JP4632299B2 - Solid catalyst component for olefin polymerization, process for producing the same and catalyst - Google Patents

Description

  The present invention relates to a solid catalyst component and a catalyst for olefin polymerization, which can obtain an olefin polymer in a high yield while maintaining high stereoregularity, and particularly exhibits excellent activity persistence.

  Conventionally, in the polymerization of olefins, solid catalyst components containing magnesium, titanium, an electron donating compound and halogen as essential components are known. Many olefin polymerization methods have been proposed in which propylene is polymerized or copolymerized in the presence of an olefin polymerization catalyst comprising the solid catalyst component, an organoaluminum compound, and an organosilicon compound. For example, Patent Document 1 (Japanese Patent Laid-Open No. 57-63310) and Patent Document 2 (Japanese Patent Laid-Open No. 57-63311) contain an electron donor of a magnesium compound, a titanium compound, and an organic dicarboxylic acid ester compound. A method of polymerizing an olefin having 3 or more carbon atoms using a catalyst comprising a combination of a solid catalyst component, an organoaluminum compound and an organosilicon compound having a Si—O—C bond is disclosed.

Patent Document 3 (Japanese Patent Laid-Open No. 1-6006) discloses a solid catalyst component for olefin polymerization containing dialkoxymagnesium, titanium tetrachloride, and dibutyl phthalate, and in the presence of this solid catalyst component. By polymerizing propylene, a stereoregular polymer is obtained in a high yield, which is effective to some extent. By the way, recently, polymers having various physical properties have been demanded, and after using a multistage polymerization apparatus, firstly propylene is polymerized to obtain polypropylene, a copolymer composed of ethylene and propylene is produced in another reactor, The polymerization time has been prolonged, such as obtaining a block copolymer, and obtaining a broad molecular weight distribution polymer that produces polymers having different molecular weights in the former stage and the latter stage. Usually, in the polymerization reaction, as the polymerization time elapses, the reduction of the titanium component, which is the active point of the solid catalyst component, by organoaluminum proceeds and the polymerization activity is lost. Due to such deactivation of the catalyst, there was a problem that in the latter half of the polymerization, the activity was lowered and the productivity was lowered, or a polymer having desired characteristics could not be obtained. In order to solve such a problem, Patent Document 4 (Japanese Patent Laid-Open No. 2003-292522) discloses that the activity sustainability is improved by using a vinylsilane compound during polymerization. However, although such a method improves the activity persistence, it has disadvantages that the stereoregularity of the polymer is lowered and the final polymer yield is low.
JP 57-63310 A JP-A-57-63311 Japanese Patent Laid-Open No. 1-6006 JP 2003-292522 A

  That is, an object of the present invention is to provide a solid catalyst component and a catalyst for olefin polymerization, which can obtain an olefin polymer while maintaining high yield and stereoregularity, and further have good activity persistence. There is.

  In such a situation, the present inventor has intensively studied to solve the problems remaining in the above-mentioned prior art, and as a result, the solid catalyst contains magnesium, titanium, a halogen atom and an electron donor and has a specific composition and characteristics. It has been found that the component exhibits high activity when subjected to polymerization of olefins, and particularly when subjected to polymerization of propylene, a propylene polymer can be obtained while maintaining high stereoregularity and high yield for a long time. The present invention has been completed.

That is, in the present invention, dialkoxymagnesium (a) is suspended in an aromatic hydrocarbon compound, then titanium tetrachloride (b) and diethyl 2,3-diethylsuccinate, 2,3-dipropylsuccinic acid. Diethyl, diethyl 2,3-diisopropyl succinate, diethyl 2,3-dibutyl succinate, diethyl 2,3-diisobutyl succinate, diethyl 2,3-di-tert-butyl succinate, dibutyl 2,3-diethyl succinate, Selected from dibutyl 2,3-dipropyl succinate, dibutyl 2,3-diisopropyl succinate, dibutyl 2,3-dibutyl succinate, dibutyl 2,3-diisobutyl succinate and dibutyl 2,3-di-tert-butyl succinate It is a solid catalyst component obtained by contacting an electron donor (c), the solid catalyst Titanium content in minute is not less 2.0 wt% or more, electron donor (c) and the molar ratio of titanium less than 1.1, provides olefin polymerization solid catalyst component is 1.5 or less Is.
In the present invention, dialkoxymagnesium (a) is suspended in an aromatic hydrocarbon compound, and then titanium tetrachloride (b) is added in an amount of 0.5 to 100 moles per mole of dialkoxymagnesium (a). And diethyl 2,3-diethyl succinate, diethyl 2,3-dipropyl succinate, diethyl 2,3-diisopropyl succinate, diethyl 2,3-dibutyl succinate, diethyl 2,3-diisobutyl succinate, 2,3 -Diethyl di-tert-butyl succinate, dibutyl 2,3-diethyl succinate, dibutyl 2,3-dipropyl succinate, dibutyl 2,3-diisopropyl succinate, dibutyl 2,3-dibutyl succinate, 2,3- electron donor selected from diisobutyl succinate, dibutyl and 2,3-di -tert- butylsuccinic dibutyl (c) 0.01 mole per mole of dialkoxymagnesium (a) is contacted, the titanium content in the solid catalyst component is 2.0% by weight or more, and the molar ratio of the electron donor (c) to titanium is 1. The present invention provides a method for producing a solid catalyst component for olefin polymerization, characterized by obtaining a solid catalyst component of 1 or more and 1.5 or less .

Further, the present invention provides (A) the above-mentioned olefin polymerization catalyst component, (B) the following general formula (1);
R ¹ _p AlQ _3-p (1)
(Wherein R ¹ represents an alkyl group having 1 to 4 carbon atoms, Q represents a hydrogen atom or a halogen atom, and p is an integer of 0 <p ≦ 3), and (C) An olefin polymerization catalyst characterized by containing an external electron donating compound.

  The catalyst for olefin polymerization of the present invention can obtain an olefin polymer in a high yield while maintaining high stereoregularity at a high level, and further shows a solid catalyst component and catalyst for olefin polymerization that exhibit sustained activity. Is to provide.

  The solid catalyst component (A) for olefin polymerization of the present invention (hereinafter sometimes simply referred to as “component (A)”) contains magnesium, titanium, a halogen atom and an electron donor, and is contained in the solid catalyst component. The titanium content is 2.0% by weight or more, preferably 2.0 to 5.0% by weight, particularly preferably 2.0 to 4.2% by weight. When titanium is less than 2% by weight, when an olefin is polymerized by forming a catalyst with an organoaluminum compound, the reduction by the organoaluminum compound easily proceeds and the polymerization activity is lowered.

  The molar ratio of the electron donor and titanium in the solid catalyst component is 1.1 or more, preferably 1.2 to 1.5, more preferably 1.2 to 1.4. When the molar ratio of the electron donor to titanium is less than 1.1, it is not preferable in that the reaction between titanium and organoaluminum easily proceeds. As a method for measuring the content of the electron donor in the solid catalyst component, a known method can be applied. For example, a suspension is obtained by adding the solid catalyst component to a mixed solution of hydrochloric acid and toluene under an inert atmosphere, After the suspension is sufficiently stirred, the toluene solution portion is separated, washed with water, and then the electron donor contained in the toluene portion is quantified by gas chromatography.

  Furthermore, 20 to 60 mol%, preferably 20 to 55 mol% of the electron donor contained when the solid catalyst component is brought into contact with triethylaluminum is extracted. When the extraction rate of the electron donor exceeds 60 mol%, when used for the polymerization of olefins, the titanium component in the solid catalyst component is excessively reduced, the polymerization activity is rapidly lost, and the extraction rate is 20 If it is less than%, the titanium component that acts on the activity of olefin polymerization in the titanium component in the solid catalyst component decreases, and the polymerization activity decreases.

  Examples of the contact between the solid catalyst component and triethylaluminum include a method in which 3 g of solid catalyst and 6.4 g of triethylaluminum are added to 100 ml of heptane under an inert atmosphere at room temperature, and stirred for 30 minutes. After contacting the solid catalyst component with triethylaluminum, the solid and liquid are separated using a glass filter, the resulting solid is thoroughly washed with heptane, dried, and the content of the electron donor in the dried product is measured. The extraction rate may be determined by the ratio between the remaining amount after 30 minutes and the content before the extraction test.

  Further, magnesium in the solid catalyst component is usually 10 to 30% by weight, electron donor is 2.4 to 20% by weight, and halogen atom is 45 to 70% by weight.

  The solid catalyst component (A) of the present invention can be obtained by contacting a magnesium compound, a titanium halide compound and an electron donor. Magnesium compounds (hereinafter sometimes simply referred to as “component (a)”) used for the preparation of the solid catalyst component include dihalogenated magnesium, dialkylmagnesium, halogenated alkylmagnesium, dialkoxymagnesium, diaryloxymagnesium, and halogenated compounds. Examples include alkoxy magnesium and fatty acid magnesium.

  Specific examples of the magnesium dihalide include magnesium dichloride, magnesium dibromide, magnesium diiodide, magnesium difluoride and the like.

As the dialkyl magnesium, a compound represented by the general formula R ⁴ R ⁵ Mg (wherein R ⁴ and R ⁵ represent an alkyl group having 1 to 10 carbon atoms and may be the same or different) is preferable. More specifically, dimethyl magnesium, diethyl magnesium, methyl ethyl magnesium, dipropyl magnesium, methyl propyl magnesium, ethyl propyl magnesium, dibutyl magnesium, methyl butyl magnesium, ethyl butyl magnesium and the like can be mentioned. These dialkyl magnesiums can be obtained by reacting metallic magnesium with a halogenated hydrocarbon or alcohol.

The halogenated alkylmagnesium is preferably a compound represented by the general formula R ⁶ MgD ¹ (wherein R ⁶ represents an alkyl group having 1 to 10 carbon atoms and D ¹ represents a halogen atom). Specific examples include ethyl magnesium chloride, propyl magnesium chloride, butyl magnesium chloride and the like. These magnesium halides can be obtained by reacting magnesium metal with a halogenated hydrocarbon or alcohol.

The dialkoxymagnesium or diaryloxymagnesium has the general formula Mg (OR ⁷ ) (OR ⁸ ) (wherein R ⁷ and R ⁸ represent an alkyl group having 1 to 10 carbon atoms or an aryl group, and may be the same or different. And more specifically, dimethoxy magnesium, diethoxy magnesium, dipropoxy magnesium, dibutoxy magnesium, diphenoxy magnesium, ethoxymethoxy magnesium, ethoxypropoxy magnesium, butoxyethoxy magnesium, and the like. Is mentioned. These dialkoxymagnesium or diaryloxymagnesium can be obtained by reacting metal magnesium with an alcohol in the presence of a halogen or a halogen-containing metal compound.

The halogenated alkoxymagnesium is preferably a compound represented by the general formula Mg (OR ⁹ ) D ² (wherein R ⁹ represents an alkyl group having 1 to 10 carbon atoms and D ² represents a halogen atom). Specific examples include methoxy magnesium chloride, ethoxy magnesium chloride, propoxy magnesium chloride, butoxy magnesium chloride and the like.

The fatty acid magnesium is preferably a compound represented by the general formula Mg (R ¹⁰ COO) ₂ (wherein R ¹⁰ represents a hydrocarbon group having 1 to 20 carbon atoms), and more specifically, lauric acid. Examples thereof include magnesium, magnesium stearate, magnesium octoate, and magnesium decanoate.

  Among these magnesium compounds in the present invention, dialkoxymagnesium is preferable, and among them, diethoxymagnesium and dipropoxymagnesium are particularly preferably used. Moreover, said magnesium compound can also be used individually or in combination of 2 or more types.

  In the present invention, when dialkoxymagnesium is used as the solid catalyst component (A) for olefin polymerization, the dialkoxymagnesium is in the form of granules or powder, and the shape thereof may be indefinite or spherical. For example, when spherical dialkoxymagnesium is used, a polymer powder having a better particle shape and a narrow particle size distribution can be obtained, and the handling operability of the produced polymer powder during the polymerization operation is improved. Problems such as blockage caused by the contained fine powder are solved.

  The spherical dialkoxymagnesium does not necessarily need to be spherical, and an elliptical or potato-shaped one is used. Specifically, the particle shape is such that the ratio (l / w) of the major axis diameter l to the minor axis diameter w is usually 3 or less, preferably 1 to 2, more preferably 1 to 1.5. is there. Such spherical dialkoxymagnesium production methods are disclosed in, for example, JP-A-58-41832, JP-A-62-51633, JP-A-3-74341, JP-A-4-368391, and JP-A-8-73388. Etc.

  The average particle size of the dialkoxymagnesium is usually 1 to 200 μm, preferably 5 to 150 μm. In the case of spherical dialkoxymagnesium, the average particle size is usually 1 to 100 μm, preferably 5 to 50 μm, and more preferably 10 to 40 μm. As for the particle size, it is desirable to use one having a small particle size distribution and a small amount of fine powder and coarse powder. Specifically, the particle size of 5 μm or less is 20% or less, preferably 10% or less. On the other hand, the particle size of 100 μm or more is 10% or less, preferably 5% or less. Further, when the particle size distribution is expressed by ln (D90 / D10) (where D90 is the cumulative particle size and the particle size at 90%, D10 is the cumulative particle size and the particle size at 10%), it is preferably 3 or less, preferably 2 or less.

As the titanium halide compound used for preparing the solid catalyst component (A) for olefin polymerization of the present invention, a tetrahalogenated titanium compound or an alkoxytitanium halide is used. Examples of the titanium halide compound include titanium tetrachloride, titanium tetrabromide, and titanium tetraiodide. Preferably, titanium tetrachloride (hereinafter sometimes simply referred to as “component (b)”) is used, but a titanium halide compound other than titanium tetrachloride can be used in combination. As this halogenated titanium compound, the general formula Ti (OR ¹¹ ) _n Cl _4-n (wherein R ¹¹ represents an alkyl group having 1 to 4 carbon atoms, and n is an integer of 1 ≦ n ≦ 3). The alkoxy titanium chloride represented by this is illustrated. Moreover, said titanium halide compound can also be used individually or in combination of 2 or more types. Specifically, Ti (OCH ₃ ) Cl ₃ , Ti (OC ₂ H ₅ ) Cl ₃ , Ti (OC ₃ H ₇ ) Cl ₃ , Ti (OnC ₄ H ₉ ) Cl ₃ , Ti (OCH ₃ ) ₂ Cl ₂ , Ti (OC ₂ H ₅ ) ₂ Cl ₂ , Ti (OC ₃ H ₇ ) ₂ Cl ₂ , Ti (OnC ₄ H ₉ ) ₂ Cl ₂ , Ti (OCH ₃ ) ₃ Cl, Ti (OC ₂ H ₅ ) _{3 Cl, Ti (OC 3 H} 7) 3 Cl, Ti (OnC 4 H 9) 3 Cl , and the like.

  In addition, in the preparation of the solid catalyst component (A) for olefin polymerization in the present invention, a halogenated silane compound or an organic acid halide can be used in combination with the halogenated titanium compound. Examples of the halogenated silane compound include silicon tetrachloride, silicon tetrabromide, and silicon tetraiodide. Silicon tetrachloride is preferably used, but halogenated silane compounds other than silicon tetrachloride can be used in combination therewith. Organic acid halides include benzoyl chloride, benzoic acid chloride, formic acid chloride, acetic acid chloride, propionic acid chloride, phthalic acid dichloride, isophthalic acid dichloride, terephthalic acid dichloride, malonic acid dichloride, succinic acid dichloride, maleic acid dichloride, fumaric acid dichloride, Glutaric acid dichloride, benzoyl bromide, benzoic acid bromide, formic acid bromide, acetic acid bromide, propionic acid bromide, phthalic acid dibromide, isophthalic acid dibromide, terephthalic acid dibromide, malonic acid dibromide, succinic acid dibromide, maleic acid dibromide , Fumaric acid dibromide, glutaric acid dibromide, benzoyl iodide, benzoic acid iodide, formic acid iodide, acetic acid eye Iodide, iodide propionic acid, diiodide phthalic acid, diiodide isophthalic acid, diiodide terephthalic acid, diiodide malonic acid, diiodide succinic acid, diiodide maleic acid, diiodide fumaric acid, diiodide glutaric acid and the like. Preferred examples include benzoyl chloride, benzoic acid chloride, phthalic acid dichloride, malonic acid dichloride, succinic acid dichloride, and maleic acid dichloride, and one or more of these may be used in combination. Moreover, you may use together a halogenated silane compound and an organic acid halide.

  The electron donors used in the preparation of the solid catalyst component (A) for olefin polymerization in the present invention and the solid catalyst component (A) include fumaric acid diesters and derivatives thereof, phthalic acid diesters and derivatives thereof. And dicarboxylic acid diester derivatives such as malonic acid diester derivatives, succinic acid diester derivatives, and maleic acid diester derivatives.

  As the dicarboxylic acid diester derivative, when the solid catalyst component and triethylaluminum are brought into contact, the malonic acid diester derivative, in that the amount extracted from the solid catalyst component can be easily adjusted to 20 to 60 mol% of the initial content, A succinic acid diester derivative or a maleic acid diester derivative is preferred, and these dicarboxylic acid diesters are substituted with two hydrocarbon groups which may be the same as each other selected from an alkyl group and a cycloalkyl group. And the compound whose sum total of carbon number of the said 2 hydrocarbon group is 4-10 is especially preferable at the point which gives a highly active and highly stereoregular catalyst.

  As malonic acid diester derivatives, propylmalonic acid, isopropylmalonic acid, butylmalonic acid, isobutylmalonic acid, sec-butylmalonic acid, tert-butylmalonic acid, pentylmalonic acid, isopentylmalonic acid, neopentylmalonic acid, hexylmalon Acid, isohexylmalonic acid, cyclopentylmalonic acid, cyclohexylmalonic acid, dimethylmalonic acid, diethylmalonic acid, dipropylmalonic acid, diisopropylmalonic acid, dibutylmalonic acid, diisobutylmalonic acid, di-sec-butylmalonic acid, di- tert-Butylmalonic acid, dipentylmalonic acid, diisopentylmalonic acid, dineopentylmalonic acid, dihexylmalonic acid, diisohexylmalonic acid, dicyclopentylmalonic acid, dicyclohexylmalonic acid, methylethylmalo Acid, methylpropylmalonic acid, methylbutylmalonic acid, methylcyclopentylmalonic acid, methylcyclohexylmalonic acid, methylethylmalonic acid, methylpropylmalonic acid, methylbutylmalonic acid, methylcyclopentylmalonic acid, methylcyclohexylmalonic acid, ethylpropylmalonic acid Acid, ethyl butyl malonic acid, ethyl cyclopentyl malonic acid, ethyl cyclohexyl malonic acid, propyl butyl malonic acid, propyl cyclopentyl malonic acid, propyl cyclohexyl malonic acid, butyl cyclopentyl malonic acid, butyl cyclohexyl malonic acid, isobutyl cyclopentyl malonic acid, isobutyl cyclohexyl malon Acid, diethyl ester, dipropyl ester, dibutyl ester, diisobutyrate of cyclopentylcyclohexylmalonic acid Ester, and the like. Of these, diethyl diethylmalonate, diethyl dipropylmalonate, diethyl diisopropylmalonate, diethyl dibutylmalonate, diethyl diisobutylmalonate, diethyl di-tert-butylmalonate, dibutyldiethylmalonate, dibutyldipropylmalonate Diethyl malonate, dibutyl malonate, dibutyl malonate dibutyl, diisobutyl malonate dibutyl, di-tert-butyl malonate dibutyl, and methylcyclopentyl malonic acid are preferred.

  Specific examples of succinic acid diester derivatives include alkyl succinic acid diesters such as propyl succinic acid, isopropyl succinic acid, butyl succinic acid, isobutyl succinic acid, sec-butyl succinic acid, tert-butyl succinic acid, pentyl succinic acid, neopentyl succinic acid Diethyl ester, dipropyl ester, dibutyl ester, and the like. Examples of the dialkyl succinic acid diester include 2,3-dimethyl succinic acid, 2,3-diethyl succinic acid, 2,3-dipropyl succinic acid, 2,3 -Diisopropyl succinic acid, 2,3-dibutyl succinic acid, 2,3-diisobutyl succinic acid, 2,3-di-sec-butyl succinic acid, 2,3-di-tert-butyl succinic acid, 2,3-dipentyl succinic acid 2,3-dineopentyl succinic acid, 2-methyl-3 Ethyl succinic acid, 2-methyl-3-propyl succinic acid, 2-methyl-3-isopropyl succinic acid, 2-methyl-3-butyl succinic acid, 2-methyl-3-isobutyl succinic acid, 2-methyl-3-tert- Butyl succinic acid, 2-methyl-3-pentyl succinic acid, 2-methyl-3-neopentyl succinic acid, 2-ethyl-3-propyl succinic acid, 2-ethyl-3-isopropyl succinic acid, 2-ethyl-3- Diethyl butyl succinate, 2-ethyl-3-isobutyl succinic acid, 2-ethyl-3-tert-butyl succinic acid, 2-ethyl-3-pentyl succinic acid, 2-ethyl-3-neopentyl succinic acid, 2-ethyl- 3-propyl succinic acid, 2-ethyl-3-isopropyl succinic acid, 2-ethyl-3-butyl succinic acid, 2-ethyl-3-isobutyl succinic acid Succinic acid, 2-ethyl-3-tert-butyl succinic acid, 2-ethyl-3-pentyl succinic acid, 2-ethyl-3-neopentyl succinic acid, 2-ethyl-3-propyl succinic acid, 2-ethyl-3 Isopropyl succinic acid, 2-ethyl-3-butyl succinic acid, 2-ethyl-3-isobutyl succinic acid di, 2-ethyl-3-tert-butyl succinic acid, 2-ethyl-3-pentyl succinic acid, 2-ethyl- Examples include diethyl esters such as 3-neopentyl succinic acid, dipropyl esters, dibutyl esters, diisobutyl esters and the like. Cycloalkyl succinic acid diesters include cyclopentyl succinic acid, cyclohexyl succinic acid, 2,3-dicyclopentyl succinic acid, 2,3-dicyclohexyl succinic acid, 2-methyl-3-cyclopentyl succinic acid, 2-methyl-3-cyclohexyl. Examples include diethyl esters such as succinic acid, 2-ethyl-3-cyclopentyl succinic acid, and 2-ethyl-3-cyclohexyl succinic acid, dipropyl esters, and dibutyl esters. Of these, diethyl 2,3-diethyl succinate, diethyl 2,3-dipropyl succinate, diethyl 2,3-diisopropyl succinate, diethyl 2,3-dibutyl succinate, diethyl 2,3-diisobutyl succinate , Diethyl 2,3-di-tert-butyl succinate, dibutyl 2,3-diethyl succinate, dibutyl 2,3-dipropyl succinate, dibutyl 2,3-diisopropyl succinate, dibutyl 2,3-dibutyl succinate, Dibutyl 2,3-diisobutyl succinate, dibutyl 2,3-di-tert-butyl succinate and the like are preferable.

  Specific examples of maleic diester derivatives include alkyl maleic diesters such as propyl maleic acid, isopropyl maleic acid, butyl maleic acid, isobutyl maleic acid, sec-butyl maleic acid, tert-butyl maleic acid, pentyl maleic acid, neopentyl. Examples thereof include diethyl esters such as maleic acid, dipropyl esters, and dibutyl esters. Examples of dialkyl maleic acid diesters include 2,3-dimethylmaleic acid, 2,3-diethylmaleic acid, 2,3-dipropylmaleic acid, 2,3-diisopropylmaleic acid, 2,3-dibutylmaleic acid, 2,3-diisobutylmaleic acid, 2,3-di-sec-butylmaleic acid, 2,3-di-tert-butylmaleic acid, 2, 3-dipentylmaleic acid, 2,3 Dineopentylmaleic acid, 2-methyl-3-ethylmaleic acid, 2-methyl-3-propylmaleic acid, 2-methyl-3-isopropylmaleic acid, 2-methyl-3-butylmaleic acid, 2-methyl- 3-isobutylmaleic acid, 2-methyl-3-tert-butylmaleic acid, 2-methyl-3-pentylmaleic acid, 2-methyl-3-neopentylmaleic acid, 2-ethyl-3-propylmaleic acid, 2 -Ethyl-3-isopropylmaleic acid, 2-ethyl-3-butylmaleic acid diethyl, 2-ethyl-3-isobutylmaleic acid, 2-ethyl-3-tert-butylmaleic acid, 2-ethyl-3-pentylmalein Acid, 2-ethyl-3-neopentylmaleic acid, 2-ethyl-3-propylmaleic acid, 2-ethyl-3-isopropyl Lumaleic acid, 2-ethyl-3-butylmaleic acid, 2-ethyl-3-isobutylmaleic acid, 2-ethyl-3-tert-butylmaleic acid, 2-ethyl-3-pentylmaleic acid, 2-ethyl-3 -Neopentylmaleic acid, 2-ethyl-3-propylmaleic acid, 2-ethyl-3-isopropylmaleic acid, 2-ethyl-3-butylmaleic acid, 2-ethyl-3-isobutylmaleic acid di, 2-ethyl Examples include diethyl esters such as -3-tert-butylmaleic acid, 2-ethyl-3-pentylmaleic acid, and 2-ethyl-3-neopentylmaleic acid, dipropyl esters, dibutyl esters, and diisobutyl esters. Cycloalkylmaleic acid diesters include cyclopentylmaleic acid, cyclohexylmaleic acid, 2,3-dicyclopentylmaleic acid, 2,3-dicyclohexylmaleic acid, 2-methyl-3-cyclopentylmaleic acid, 2-methyl-3-cyclohexyl. Examples thereof include diethyl esters such as maleic acid, 2-ethyl-3-cyclopentylmaleic acid, and 2-ethyl-3-cyclohexylmaleic acid, dipropyl esters, and dibutyl esters. Of these, diethyl 2,3-diethyl maleate, diethyl 2,3-dipropyl maleate, diethyl 2,3-diisopropyl maleate, diethyl 2,3-dibutyl maleate, diethyl 2,3-diisobutyl maleate 2,3-di-tert-butyl maleate diethyl, 2,3-diethyl maleate dibutyl, 2,3-dipropyl maleate dibutyl, 2,3-diisopropyl maleate dibutyl, 2,3-dibutyl maleate dibutyl 2,3-diisobutyl maleate dibutyl, 2,3-di-tert-butyl maleate dibutyl and the like are preferable. Moreover, the said component (c) can be used individually or in combination of 2 or more types.

  In the preparation of the solid catalyst component (A) for olefin polymerization in the present invention, in addition to the above essential components, aluminum trichloride, diethoxyaluminum chloride, diisopropoxyaluminum chloride, ethoxyaluminum dichloride, isopropoxyaluminum dichloride. , Aluminum compounds such as butoxyaluminum dichloride and triethoxyaluminum, or metal salts of organic acids such as sodium stearate, magnesium stearate and aluminum stearate, or liquid or viscous chain, partially hydrogenated, cyclic or modified at room temperature Polysiloxanes such as polysiloxanes can be used. As the chain polysiloxane, dimethylpolysiloxane and methylphenylpolysiloxane are used. As the partially hydrogenated polysiloxane, methylhydrogen polysiloxane having a hydrogenation rate of 10 to 80% is used. As the cyclic polysiloxane, hexamethylcyclopentane is used. Siloxane, 2,4,6-trimethylcyclotrisiloxane, 2,4,6,8-tetramethylcyclotrisiloxane, and modified polysiloxanes include higher fatty acid group-substituted dimethylsiloxane, epoxy group-substituted dimethylsiloxane, An oxyalkylene group-substituted dimethylsiloxane is exemplified.

  The solid catalyst component (A) for olefin polymerization can be prepared by contacting the component (a), the component (b), and the component (c) as described above. Although it is possible to perform the treatment in the absence of a solvent, it is preferable to perform the treatment in the presence of the solvent in consideration of ease of operation. Examples of the inert organic solvent used include saturated hydrocarbon compounds such as hexane, heptane, and cyclohexane, aromatic hydrocarbon compounds such as benzene, toluene, xylene, and ethylbenzene, orthodichlorobenzene, methylene chloride, carbon tetrachloride, dichloroethane, and the like. Among them, aromatic hydrocarbon compounds which have a boiling point of about 90 to 150 ° C. and are liquid at room temperature, specifically, toluene, xylene and ethylbenzene are preferably used. In particular, the activity and stereospecificity of the solid catalyst component obtained by using toluene, xylene, and ethylbenzene for contact with each component or for washing after contact can be further improved.

  Further, as a method for preparing the solid catalyst component (A) for olefin polymerization, the magnesium compound of the above component (a) is dissolved in alcohol, titanium compound, carbonic acid or the like, and the component (b) or the component (b). And a method of obtaining a solid component by depositing a solid substance by contact with the component (c) or heat treatment, etc., and suspending the component (a) in the component (b) or an inert hydrocarbon compound solvent, etc. c) or a method in which the component (c) and the component (b) are contacted to obtain the solid catalyst component (A) for olefin polymerization.

  Among these, the particles of the solid catalyst component obtained by the former method are almost spherical and the particle size distribution is sharp. Also in the latter method, a spherical solid catalyst component having a sharp particle size distribution can be obtained by using a spherical magnesium compound, and without using a spherical magnesium compound, for example, using a spray device. By forming particles by a so-called spray drying method in which a solution or suspension is sprayed and dried, a solid catalyst component having a spherical shape and a sharp particle size distribution can be obtained.

  The contact of each component is performed with stirring in a container equipped with a stirrer in an inert gas atmosphere and in a state where moisture and the like are removed. The contact temperature may be a relatively low temperature range around room temperature when the mixture is simply brought into contact with stirring and mixed, or dispersed or suspended for modification, but the product is allowed to react after contact. When obtaining, the temperature range of 40-130 degreeC is preferable. If the temperature during the reaction is less than 40 ° C., the reaction does not proceed sufficiently, resulting in insufficient performance of the prepared solid catalyst component, and if it exceeds 130 ° C., evaporation of the solvent used becomes remarkable. Therefore, it becomes difficult to control the reaction. The reaction time is 1 minute or longer, preferably 10 minutes or longer, more preferably 30 minutes or longer.

Below, the preparation method of the solid catalyst component (A) for olefin polymerization is illustrated.
(1) Magnesium chloride (a) is dissolved in tetraalkoxytitanium and then contacted with polysiloxane to obtain a solid product. The solid product and titanium tetrachloride (b) are reacted, and then component (c) To prepare a solid catalyst component (A) for olefin polymerization by catalytic reaction. In this case, the solid catalyst component (A) for olefin polymerization can be preliminarily polymerized with an organoaluminum compound, an organosilicon compound and an olefin.

  (2) Anhydrous magnesium chloride (a) and 2-ethylhexyl alcohol are reacted to form a homogeneous solution, and then the homogeneous solution is contacted with phthalic anhydride, and then this solution is mixed with titanium tetrachloride (b) and the component (c ) Is contacted to obtain a solid product, and titanium tetrachloride (b) is further contacted with the solid product to prepare a solid catalyst component (A) for olefin polymerization.

  (3) An organomagnesium compound (a) is synthesized by reacting magnesium metal, butyl chloride and dibutyl ether, and the organomagnesium compound is contacted with tetrabutoxytitanium and tetraethoxytitanium to obtain a solid product. A method of preparing a solid catalyst component (A) for olefin polymerization by contacting the solid product with component (c), dibutyl ether and titanium tetrachloride (b). At this time, the solid catalyst component (A) for olefin polymerization can also be prepared by preliminarily polymerizing the solid component with an organoaluminum compound, an organosilicon compound and an olefin.

(4) An organomagnesium compound (a) such as dibutylmagnesium and an organoaluminum compound are contact-reacted with an alcohol such as butanol or 2-ethylhexyl alcohol in the presence of a hydrocarbon compound solvent to obtain a homogeneous solution. For example, a silicon compound such as SiCl ₄ , HSiCl ₃ , polysiloxane or the like is contacted to obtain a solid product, and then in the presence of an aromatic hydrocarbon compound solvent, the solid product is mixed with titanium tetrachloride (b) and components ( A method of obtaining a solid catalyst component (A) for polymerization of olefins by contacting c) with titanium tetrachloride (b) after contact reaction.

  (5) Magnesium chloride (a), tetraalkoxytitanium and aliphatic alcohol are contact-reacted in the presence of an aliphatic hydrocarbon compound to form a homogeneous solution, and after adding titanium tetrachloride (b) to the solution, the temperature is increased. The solid product is precipitated, the component (c) is brought into contact with the solid product, and further reacted with titanium tetrachloride (b) to obtain the solid catalyst component (A) for olefin polymerization.

  (6) Metal magnesium powder, alkyl monohalogen compound and iodine are contact-reacted, and then tetraalkoxytitanium, acid halide and aliphatic alcohol are contact-reacted in the presence of an aliphatic hydrocarbon compound to obtain a homogeneous solution (a ), And after adding titanium tetrachloride (b) to the solution, the temperature is raised to precipitate a solid product, which is brought into contact with component (c) and further reacted with titanium tetrachloride (b). And preparing a solid catalyst component (A) for olefin polymerization.

  (7) After diethoxymagnesium (a) is suspended in an alkylbenzene or halogenated hydrocarbon compound solvent, it is brought into contact with titanium tetrachloride (b), and then heated to contact with component (c) to form a solid. A method for preparing a solid catalyst component (A) for olefin polymerization by obtaining a product, washing the solid product with alkylbenzene, and then again contacting with titanium tetrachloride (b) in the presence of alkylbenzene. In this case, the solid component can be heat-treated in the presence or absence of a hydrocarbon compound solvent to obtain a solid catalyst component (A) for olefin polymerization.

  (8) After diethoxymagnesium (a) is suspended in alkylbenzene, it is contacted with titanium tetrachloride (b) and component (c) to obtain a solid product, and the solid product is washed with alkylbenzene. Then, the method of making it contact with titanium tetrachloride (b) again in presence of alkylbenzene and obtaining the solid catalyst component (A) for olefin polymerization. At this time, the solid component and titanium tetrachloride (b) can be contacted twice or more to obtain the solid catalyst component (A) for olefin polymerization.

(9) Grinding obtained by co-grinding a silicon compound represented by diethoxymagnesium (a), calcium chloride and Si (OR ¹⁵ ) ₄ (wherein R ¹⁵ represents an alkyl group or an aryl group) A solid catalyst for olefin polymerization is prepared by suspending a solid substance in an aromatic hydrocarbon compound, then contacting it with titanium tetrachloride (b) and component (c), and then further contacting titanium tetrachloride (b). A method for preparing component (A).

  (10) Diethoxymagnesium (a) and component (c) are suspended in alkylbenzene, the suspension is added to titanium tetrachloride (b) and reacted to obtain a solid product. A method of obtaining a solid catalyst component (A) for polymerizing olefins by washing titanium tetrachloride (b) again in the presence of alkylbenzene after washing the product with alkylbenzene.

  (11) Olefin polymerization by contacting aliphatic magnesium such as calcium halide and magnesium stearate with titanium tetrachloride (b) and component (c), and then further contacting with titanium tetrachloride (b). A method for preparing a solid catalyst component (A).

  (12) After diethoxymagnesium (a) is suspended in an alkylbenzene or halogenated hydrocarbon compound solvent, it is brought into contact with titanium tetrachloride (b), and then heated to cause contact reaction with component (c). A method of preparing a solid catalyst component (A) for olefin polymerization by obtaining a solid product, washing the solid product with alkylbenzene, and then contacting with titanium tetrachloride (b) again in the presence of alkylbenzene. The method for preparing the solid catalyst component (A) for olefin polymerization by contacting aluminum chloride in any stage of the suspension / contact and the contact reaction.

  (13) Diethoxymagnesium (a), 2-ethylhexyl alcohol and carbon dioxide are contact-reacted in the presence of toluene to obtain a homogeneous solution, and this solution is contacted with titanium tetrachloride (b) and component (c). To obtain a solid product, which is further dissolved in tetrahydrofuran, and then further solid product is precipitated. The solid product is reacted with titanium tetrachloride (b), and optionally with titanium tetrachloride (b ) Is repeated to prepare a solid catalyst component (A) for olefin polymerization. In this case, for example, a silicon compound such as tetrabutoxysilane may be used in any of the contact, contact reaction, and dissolution steps.

  (14) Magnesium chloride (a), an organic epoxy compound and a phosphoric acid compound are suspended in a hydrocarbon compound solvent such as toluene, and then heated to obtain a homogeneous solution. To this solution, phthalic anhydride and titanium tetrachloride are added. (B) is contact-reacted to obtain a solid product, the solid product is contacted with component (c) and reacted, and the resulting reaction product is washed with alkylbenzene, and then again in the presence of alkylbenzene. A method for obtaining a solid catalyst component (A) for olefin polymerization by contacting titanium chloride (b).

  (15) The dialkoxymagnesium (a), the titanium compound and the component (c) are contact-reacted in the presence of toluene, the resulting reaction product is contacted with a silicon compound such as polysiloxane, and further titanium tetrachloride ( A method of obtaining a solid catalyst component (A) for polymerization of olefins by bringing b) into contact and then bringing a metal salt of an organic acid into contact and then bringing titanium tetrachloride (b) into contact again.

  (16) The dialkoxymagnesium (a) and the component (c) are suspended in an aromatic hydrocarbon solvent, heated to contact with silicon tetrachloride, and then contacted with titanium tetrachloride to obtain a solid product. The solid product is washed with an aromatic hydrocarbon solution, and then contacted with titanium tetrachloride again in the presence of the aromatic hydrocarbon to prepare a solid catalyst component (A) for olefin polymerization. In this case, the solid component may be heat-treated in the presence or absence of a hydrocarbon solvent to obtain a solid catalyst component (A) for olefin polymerization.

  As a preferred method for preparing the solid catalyst component (A) for olefin polymerization of the present invention, the component (a) is suspended in a liquid aromatic hydrocarbon compound such as toluene at room temperature, and then the component (b). Mentioning a method for preparing a solid catalyst component (A) for olefin polymerization by contacting the component (c) after contacting the component, or contacting the component (b) after contacting the component (c) Can do.

  Furthermore, the following methods are mentioned as a more preferable preparation method of the solid catalyst component (A) for olefin polymerization used in the present invention. For example, a suspension is formed by suspending dialkoxymagnesium in a liquid aromatic hydrocarbon compound at room temperature, and then titanium tetrachloride is added to this suspension at -20 to 100 ° C, preferably -10 to 70. It contacts at 0 degreeC, More preferably, 0-30 degreeC, It is made to react at 40-130 degreeC, More preferably, it is 70-120 degreeC. At this time, before or after the titanium tetrachloride is brought into contact with the above suspension, the component (c) is brought into contact at −20 to 130 ° C. to obtain a solid reaction product. After washing this solid reaction product with a liquid aromatic hydrocarbon compound at room temperature, titanium tetrachloride is contacted again at 40 to 130 ° C., more preferably at 70 to 120 ° C. in the presence of the aromatic hydrocarbon compound. The reaction is followed by washing with a liquid hydrocarbon compound at room temperature to obtain a solid catalyst component (A) for olefin polymerization.

  The amount of each compound used varies depending on the preparation method and cannot be defined unconditionally. For example, component (b) is 0.5 to 100 mol, preferably 0.5 to 50 mol, per mol of component (a), More preferably, it is 1-10 mol, and a component (c) is 0.01-10 mol, Preferably it is 0.01-1 mol, More preferably, it is 0.02-0.6 mol.

  In the solid catalyst component (A) for olefin polymerization used in the present invention, when the solid catalyst component is brought into contact with triethylaluminum, the extraction amount of the electron donor is mainly 20 to 60 mol%. What is necessary is just to adjust the kind and content of an electron donor, and although it was illustrated as what was illustrated especially as an electron donor and preferable, it can be adjusted more easily if content is selected.

  The organoaluminum compound (B) (hereinafter sometimes referred to as “component (B)”) used in forming the olefin polymerization catalyst of the present invention is a compound represented by the above general formula (1). Can be used. Specific examples of such an organoaluminum compound (B) include triethylaluminum, diethylaluminum chloride, triisobutylaluminum, diethylaluminum bromide, and diethylaluminum hydride, and one or more can be used. Triethylaluminum and triisobutylaluminum are preferable.

  The external electron donating compound (C) (hereinafter sometimes referred to as “component (C)”) used in forming the olefin polymerization catalyst of the present invention is used for the preparation of the solid catalyst component described above. The same electron donors can be used, among which ethers such as 9,9-bis (methoxymethyl) fluorene, 2-isopropyl-2-isopentyl-1,3-dimethoxypropane, methyl benzoate and Esters such as ethyl benzoate and organosilicon compounds.

As said organosilicon compound, following General formula (2);
R ² _q Si (OR ³ ) _4-q (2)
(In the formula, R ² represents an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group, a phenyl group, a vinyl group, an allyl group, or an aralkyl group, and may be the same or different, and R ³ represents 1 to 4 carbon atoms. And an alkyl group, a cycloalkyl group, a phenyl group, a vinyl group, an allyl group, and an aralkyl group, which may be the same or different, and q is an integer of 0 ≦ q ≦ 3). It is done. Examples of such an organosilicon compound include phenylalkoxysilane, alkylalkoxysilane, phenylalkylalkoxysilane, cycloalkylalkoxysilane, and cycloalkylalkylalkoxysilane.

  Specific examples of the organosilicon compounds include trimethylmethoxysilane, trimethylethoxysilane, tripropylmethoxysilane, tripropylethoxysilane, tributylmethoxysilane, triisobutylmethoxysilane, tri-tert-butylmethoxysilane, tributylethoxysilane. , Tricyclohexylmethoxysilane, tricyclohexylethoxysilane, cyclohexyldimethylmethoxysilane, cyclohexyldiethylmethoxysilane, cyclohexyldiethylethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, dipropyldimethoxysilane, diisopropyldimethoxysilane, dipropyldiethoxysilane, Diisopropyldiethoxysilane, dibutyldimethoxysilane, diisobutyldi Toxisilane, di-tert-butyldimethoxysilane, dibutyldiethoxysilane, butylmethyldimethoxysilane, bis (2-ethylhexyl) dimethoxysilane, bis (2-ethylhexyl) diethoxysilane, dicyclopentyldimethoxysilane, dicyclopentyldiethoxysilane, Dicyclohexyldimethoxysilane, dicyclohexyldiethoxysilane, bis (3-methylcyclohexyl) dimethoxysilane, bis (4-methylcyclohexyl) dimethoxysilane, bis (3,5-dimethylcyclohexyl) dimethoxysilane, cyclohexylcyclopentyldimethoxysilane, cyclohexylcyclopentyldiethoxy Silane, cyclohexylcyclopentyl dipropoxysilane, 3-methylcyclohexylcyclopenty Dimethoxysilane, 4-methylcyclohexylcyclopentyldimethoxysilane, 3,5-dimethylcyclohexylcyclopentyldimethoxysilane, 3-methylcyclohexylcyclohexyldimethoxysilane, 4-methylcyclohexylcyclohexyldimethoxysilane, 3,5-dimethylcyclohexylcyclohexyldimethoxysilane, cyclopentylmethyldimethoxy Silane, cyclopentylmethyldiethoxysilane, cyclopentylethyldiethoxysilane, cyclopentyl (isopropyl) dimethoxysilane, cyclopentyl (isobutyl) dimethoxysilane, cyclohexylmethyldimethoxysilane, cyclohexylmethyldiethoxysilane, cyclohexylethyldimethoxysilane, cyclohexylethyldiethoxysilane , Cyclohexyl (propyl) dimethoxysilane, cyclohexyl (isopropyl) dimethoxysilane, cyclohexyl (propyl) diethoxysilane, cyclohexyl (isobutyl) dimethoxysilane, cyclohexyl (butyl) diethoxysilane, cyclohexyl (pentyl) dimethoxysilane, cyclohexyl (pentyl) Diethoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, phenylmethyldimethoxysilane, phenylmethyldiethoxysilane, phenylethyldimethoxysilane, phenylethyldiethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, Ethyltriethoxysilane, propyltrimethoxysilane, isopropyltrimethoxysilane, Pyrtriethoxysilane, isopropyltriethoxysilane, butyltrimethoxysilane, isobutyltrimethoxysilane, tert-butyltrimethoxysilane, butyltriethoxysilane, 2-ethylhexyltrimethoxysilane, 2-ethylhexyltriethoxysilane, cyclopentyltrimethoxysilane , Cyclopentyltriethoxysilane, cyclohexyltrimethoxysilane, cyclohexyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, tetrabutoxy A silane etc. can be mentioned. Among the above, dipropyldimethoxysilane, diisopropyldimethoxysilane, dibutyldimethoxysilane, diisobutyldimethoxysilane, di-tert-butyldimethoxysilane, dibutyldiethoxysilane, tert-butyltrimethoxysilane, dicyclohexyldimethoxysilane, dicyclohexyldiethoxysilane, Cyclohexylmethyldimethoxysilane, cyclohexylmethyldiethoxysilane, cyclohexylethyldimethoxysilane, cyclohexylethyldiethoxysilane, dicyclopentyldimethoxysilane, dicyclopentyldiethoxysilane, cyclopentylmethyldimethoxysilane, cyclopentylmethyldiethoxysilane, cyclopentylethyldiethoxysilane, Cyclohexylcyclopentyl dimeth Sisilane, cyclohexylcyclopentyldiethoxysilane, 3-methylcyclohexylcyclopentyldimethoxysilane, 4-methylcyclohexylcyclopentyldimethoxysilane, 3,5-dimethylcyclohexylcyclopentyldimethoxysilane are preferably used, and the organosilicon compound (C) is one or two. It can be used in combination of more than one species.

  Next, the catalyst for olefin polymerization of the present invention contains the above-described solid catalyst component (A), component (B), and component (C) for olefin polymerization, and polymerization of olefins in the presence of the catalyst. Copolymerization is performed. Examples of olefins include ethylene, propylene, 1-butene, 1-pentene, 4-methyl-1-pentene, and vinylcyclohexane. These olefins can be used alone or in combination of two or more. In particular, ethylene, propylene and 1-butene are preferably used. Particularly preferred is propylene. In the case of polymerization of propylene, copolymerization with other olefins can also be performed. Examples of olefins to be copolymerized include ethylene, 1-butene, 1-pentene, 4-methyl-1-pentene, vinylcyclohexane, and the like, and these olefins can be used alone or in combination of two or more. In particular, ethylene and 1-butene are preferably used.

  The amount ratio of each component is arbitrary as long as it does not affect the effect of the present invention, and is not particularly limited. However, the component (B) is usually in the solid catalyst component (A) for olefin polymerization. 1 to 2000 mol, preferably 50 to 1000 mol, per 1 mol of titanium atom. Component (C) is used in an amount of 0.002 to 10 mol, preferably 0.01 to 2 mol, particularly preferably 0.01 to 0.5 mol, per mol of component (B).

  The order of contact of each component is arbitrary, but the organoaluminum compound (B) is first charged into the polymerization system, then the organosilicon compound (C) is contacted, and the solid catalyst component (A) for olefin polymerization is further added. It is desirable to contact.

  The polymerization method in the present invention can be carried out in the presence or absence of an organic solvent, and the olefin monomer such as propylene can be used in any state of gas and liquid. The polymerization temperature is 200 ° C. or lower, preferably 100 ° C. or lower, and the polymerization pressure is 10 MPa or lower, preferably 5 MPa or lower. Moreover, any of a continuous polymerization method and a batch type polymerization method is possible. Furthermore, the polymerization reaction may be performed in one stage or in two or more stages.

  Furthermore, in polymerizing olefins using the catalyst containing the solid catalyst component for olefin polymerization (A), component (B), and component (C) in the present invention (also referred to as main polymerization), catalytic activity and steric properties are considered. In order to further improve the regularity and the particle properties of the resulting polymer, it is desirable to perform prepolymerization prior to the main polymerization. In the prepolymerization, the same olefins as in the main polymerization or monomers such as styrene can be used.

  In carrying out the prepolymerization, the order of contacting the respective components and monomers is arbitrary, but preferably, the component (B) is first charged into the prepolymerization system set to an inert gas atmosphere or an olefin gas atmosphere, and then the olefin. After contacting the solid catalyst component (A) for homopolymerization, an olefin such as propylene and / or one or more other olefins are contacted. When the prepolymerization is performed by combining the component (C), the component (B) is first charged into the prepolymerization system set to an inert gas atmosphere or an olefin gas atmosphere, and then the component (C) is contacted. A method of contacting an olefin such as propylene and / or one or other two or more olefins after contacting the solid catalyst component (A) for olefin polymerization is desirable.

  When olefins are polymerized in the presence of an olefin polymerization catalyst formed according to the present invention, the olefin weight is maintained in a high yield while maintaining high stereoregularity compared to the case of using a conventional catalyst. A coalescence can be obtained and it shows excellent activity persistence.

Hereinafter, examples of the present invention will be described in detail while comparing with comparative examples. Examples 1, 3 and 4 are reference examples in the present invention.

[Preparation of solid catalyst component (A)]
A 500 ml round bottom flask, which was sufficiently replaced with nitrogen gas and equipped with a stirrer, was charged with 10 grams of diethoxymagnesium and 80 ml of toluene to form a suspended state. Next, 20 ml of titanium tetrachloride was added to the suspension, and the temperature was raised. When the temperature reached 80 ° C, 3.6 g of diethyl diisobutylmalonate was added, and the temperature was further raised to 110 ° C. Thereafter, the reaction was carried out with stirring for 1 hour while maintaining a temperature of 110 ° C. After completion of the reaction, the mixture was washed 3 times with 100 ml of toluene at 90 ° C., 20 ml of titanium tetrachloride and 80 ml of toluene were newly added, the temperature was raised to 110 ° C., and the reaction was carried out with stirring for 1 hour. After completion of the reaction, the solid catalyst component was obtained by washing 7 times with 100 ml of heptane at 40 ° C. The solid liquid in the solid catalyst component was separated, and the titanium content in the solid content was measured. The titanium content is shown in Table 1.

[Measurement of electron donor content in solid catalyst component]
A magnetic stirring bar and 3 g of a solid catalyst component were placed in a flask with an internal volume of 200 ml that was completely replaced with nitrogen gas, and 10 ml of 4N hydrochloric acid and 20 ml of toluene were added thereto to obtain a suspension. After the suspension was shaken well, the toluene solution portion was separated and washed 3 times with 10 ml of distilled water. The electron donor contained in the obtained toluene moiety was quantified using gas chromatography.

[Extraction test of electron donor with triethylaluminum]
A magnetic stir bar, 100 ml of heptane, 3 grams of solid catalyst, and 6.4 grams of triethylaluminum were added to a flask with an internal volume of 200 milliliters completely replaced with nitrogen gas and stirred at room temperature. After 30 minutes, the solid and liquid were separated using a glass filter, and the obtained solid was washed with 100 ml of heptane three times and dried under vacuum. The content of the electron donor in the solid was measured according to the method for measuring the content of the electron donor in the solid catalyst component. The extraction rate was determined from the ratio between the remaining amount after 30 minutes and the content before the extraction test. The extraction rate of the electron donor is shown in Table 1.

[Formation and polymerization of polymerization catalyst]
Into an autoclave with a stirrer having an internal volume of 2.0 liters completely replaced with nitrogen gas, 1.32 mmol of triethylaluminum, 0.13 mmol of cyclohexylmethyldimethoxysilane and 0.0026 mmol of the solid catalyst component as titanium atoms were charged, A polymerization catalyst was formed. Thereafter, 2.0 liters of hydrogen gas and 1.4 liters of liquefied propylene were charged, preliminarily polymerized at 20 ° C. for 5 minutes, and then heated up, and polymerization reaction was performed at 70 ° C. for 1 hour and 2 hours. Table 2 shows the polymerization activity per gram of the solid catalyst component, the ratio of boiling n-heptane insoluble matter (HI) in the produced polymer, and the melt index value (MI) of the produced polymer (a).

The polymerization activity per solid catalyst component used here was calculated by the following equation.
Polymerization activity = produced polymer (g) / solid catalyst component (g)
Moreover, the ratio (HI) of the insoluble portion of boiling heptane in the produced polymer was defined as the proportion (% by weight) of the polymer insoluble in heptane when the produced polymer was extracted with boiling heptane for 6 hours.
Furthermore, the melt index value (MI) of the produced polymer (a) was measured according to ASTM D 1238 and JIS K 7210.

  A solid component was prepared in the same manner as in Example 1 except that 2.8 grams of diethyl 2,3-diisopropyl succinate was used instead of 3.6 grams of diethyl diisobutylmalonate, and a polymerization catalyst was formed and polymerized. It was. Table 1 shows the titanium content, the molar ratio of the electron donor to the titanium content, and the electron donor extraction rate, and Table 2 shows the polymerization results.

  A solid component was prepared in the same manner as in Example 1 except that 2.6 g of diethyl 2,3-diethyl maleate was used instead of 3.6 g of diethyl diisobutylmalonate, and a polymerization catalyst was formed and polymerized. It was. Table 1 shows the titanium content, the molar ratio of the electron donor to the titanium content, and the electron donor extraction rate, and Table 2 shows the polymerization results.

  A solid component was prepared in the same manner as in Example 1 except that 3.2 g of diethyl methylcyclopentylmalonate was used instead of 3.6 g of diethyl diisobutylmalonate, and a polymerization catalyst was formed and polymerized. Table 1 shows the titanium content, the molar ratio of the electron donor to the titanium content, and the electron donor extraction rate, and Table 2 shows the polymerization results.

Comparative Example 1
A solid component was prepared in the same manner as in Example 1 except that 2.1 grams of diethyl malonate was used instead of 3.6 grams of diethyl diisobutylmalonate, and a polymerization catalyst was formed and polymerized. Table 1 shows the titanium content, the molar ratio of the electron donor to the titanium content, and the electron donor extraction rate, and Table 2 shows the polymerization results.

Comparative Example 2
A solid component was prepared in the same manner as in Example 1 except that 2.9 g of dibutyl phthalate was used instead of 3.6 g of diethyl diisobutylmalonate, and a polymerization catalyst was formed and polymerized. Table 1 shows the titanium content, the molar ratio of the electron donor to the titanium content, and the electron donor extraction rate, and Table 2 shows the polymerization results.

Comparative Example 3
A solid component was prepared in the same manner as in Example 1 except that 2.3 g of diethyl 2-methyl-3-ethylsuccinate was used instead of 3.6 g of diethyl diisobutylmalonate, and the polymerization catalyst was further formed and polymerized. went. Table 1 shows the titanium content, the molar ratio of the electron donor to the titanium content, and the electron donor extraction rate, and Table 2 shows the polymerization results.

  From the results shown in Table 1, by polymerizing olefins using the solid catalyst component and catalyst of the present invention, an olefin polymer having higher stereoregularity can be obtained in a high yield, and the activity sustainability is excellent. I understand that.

It is a flowchart figure which shows the process of preparing the polymerization catalyst of this invention.

Claims (12)

Dialkoxymagnesium (a) is suspended in an aromatic hydrocarbon compound, then titanium tetrachloride (b) and diethyl 2,3-diethyl succinate, diethyl 2,3-dipropyl succinate, 2,3- Diethyl succinate, diethyl 2,3-dibutyl succinate, diethyl 2,3-diisobutyl succinate, diethyl 2,3-di-tert-butyl succinate, dibutyl 2,3-diethyl succinate, 2,3-dipropyl An electron donor selected from dibutyl succinate, dibutyl 2,3-diisopropyl succinate, dibutyl 2,3-dibutyl succinate, dibutyl 2,3-diisobutyl succinate and dibutyl 2,3-di-tert-butyl succinate (c ) a solid catalyst component obtained by contacting a titanium content of the solid catalyst component .0 is a weight% or more, electron donor (c) and the molar ratio of titanium less than 1.1, olefin polymerization solid catalyst component, wherein 1.5 or less.   2. The solid catalyst component for olefin polymerization according to claim 1, wherein the solid catalyst component is obtained by contacting titanium tetrachloride after contacting (b) and (c). The solid catalyst component for olefin polymerization according to claim 1 or 2, wherein the aromatic hydrocarbon compound is alkylbenzene. Dialkoxymagnesium (a) is suspended in an aromatic hydrocarbon compound, and then titanium tetrachloride (b) is added in an amount of 0.5 to 100 mol and 2,3-diethyl per mol of dialkoxymagnesium (a). Diethyl succinate, diethyl 2,3-dipropyl succinate, diethyl 2,3-diisopropyl succinate, diethyl 2,3-dibutyl succinate, diethyl 2,3-diisobutyl succinate, 2,3-di-tert-butyl succinate Diethyl 2,3-diethyl succinate, dibutyl 2,3-dipropyl succinate, dibutyl 2,3-diisopropyl succinate, dibutyl 2,3-dibutyl succinate, dibutyl 2,3-diisobutyl succinate and 2 , the electron donor is selected from 3-di -tert- butylsuccinic acid dibutyl (c) Jiarukokishima The titanium content in the solid catalyst component is 2.0% by weight or more, and the molar ratio of the electron donor (c) to titanium is 1.1% per 1 mole of nesium (a). As mentioned above, the manufacturing method of the solid catalyst component for olefin polymerization characterized by obtaining 1.5 or less solid catalyst components . The method for producing a solid catalyst component for olefin polymerization according to claim 4, wherein after contacting (b) and (c), titanium tetrachloride is further contacted. 5. The method for producing a solid catalyst component for olefin polymerization according to claim 4, wherein after the (b) and (c) are contacted, the obtained solid reaction product is washed with a hydrocarbon compound. 6. The solid for olefin polymerization according to claim 5 , wherein said solid reaction product is washed with a hydrocarbon compound after contacting said (b) and (c) and contacting titanium tetrachloride. A method for producing a catalyst component. The method for producing a solid catalyst component for olefin polymerization according to claim 4, wherein titanium tetrachloride (b) is brought into contact with the suspension at a temperature of -20 to 100 ° C and reacted at 40 to 130 ° C. . The method for producing a solid catalyst component for olefin polymerization according to claim 5, wherein the contact temperature of titanium tetrachloride after contacting the electron donor (c) is 40 to 130 ° C. The method for producing a solid catalyst component for olefin polymerization according to any one of claims 4 to 9 , wherein the aromatic hydrocarbon compound is alkylbenzene. (A) Solid catalyst component for olefin polymerization according to any one of claims 1 to 3 , (B) the following general formula (1); R ¹ _p AlQ _3-p (1)
(Wherein R ¹ represents an alkyl group having 1 to 4 carbon atoms, Q represents a hydrogen atom or a halogen atom, and p is an integer of 0 <p ≦ 3), and (C) An olefin polymerization catalyst comprising an external electron donating compound. The (C) external electron donating compound is represented by the following general formula (2):
R ² _q Si (OR ³ ) _4-q (2)
(In the formula, R ² represents an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group, a phenyl group, a vinyl group, an allyl group, or an aralkyl group, and may be the same or different. R ³ has 1 to 4 carbon atoms. An alkyl group, a cycloalkyl group, a phenyl group, a vinyl group, an allyl group or an aralkyl group, which may be the same or different, and q is an integer of 0 ≦ q ≦ 3. The olefin polymerization catalyst according to claim 11 , wherein:

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