compound represented by the general formula (I) and the organosilicon compound represented by the general formula (II) are as described above.

[0088] Further, in the method for producing a catalyst for olefin polymerization according to the present invention, the contact between (A) the solid catalyst component for olefin polymerization and (B) the organoaluminum compound may be carried out in the presence of one or more external electron donor compounds selected from the organosilicon compound represented by the general formula (I) and the organosilicon compound represented by the general formula (II), or may be carried out in the absence of the external electron donor compound.

[0089] In the method for producing a catalyst for olefin polymerization according to the present invention, when the contact of (A) a solid catalyst component for olefin polymerization and (B) an organoaluminum compound is carried out in the absence of one or more external electron donor compounds selected from the organosilicon compounds represented by the general formula (I) and the organosilicon compounds represented by the general formula (II), after (A) the solid catalyst component for olefin polymerization and (B) the organoaluminum compound are brought into contact with each other, the contact-treated product obtained thereby is further brought into contact with one or more external electron donor compounds selected from the organosilicon compounds represented by the general formula (I) and the organosilicon compounds represented by the general formula (II). This is preferable.

[0090] In the method for producing a catalyst for olefin polymerization according to the present invention, the amount of the (B) organoaluminum compound contacted during the formation of the polymerization catalyst is preferably 0.1 to 1000.0 moles, more preferably 1.0 to 900.0 moles, and even more preferably 20.0 to 800.0 moles per mole of titanium atoms in the (A) solid catalyst component for olefin polymerization.

[0091] In the method for producing a catalyst for olefin polymerization according to the present invention, the amount of the one or more external electron donor compounds selected from the organosilicon compounds represented by the general formula (I) and the organosilicon compounds represented by the general formula (II) contacted is preferably 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 (B) organoaluminum compound.

[0092] In the method for producing a catalyst for olefin polymerization according to the present invention, the concentration of the inert gas in the atmosphere during the preparation of the polymerization catalyst is preferably 0.0 to 1.0 mol / L, more preferably 0.0 to 0.5 mol / L, and even more preferably 0.0 to 0.1 mol / L.

[0093] Examples of the inert gas include one or more selected from nitrogen gas, helium gas, neon gas, argon gas, and the like.

[0094] In the method for producing a catalyst for olefin polymerization according to the present invention, the polymerization catalyst may be produced in the presence of olefins to be polymerized or in the absence of olefins to be polymerized.

[0095] In the method for producing a catalyst for olefin polymerization according to the present invention, the temperature at which each component is brought into contact during the preparation of the polymerization catalyst is preferably 40°C or lower, more preferably 0°C to 40°C, still more preferably 10°C to 40°C, and particularly preferably 10°C to 20°C.

[0096] In the method for producing a catalyst for olefin polymerization according to the present invention, the treatment time when each component is subjected to a contact treatment is preferably 10 seconds to 60 minutes, more preferably 30 seconds to 30 minutes, still more preferably 1 minute to 30 minutes, and particularly preferably 1 minute to 10 minutes.

[0097] When (A) a solid catalyst component for olefin polymerization, (B) an organoaluminum compound, and (C) at least one external electron donor compound selected from an organosilicon compound represented by the general formula (I) and an organosilicon compound represented by the general formula (II) are brought into contact during the preparation of the polymerization catalyst, the reaction starts instantaneously, and the target catalyst for olefin polymerization can be formed. In the production method according to the present invention, the target catalyst for olefin polymerization can be prepared by the above contact treatment.

[0098] According to the present invention, even though an internal electron donor compound having no phthalate structure is used, when used for the polymerization of olefins, it is possible to provide a method for producing a catalyst for olefin polymerization capable of preparing an olefin polymer having a practically sufficiently wide molecular weight distribution and a high melt flow rate (MFR).

[0099] Next, the method for producing an olefin polymer according to the present invention will be described. The method for producing an olefin polymer according to the present invention is characterized in that polymerization of olefins is carried out using the olefin polymerization catalyst according to the present invention or the olefin polymerization catalyst obtained by the production method according to the present invention.

[0100] When polymerizing olefins using the olefin polymerization catalyst according to the present invention, the olefin polymerization catalyst obtained after preparing the above olefin polymerization catalyst can be isolated and contacted with olefins, or the above olefin polymerization catalyst can be directly contacted with olefins (without isolation) after preparation to be subjected to the polymerization treatment.

[0101] The polymerization of olefins may be homopolymerization of olefins or copolymerization, and may be random copolymerization or block copolymerization.

[0102] Examples of the olefins to be polymerized include one or more selected from ethylene, propylene, 1-butene, 1-pentene, 4-methyl-1-pentene, vinylcyclohexane, 1-hexene, 1,5-hexadiene, etc. Among these, one or more selected from ethylene, propylene, 4-methyl-1-pentene, 1-hexene and 1,5-hexadiene are preferred, and ethylene and propylene are particularly preferred.

[0103] In the method for producing an olefin polymer according to the present invention, the obtained olefin polymer may be a propylene-based block copolymer. In the present application documents, the propylene-based block copolymer means a block copolymer of propylene and olefins other than propylene.

[0104] When copolymerizing olefins, for example, when copolymerizing propylene with olefins other than propylene, examples of the olefin copolymerized with propylene include one or more selected from ethylene, 1-butene, 1-pentene, 4-methyl-1-pentene, vinylcyclohexane, etc. Among them, one or more selected from ethylene and 1-butene are preferred.

[0105] For example, when copolymerizing propylene with other olefins, examples include random copolymerization in which propylene and a small amount of ethylene are used as comonomers and polymerized in one step, and so-called propylene-ethylene block copolymerization in which propylene is homopolymerized in the first stage (first polymerization tank) and then propylene and ethylene are copolymerized in the second stage (second polymerization tank) or in two or more multi-stages (multi-stage polymerization tanks).

[0106] The polymerization temperature of olefins is preferably from room temperature or higher to 200 °C or lower, and more preferably from room temperature or higher to 100 °C or lower. Here, the room temperature means 20 °C.

[0107] The polymerization pressure of olefins is preferably 10 MPa or lower, and more preferably 6 MPa or lower.

[0108] Olefins may be polymerized by a continuous polymerization method or a batch polymerization method. Further, the polymerization reaction may be carried out in one step or in two or more multi-steps.

[0109] When carrying out the polymerization reaction of the above olefins, the polymerization atmosphere may be either an inert gas atmosphere or a gas atmosphere of olefins to be polymerized such as the above propylene.

[0110] According to the present invention, it is possible to provide a method for easily producing an olefin polymer having a practically sufficiently wide molecular weight distribution and a high melt flowability (MFR).

Examples

[0111] Next, the present invention will be described more specifically with reference to examples, which are merely illustrative and do not limit the present invention.

[0112] In the following evaluations, the content of titanium atoms and the content of the internal electron donor compound in the solid catalyst component mean the values measured by the methods described above.

[0113] In addition, the polymerization activity (g-pp / g-catalyst) during the polymerization reaction shown below was calculated by the following methods, respectively. Furthermore, the bulk density (BD) (g / ml), melt flowability (MFR), xylene solubles (XS), and molecular weight distribution of the obtained polypropylene were measured by the following methods, respectively.

[0114] <Polymerization activity> As the propylene polymerization activity, the polymerization activity (g-pp / g-catalyst) per 1 g of the solid catalyst component for olefin polymerization was determined by the following formula. Polymerization activity (g-pp / g-catalyst) = mass of the obtained polymer (g) / mass of the solid catalyst component for olefin polymerization (g)

[0115] <Bulk density (BD)> The bulk density (BD) of the polymer was measured according to JIS K6721.

[0116] <Melt flowability (MFR)> The melt flow rate (MFR) (g / 10 minutes) indicating the melt flowability of the obtained polymer was measured according to ASTM D 1238 and JIS K 7210.

[0117] <Xylene solubles (XS)> Into a flask equipped with a stirrer, 4.0 g of the polymer (polypropylene) and 200 mL of p-xylene were charged. Next, the external temperature was set to about 150 °C, and stirring was continued for 2 hours while maintaining the reflux of p-xylene (boiling point 137 - 138 °C) in the flask to dissolve the above polymer. Then, the solution was cooled to 23 °C over 1 hour, and the insoluble component and the soluble component were separated by filtration. The solution of the above dissolution components was sampled, p-xylene was distilled off by heating under reduced pressure, the weight of the obtained residue was determined, and the relative ratio (mass %) to the produced polymer (polypropylene) was calculated to obtain the xylene soluble content (XS).

[0118] <Molecular weight distribution> The molecular weight distribution of the obtained polymer was measured and determined under the following conditions by gel permeation chromatography (GPC) (GPC V2000 manufactured by Waters), and 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. Solvent: o-dichlorobenzene (ODCB) Temperature: 140 °C (SEC) Column: Shodex GPC UT-806M Sample concentration: 1 g / liter-ODCB (50 mg / 50 mL-ODCB) Injection volume: 0.5 mL Flow rate: 1.0 mL / min

[0119] (Example 1) (1) Preparation of solid catalyst component for olefin polymerization A 500 mL round bottom flask sufficiently replaced with nitrogen gas and equipped with a stirrer was charged with 20 g of diethoxymagnesium, and 110 mL of toluene, 1.5 mL of 2-isopropyl-2-isopentyl-1,3-dimethoxypropane (IIDMP), and 40 mL of titanium tetrachloride were added thereto to form a turbid liquid. Thereafter, the above turbid liquid was heated, and during the heating, 1.5 mL of IIDMP and 2.9 mL of 2-ethoxyethyl-1-ethyl carbonate (EEECA) were added, and the reaction was carried out with stirring at 100 °C for 3 hours. After completion of the reaction, the obtained solid product was washed 4 times with 150 mL of toluene at 90 °C, 40 mL of titanium tetrachloride and 80 mL of toluene were newly added, the temperature was raised to 100 °C, and the reaction was carried out with stirring for 15 minutes. After repeating the same reaction 3 times, it was washed 6 times with 150 mL of n-heptane at 40 °C to obtain the target solid catalyst component. The obtained solid catalyst component had a titanium content ratio of 2.2% by mass and an internal electron donor compound content ratio of 8.4% by mass (4.9% by mass of IIDMP and 3.5% by mass of EEECA).

[0120] (2) Formation of Catalyst for Olefin Polymerization Into an autoclave with a volume of 2.0 liters equipped with a stirrer that was completely replaced with nitrogen gas, 1.32 mmol of triethylaluminum, 0.13 mmol of cyclohexylcyclopentyl dimethoxysilane, and 0.0026 mmol of the solid catalyst component for olefin polymerization obtained in (1) above in terms of titanium atoms were charged to prepare a catalyst for olefin polymerization.

[0121] (3) Production of Polypropylene Into the autoclave filled with the catalyst for olefin polymerization, 4.0 liters of hydrogen gas and 1.4 liters of liquefied propylene were charged. After pre-polymerization was carried out at 20°C for 5 minutes, the temperature was raised, and a polymerization reaction was carried out at 70°C for 1 hour to obtain polypropylene.

[0122] The polymerization activity (g-pp / g-catalyst) during the above polymerization reaction was determined, and the physical properties of the obtained polypropylene were evaluated. The results are shown in Table 1.

[0123] (Example 2) In Example 1, polypropylene was obtained in the same manner as in Example 1 except that 4.0 liters of hydrogen gas was changed to 5.5 liters.

[0124] The polymerization activity (g-pp / g-catalyst) during the above polymerization reaction was determined, and the physical properties of the obtained polypropylene were evaluated. The results are shown in Table 1.

[0125] (Example 3) In Example 1, polypropylene was obtained in the same manner as in Example 1 except that cyclohexylcyclopentyl dimethoxysilane was changed to dicyclohexyl dimethoxysilane.

[0126] The polymerization activity (g-pp / g-catalyst) during the above polymerization reaction was determined, and the physical properties of the obtained polypropylene were evaluated. The results are shown in Table 1.

[0127] (Comparative Example 1) In Example 1, polypropylene was obtained in the same manner as in Example 1, except that cyclohexylcyclopentyldimethoxysilane was changed to cyclohexylmethyldimethoxysilane.

[0128] The polymerization activity (g-pp / g-catalyst) during the above polymerization reaction was determined, and the physical properties of the obtained polypropylene were evaluated. The results are shown in Table 1.

[0129] (Comparative Example 2) In Example 1, polypropylene was obtained in the same manner as in Example 1, except that cyclohexylcyclopentyldimethoxysilane was changed to dicyclopentyldimethoxysilane.

[0130] The polymerization activity (g-pp / g-catalyst) during the above polymerization reaction was determined, and the physical properties of the obtained polypropylene were evaluated. The results are shown in Table 1.

[0131] (Comparative Example 3) In Example 1, polypropylene was obtained in the same manner as in Example 1, except that cyclohexylcyclopentyldimethoxysilane was changed to diisopropyldimethoxysilane.

[0132] The polymerization activity (g-pp / g-catalyst) during the above polymerization reaction was determined, and the physical properties of the obtained polypropylene were evaluated. The results are shown in Table 1.

[0133] (Comparative Example 4) In Example 1, polypropylene was obtained in the same manner as in Example 1, except that cyclohexylcyclopentyldimethoxysilane was changed to bis(ethylamino)dicyclopentylsilane.

[0134] The polymerization activity (g-pp / g-catalyst) during the above polymerization reaction was determined, and the physical properties of the obtained polypropylene were evaluated. The results are shown in Table 1.

[0135] (Example 4) (1) Preparation of solid catalyst component for olefin polymerization 20 g of diethoxymagnesium was charged into a 500 mL round-bottom flask sufficiently replaced with nitrogen gas and equipped with a stirrer, and 110 mL of toluene and 40 mL of titanium tetrachloride were added thereto to form a turbid liquid. Thereafter, the above turbid liquid was heated, and 1.0 mL of IIDMP and 2.6 mL of EEECA were added during the heating, and the reaction was carried out with stirring at 100 °C for 1.5 hours. After the reaction was completed, the obtained solid product was washed 4 times with 150 mL of toluene at 90 °C, 20 mL of titanium tetrachloride and 100 mL of toluene were newly added, the temperature was raised to 100 °C, and the reaction was carried out with stirring for 15 minutes. After repeating the same reaction 3 times, it was washed 6 times with 150 mL of n-heptane at 40 °C to obtain the target solid catalyst component. The obtained solid catalyst component had a titanium content ratio of 2.4% by mass and an internal electron donor compound content ratio of 6.7% by mass (IIDMP 2.2% by mass, EEECA 4.5% by mass).

[0136] (2) Formation of catalyst for olefin polymerization and production of polypropylene A catalyst for olefin polymerization was formed in the same manner as in Example 1(2) except that the solid catalyst component for olefin polymerization obtained in (1) was used, and polypropylene was obtained in the same manner as in Example 1(3).

[0137] The polymerization activity (g-pp / g-catalyst) during the above polymerization reaction was determined, and the physical properties of the obtained polypropylene were evaluated. The results are shown in Table 1.

[0138] (Example 5) (1) Preparation of solid catalyst component for olefin polymerization 20 g of diethoxymagnesium was charged into a 500 mL round-bottom flask filled with nitrogen gas and equipped with a stirrer, and 75 mL of toluene, 1.6 mL of EEECA, and 75 mL of titanium tetrachloride were added thereto to form a turbid liquid. Thereafter, the temperature of the above turbid liquid was raised, and 1.6 mL of EEECA was added during the temperature rise, and the reaction was carried out with stirring at 100 °C for 1.5 hours. After the reaction was completed, the obtained solid product was washed 4 times with 150 mL of toluene at 90 °C, 40 ml of titanium tetrachloride and 80 mL of toluene were newly added, the temperature was raised to 100 °C, and the reaction was carried out with stirring for 15 minutes. After repeating the same reaction 3 times, it was washed 6 times with 150 mL of n-heptane at 40 °C to obtain the target solid catalyst component. The obtained solid catalyst component had a titanium content ratio of 2.4% by mass and an internal electron donor compound content ratio of 6.7% by mass (IIDMP 0% by mass, EEECA 6.7% by mass).

[0139] (2) Formation of Catalyst for Olefin Polymerization and Production of Polypropylene A catalyst for olefin polymerization was formed in the same manner as in Example 1(2) except that the solid catalyst component for olefin polymerization obtained in (1) was used, and polypropylene was obtained in the same manner as in Example 1(3).

[0140] The polymerization activity (g-pp / g-catalyst) during the above polymerization reaction was determined, and the physical properties of the obtained polypropylene were evaluated. The results are shown in Table 1.

[0141] (Example 6) (1) Formation of Catalyst for Olefin Polymerization A catalyst for olefin polymerization was prepared by charging 2.4 mmol of triethylaluminum, 0.24 mmol of cyclohexylcyclopentyldimethoxysilane, and 0.003 mmol of the solid catalyst component for olefin polymerization obtained in Example 1 in terms of titanium atoms into a 2.0-liter autoclave equipped with a stirrer and completely replaced with nitrogen gas.

[0142] (2) Production of Ethylene-Propylene Block Copolymer Into the autoclave with a stirrer containing the prepared polymerization catalyst, 15 moles of liquefied propylene and 0.20 MPa (partial pressure) of hydrogen gas were charged. After performing prepolymerization at 20°C for 5 minutes, the temperature was raised, and a first-stage homopolypropylene (homo-PP) polymerization reaction was carried out at 70°C for 45 minutes. Then, the pressure was returned to normal pressure, and then the inside of the reactor was purged with nitrogen gas, and then the autoclave was weighed. After subtracting the tare weight of the autoclave, the polymerization activity of the homo stage (first stage) was calculated by the following formula. The following polymerization activity (g-PP / g-cat) indicates the amount of polymer produced per 1 g of the solid catalyst component. <Calculation formula for polymerization activity> Polymerization activity (g-PP / g-cat) = (Amount of produced polymer (g) / (Solid catalyst component (g)) Next, ethylene / propylene / hydrogen were charged into the reactor so that the molar ratios were 0.85 / 1.15 / 0.043, respectively. After raising the temperature to 70°C, while introducing ethylene / propylene / hydrogen at a rate of 1.7 / 2.3 / 0.086 liters per minute, respectively, a reaction was carried out under the conditions of 1.2 MPa, 70°C, and 1 hour to obtain an ethylene-propylene block copolymer. The copolymerization (ICP) activity (g-ICP / (g-cat) at the time of forming the obtained ethylene-propylene copolymer was calculated by the following formula. <Calculation formula for ethylene-propylene block copolymerization activity> Copolymerization (ICP) activity (g-ICP / g-cat) = ((I(g) - G(g)) / (Mass of the solid catalyst component contained in the olefin polymerization catalyst (g)) Here, I is the mass (g) of the autoclave after the copolymerization reaction, and G is the mass (g) of the autoclave after removing unreacted monomers after the homo-PP polymerization. The results are shown in Table 2.

[0143] (Example 7) In Example 6, an ethylene-propylene block copolymer was obtained in the same manner as in Example 6, except that cyclohexylcyclopentyl dimethoxysilane was changed to dicyclohexyl dimethoxysilane.

[0144] The ethylene-propylene block copolymerization activity during the above polymerization reaction was determined, and the physical properties of the obtained ethylene-propylene block copolymer were evaluated. The results are shown in Table 2.

[0145] (Comparative Example 5) In Example 6, an ethylene-propylene block copolymer was obtained in the same manner as in Example 7, except that cyclohexylcyclopentyldimethoxysilane was changed to cyclohexylmethyldimethoxysilane.

[0146] The ethylene-propylene block copolymerization activity during the above polymerization reaction was determined, and the physical properties of the obtained ethylene-propylene block copolymer were evaluated. The results are shown in Table 2.

[0147] (Reference Example 1) (1) Preparation of Solid Catalyst Component for Olefin Polymerization 20 g of diethoxymagnesium was charged into a 500 mL round-bottom flask sufficiently replaced with nitrogen gas and equipped with a stirrer, and 140 mL of toluene, 3.6 mL of di-n-butyl phthalate, and 60 mL of titanium tetrachloride were added thereto to form a turbid liquid. Thereafter, the above turbid liquid was heated, and reacted with stirring at 90 °C for 3 hours. After completion of the reaction, the obtained solid product was washed 4 times with 150 mL of toluene at 90 °C, 60 mL of titanium tetrachloride and 60 mL of toluene were newly added, the temperature was raised to 115 °C, and reacted with stirring for 15 minutes. After the reaction, it was washed 6 times with 150 mL of n-heptane at 40 °C to obtain the target solid catalyst component. The obtained solid catalyst component had a titanium content ratio of 2.9% by mass and a phthalate compound content ratio of 18.4% by mass.

[0148] (2) Formation of Catalyst for Olefin Polymerization and Production of Polypropylene A catalyst for olefin polymerization was formed in the same manner as in Example 1(2), except that the solid catalyst component for olefin polymerization obtained in (1) was used, and polypropylene was obtained in the same manner as in Example 1(3). The polymerization activity (g-pp / g-catalyst) during the above polymerization reaction was determined, and the physical properties of the obtained polypropylene were evaluated. The results are shown in Table 1.

[0149] (Reference Example 2) In Reference Example 1, polypropylene was obtained in the same manner as in Reference Example 1, except that cyclohexylcyclopentyldimethoxysilane was changed to dicyclohexyldimethoxysilane.

[0150] The polymerization activity (g-pp / g-catalyst) during the above polymerization reaction was determined, and the physical properties of the obtained polypropylene were evaluated. The results are shown in Table 1.

[0151] (Reference Example 3) In Reference Example 1, polypropylene was obtained in the same manner as in Reference Example 1, except that cyclohexylcyclopentyldimethoxysilane was changed to bis(perhydroisoquinolino)dimethoxysilane.

[0152] The polymerization activity (g-pp / g-catalyst) during the above polymerization reaction was determined, and the physical properties of the obtained polypropylene were evaluated. The results are shown in Table 1.

[0153] [Table 1]

[0154] [Table 2]

[0155] From Table 1, in Examples 1 to 5, homopolymerization of propylene was carried out using a catalyst for olefin polymerization comprising (A) a solid catalyst component for olefin polymerization containing a compound having no phthalate structure as an internal electron donor compound, (B) an organoaluminum compound, and (C) an external electron donor compound composed of a specific organosilicon compound. Therefore, compared with the case of carrying out homopolymerization of propylene using a catalyst for olefin polymerization containing a solid catalyst component for olefin polymerization having a phthalate ester as an internal electron donor compound described in Comparative Examples 1 to 3, it can be seen that an olefin polymer having a sufficiently wide molecular weight distribution in practical use and better melt flowability (MFR) can be prepared. Also, from Table 2, in Examples 6 to 7 as well, homopolymerization of propylene was carried out using a catalyst for olefin polymerization comprising (A) a solid catalyst component for olefin polymerization containing a compound having no phthalate structure as an internal electron donor compound, (B) an organoaluminum compound, and (C) an external electron donor compound composed of a specific organosilicon compound. Therefore, it can be seen that an olefin polymer having excellent melt flowability (MFR) can be prepared. Further, it can be seen that excellent copolymerization activity can be exhibited in the copolymerization reaction of olefins using the above-mentioned specific catalyst for olefin polymerization.

[0156] On the other hand, from Table 1, in Comparative Examples 1 to 4, since the catalyst for olefin polymerization does not have an external electron donor compound composed of a specific organosilicon compound, it can be seen that the molecular weight distribution of the polymer obtained when used for the polymerization of olefins is inferior.

[0157] Also, from Table 2, in Comparative Example 5, since the catalyst for olefin polymerization does not have an external electron donor compound composed of a specific organosilicon compound, it can be seen that the copolymerization activity is inferior when the catalyst for olefin polymerization is used in a copolymerization reaction.

Industrial Applicability

[0158] According to the present invention, even though an internal electron-donating compound having no phthalate structure is used, when subjected to the polymerization of olefins, it is possible to provide an olefin polymerization catalyst capable of preparing an olefin polymer having a practically sufficiently wide molecular weight distribution and a high melt flowability (MFR), and it is also possible to provide a method for producing the olefin polymerization catalyst and a method for producing the olefin polymer.

Claims

1. (A) A solid catalyst component for olefin polymerization containing titanium, magnesium, a halogen, and a compound having no phthalate structure as an internal electron donor compound; (B) An organoaluminum compound; (C) One or more external electron donor compounds selected from the following general formula (I) SiR １ ２ (OR ２ ) ２ (I) (However, R １ is a cycloalkyl group having 6 or more carbon atoms, and R ２ is an alkyl group having 1 to 5 carbon atoms.) The organosilicon compound represented by and The following general formula (II) SiR ３ R ４ (OR ５ ) (OR ６ ) (II) (However, R ３ is a cycloalkyl group having 6 or more carbon atoms or a derivative thereof, R ４ is a cycloalkyl group having 5 or more carbon atoms or a derivative thereof, R ５ and R ６ are alkyl groups having 1 to 3 carbon atoms, R ５ and R ６ may be the same as or different from each other.) An organosilicon compound represented by A catalyst for olefin polymerization, characterized by comprising: A catalyst for olefin polymerization.

2. The solid catalyst component for olefin polymerization in (A) contains an ether carbonate compound as an internal electron donor compound, and contains 30 to 100 mol% of the ether carbonate compound based on the total content of the internal electron donor compounds. The catalyst for olefin polymerization according to Claim 1.

3. The organoaluminum compound in (B) is one or more represented by the following general formula (III) R ７ ｐ AlQ ３－ｐ (III) (wherein, R １ 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 there are a plurality of R ７ , each R ７ may be the same as or different from each other, and when there are a plurality of Q, each Q may be the same as or different from each other.) A catalyst for olefin polymerization according to Claim 1. The catalyst for olefin polymerization according to Claim 1.

4. The external electron donor compound in (C) is one or more selected from dicyclohexyldimethoxysilane and cyclohexylcyclopentyldimethoxysilane. The catalyst for olefin polymerization according to Claim 1.

5. A method for producing a catalyst for olefin polymerization, comprising: (A) A solid catalyst component for olefin polymerization containing titanium, magnesium, a halogen, and a compound having no phthalate structure as an internal electron donor compound; (B) An organoaluminum compound; (C) One or more external electron donor compounds selected from the following general formula (I) SiR １ ２ (OR ２ ) ２ (I) (However, R １ is a cycloalkyl group having 6 or more carbon atoms, and R ２ is an alkyl group having 1 to 5 carbon atoms.) The organosilicon compound represented by and The following general formula (II) SiR ３ R ４ (OR ５ ) (OR ６ ) (II) (However, R ３ is a cycloalkyl group having 6 or more carbon atoms and / or a derivative thereof, R ４ is a cycloalkyl group having 5 or more carbon atoms or a derivative thereof, R ５ and R ６ are alkyl groups having 1 to 3 carbon atoms, which may be the same as or different from each other.) An organosilicon compound represented by Contacting them with each other to obtain a catalyst for olefin polymerization. A method for producing a catalyst for olefin polymerization, characterized by: A method for producing a catalyst for olefin polymerization.

6. A method for producing an olefin polymer, characterized by polymerizing olefins using the catalyst for olefin polymerization according to any one of Claims 1 to 4 or the catalyst for olefin polymerization obtained by the production method according to Claim 5.

7. The method for producing an olefin polymer according to Claim 6, wherein the obtained olefin polymer is a propylene-based block copolymer.

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