JP2006199738A - Solid catalyst component and catalyst for polymerizing olefins - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a solid catalyst component and a catalyst for polymerizing olefins which can obtain olefin polymers with a high yield and, in particular, can obtain a propylene polymer having a high hydrogen response and a wide molecular weight distribution while keeping a high stereoregularity and a high yield. <P>SOLUTION: The solid catalyst component and the catalyst for polymerizing olefins are prepared by bringing a magnesium compound, titanium tetrachloride and a succinic acid diester derivative into contact with one another in an aromatic hydrocarbon compound. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a solid catalyst component and a catalyst for olefin polymerization that can obtain an olefin polymer having a high hydrogen response while maintaining a high degree of stereoregularity and high yield, and having a broad molecular weight distribution.

  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, it has been pointed out that the polymer obtained by using the catalyst as described above has a molecular weight distribution that is not sufficiently wide when producing a biaxially oriented polypropylene film (BOPP). Patent Document 4 (Japanese Patent Application Laid-Open No. 2001-240634) discloses a method of using an organic cyclic aminosilane compound as an electron donor used during polymerization. Although this method can broaden the molecular weight distribution, the activity is low and improvement is required. Patent Document 5 (Japanese Patent Publication No. 2002-542347) discloses that the molecular weight distribution can be widened while maintaining the activity by using a succinic acid diester as the solid catalyst component. However, this method does not have sufficient stereoregularity, and further improvement is required.
JP-A-57-63310 (Claims) JP-A-57-63311 (Claims) JP-A-1-6006 (Claims) JP 2001-240634 A (Claims) JP 2002-542347 A (Claims, paragraph 0024)

  That is, an object of the present invention is to provide a solid catalyst component and a catalyst for olefin polymerization that exhibit a high hydrogen response while maintaining a high stereoregularity and a high yield of a propylene polymer, and further have a broad molecular weight distribution. It is in.

  In such a situation, the present inventor made extensive studies to solve the problems remaining in the prior art, and as a result, the magnesium compound, titanium compound and succinic diester derivative were brought into contact with each other in an aromatic hydrocarbon compound. Propylene polymer that exhibits high activity when subjected to polymerization of olefins, and exhibits high hydrogen response while maintaining high stereoregularity and high yield, particularly when subjected to propylene polymerization Furthermore, the present inventors have found that this polymer has a broad molecular weight distribution, and have completed the present invention.

  That is, the present invention is prepared by contacting a magnesium compound (a), a titanium compound (b), and a succinic diester derivative (c) represented by the following chemical formula (1) in an aromatic hydrocarbon compound (d). A solid catalyst component for olefin polymerization is provided.

(Wherein R ^{3 to} R ⁶ represent a hydrogen atom, a halogen atom or an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group, an aryl group, a vinyl group, an allyl group, an aralkyl group, and may be the same or different; At least one is a substituent other than a hydrogen atom, and R ¹ and R ^{2 each} represent an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group, an aryl group, a vinyl group, an allyl group, or an aralkyl group, May be different.)

The present invention also provides: (A) the solid catalyst component for olefin polymerization, (B) the following general formula (1); R ⁷ _p AlQ _3-p (1)
(Wherein R ⁷ 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) It provides an olefin polymerization catalyst characterized by containing an electron donating compound.

  The olefin polymerization catalyst of the present invention can provide an olefin polymer having a high hydrogen response while maintaining a high stereoregularity in a high yield and a broad molecular weight distribution. Therefore, it is useful in the production of a copolymer of olefins having high functionality.

  Magnesium compounds (a) (hereinafter sometimes simply referred to as “component (a)”) used in the preparation of the solid catalyst component (A) for olefin polymerization of the present invention include magnesium dihalide, dialkylmagnesium, and halogenated compounds. Examples thereof include alkyl magnesium, dialkoxy magnesium, diaryloxy magnesium, halogenated alkoxy magnesium, and fatty acid magnesium. Among these magnesium compounds, magnesium dihalide, a mixture of magnesium dihalide and dialkoxymagnesium, and dialkoxymagnesium are preferable, and dialkoxymagnesium is particularly preferable.

The dialkoxymagnesium or diaryloxymagnesium has the general formula Mg (OR ¹⁰ ) (OR ¹¹ ) (wherein R ¹⁰ and R ¹¹ represent an alkyl group or aryl group having 1 to 10 carbon atoms, and may be the same or different. And more specifically, dimethoxymagnesium, diethoxymagnesium, dipropoxymagnesium, dibutoxymagnesium, diphenoxymagnesium, ethoxymethoxymagnesium, ethoxypropoxymagnesium, butoxyethoxymagnesium and the like. Can be 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 ¹² ) D ² (wherein R ¹² 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.

  Of dialkoxymagnesium suitable as the magnesium compound (a), diethoxymagnesium and dipropoxymagnesium are particularly preferred. 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.

A titanium compound is used for preparation of the solid catalyst component (A) for olefin polymerization in the present invention. As the titanium compound, titanium halide or alkoxy titanium halide is used. Examples of titanium halides include titanium tetrachloride, titanium tetrabromide, and titanium tetraiodide. Of these, titanium tetrachloride is preferred. Titanium tetrachloride (hereinafter sometimes simply referred to as “component (b)”) can be used alone or in combination with an alkoxy titanium halide other than titanium tetrachloride. The alkoxytitanium halide has the general formula Ti (OR ¹³ ) _n Cl _4-n (wherein R ¹³ represents an alkyl group having 1 to 4 carbon atoms, and n is an integer of 1 ≦ n ≦ 3). The alkoxy titanium chloride represented is illustrated. Moreover, said alkoxy titanium chloride 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.

The succinic acid diester derivative (hereinafter sometimes simply referred to as “component (c)”) used in the preparation of the solid catalyst component (A) for olefin polymerization in the present invention is a compound represented by the above chemical formula (1). It is. R ^{3 to} R ⁶ represent a hydrogen atom, a halogen atom or an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group, an aryl group, a vinyl group, an allyl group, or an aralkyl group, and may be the same or different, and at least one of them is A substituent other than a hydrogen atom. When all of R ^{3 to} R ⁵ are hydrogen atoms, R ⁶ is preferably an alkyl group having 3 to 12 carbon atoms, a cycloalkyl group, an aryl group, a vinyl group, an allyl group, or an aralkyl group. When R ^{3 to} R ⁵ are all hydrogen atoms and R ⁶ is 1 or 2 carbon atoms, R ¹ and R ² are alkyl groups, cycloalkyl groups, aryl groups, vinyl groups having 3 to 8 carbon atoms, An allyl group and an aralkyl group are preferred. R ¹ and R ^2, which are ester residues of two carbonyls, represent an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group, an aryl group, a vinyl group, an allyl group, and an aralkyl group, which may be the same or different. Good. When at least one group of R ^{3 to} R ⁶ is a halogen atom, the melt index of the olefin polymer obtained using the prepared solid catalyst component for olefin polymerization is remarkably improved. Two groups of ^{3 to} R ⁶ are two halogen atoms, and it is particularly preferable for the same reason that the two halogen atoms are bonded to different carbon atoms. Among these succinic diester derivatives, alkyl succinic diester, cycloalkyl succinic diester, aryl succinic diester, vinyl succinic diester, allyl succinic diester, aralkyl succinic diester, dialkyl succinic diester, alkyl cycloalkyl succinic diester, alkyl Phenyl succinic acid diester, alkyl vinyl succinic acid diester, alkyl allyl succinic acid diester, alkyl aralkyl succinic acid diester, dicycloalkyl succinic acid diester, diaryl succinic acid diester, divinyl succinic acid diester, diallyl succinic acid diester, diaralkyl succinic acid diester , Trialkyl succinic acid diester, alkyl halogenated succinic acid diester, halogenated succinic acid Esters, dihalogenated succinic acid diester, dialkyl halogenated succinic acid diester, alkyl di halogenated succinic acid diester are preferable. Among these, alkyl succinic acid diesters, dialkyl succinic acid diesters, cycloalkyl succinic acid diesters, halogenated succinic acid diesters, dihalogenated succinic acid diesters, alkyl halogenated succinic acid diesters are particularly preferable, and dialkyl succinic acid diesters and dihalogens are more preferable. Succinic acid diester. In the case of an alkyl succinic acid diester, the alkyl group is preferably a linear or branched alkyl group having 3 to 10 carbon atoms, particularly preferably an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, or a tert-butyl group. It is a group. In the case of a cycloalkyl succinic acid diester, the cycloalkyl group is preferably a cyclopentyl group or a cyclohexyl group. In the case of a dialkyl succinic acid diester, the alkyl group is preferably a linear or branched one having 1 to 10 carbon atoms, particularly preferably an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, A tert-butyl group. In the case of a cycloalkyl succinic acid diester, the cycloalkyl group is preferably a cyclopentyl group or a cyclohexyl group. In addition, R ¹ and R ² which are ester residues in the chemical formula (1) are preferably alkyl groups, and particularly preferably linear or branched alkyl groups having 1 to 4 carbon atoms.

  Specific examples of alkyl succinic acid diesters include diethyl propyl succinate, diethyl isopropyl succinate, diethyl butyl succinate, diethyl isobutyl succinate, diethyl sec-butyl succinate, diethyl tert-butyl succinate, diethyl pentyl succinate, neo-pentyl succinate. Diethyl propyl, propyl succinate dipropyl, isopropyl succinate dipropyl, butyl succinate dipropyl, isobutyl succinate dipropyl, sec-butyl succinate dipropyl, tert-butyl succinate dipropyl, pentyl succinate dipropyl, neo-pentyl succinate dipropyl, propyl succinate dibutyl , Dibutyl isopropyl succinate, dibutyl butyl succinate, dibutyl isobutyl succinate, dibutyl sec-butyl succinate Examples include dibutyl tert-butyl succinate, dibutyl pentyl succinate, and dibutyl neo-pentyl succinate. Dialkyl succinate diesters include diethyl 2,3-dimethyl succinate, diethyl 2,3-diethyl succinate, 2, 3 -Diethyl dipropyl succinate, diethyl 2,3-diisopropyl succinate, diethyl 2,3-dibutyl succinate, diethyl 2,3-diisobutyl succinate, diethyl 2,3-di-sec-butyl succinate, 2,3- Diethyl tert-butyl succinate, diethyl 2,3-dipentyl succinate, diethyl 2,3-di-neo-pentyl succinate, dipropyl 2,3-dimethyl succinate, dipropyl 2,3-diethyl succinate, 2, 3-dipropyl succinate dipropyl, 2,3-diisopropyl Dipropyl succinate, dipropyl 2,3-dibutyl succinate, dipropyl 2,3-diisobutyl succinate, dipropyl 2,3-di-sec-butyl succinate, dipropyl 2,3-di-tert-butyl succinate, 2,3- Dipropyl dipentyl succinate, dipropyl 2,3-di-neo-pentyl succinate, dibutyl 2,3-dimethyl succinate, dibutyl 2,3-diethyl succinate, dibutyl 2,3-dipropyl succinate, 2,3- Dibutyl diisopropyl succinate, dibutyl 2,3-dibutyl succinate, dibutyl 2,3-diisobutyl succinate, dibutyl 2,3-di-sec-butyl succinate, dibutyl 2,3-di-tert-butyl succinate, 2,3 -Dibutyl dipentyl succinate, dibutyl 2,3-di-neo-pentyl succinate, 2- Diethyl methyl-3-ethyl succinate, diethyl 2-methyl-3-propyl succinate, diethyl 2-methyl-3-isopropyl succinate, diethyl 2-methyl-3-butyl succinate, diethyl 2-methyl-3-isobutyl succinate 2-methyl-3-tert-butyl succinate, diethyl 2-methyl-3-pentyl succinate, diethyl 2-methyl-3-neo-pentyl succinate, dipropyl 2-methyl-3-ethyl succinate, 2-methyl Dipropyl-3-propyl succinate, dipropyl 2-methyl-3-isopropyl succinate, dipropyl 2-methyl-3-butyl succinate, dipropyl 2-methyl-3-isobutyl succinate, 2-methyl-3-tert-butyl succinic acid Dipropyl, 2-methyl-3-pentyl succinate dipropyl 2-methyl-3-neo-pentyl succinate dipropyl, 2-methyl-3-ethyl succinate dibutyl, 2-methyl-3-propyl succinate dibutyl, 2-methyl-3-isopropyl succinate dibutyl, 2-methyl-3 -Dibutyl butyl succinate, dibutyl 2-methyl-3-isobutyl succinate, dibutyl 2-methyl-3-tert-butyl succinate, dibutyl 2-methyl-3-pentyl succinate, 2-methyl-3-neo-pentyl succinic acid Dibutyl, diethyl 2-ethyl-3-propyl succinate, diethyl 2-ethyl-3-isopropyl succinate, diethyl 2-ethyl-3-butyl succinate, diethyl 2-ethyl-3-isobutyl succinate, 2-ethyl-3 -Diethyl tert-butyl succinate, die 2-ethyl-3-pentyl succinate , Diethyl 2-ethyl-3-neo-pentyl succinate, dipropyl 2-ethyl-3-propyl succinate, dipropyl 2-ethyl-3-isopropyl succinate, dipropyl 2-ethyl-3-butyl succinate, 2-ethyl -3-Isobutyl succinate dipropyl, 2-ethyl-3-tert-butyl succinate dipropyl, 2-ethyl-3-pentyl succinate dipropyl, 2-ethyl-3-neo-pentyl succinate dipropyl, 2-ethyl-3- Dibutyl propyl succinate, dibutyl 2-ethyl-3-isopropyl succinate, dibutyl 2-ethyl-3-butyl succinate, dibutyl 2-ethyl-3-isobutyl succinate, dibutyl 2-ethyl-3-tert-butyl succinate, 2 -Ethyl-3-pentylsuccinic acid dibutyl, 2-ethyl-3-ne o-pentyl succinate dibutyl and the like.

  Cycloalkyl succinic acid diesters include diethyl cyclopentyl succinate, diethyl cyclohexyl succinate, dipropyl cyclopentyl succinate, dipropyl cyclohexyl succinate, dibutyl cyclopentyl succinate, dibutyl cyclohexyl succinate, diethyl 2,3-dicyclopentyl succinate, 2, Diethyl 3-dicyclohexyl succinate, dipropyl 2,3-dicyclopentyl succinate, dipropyl 2,3-dicyclohexyl succinate, dibutyl 2,3-dicyclopentyl succinate, dibutyl 2,3-dicyclohexyl succinate, 2-methyl-3 -Diethyl cyclopentyl succinate, diethyl 2-methyl-3-cyclohexyl succinate, dipropyl 2-methyl-3-cyclopentyl succinate, 2-methyl-3-cyclohex Dipropyl succinate, dibutyl 2-methyl-3-cyclopentyl succinate, dibutyl 2-methyl-3-cyclohexyl succinate, diethyl 2-ethyl-3-cyclopentyl succinate, diethyl 2-ethyl-3-cyclohexyl succinate, 2- Examples thereof include dipropyl ethyl-3-cyclopentyl succinate, dipropyl 2-ethyl-3-cyclohexyl succinate, dibutyl 2-ethyl-3-cyclopentyl succinate, dibutyl 2-ethyl-3-cyclohexyl succinate and the like.

  Dihalogenated succinic acid diesters include diethyl 2,3-dichlorosuccinate, diethyl 2,3-dibromosuccinate, diethyl 2,3-diiodosuccinate, dipropyl 2,3-dichlorosuccinate, and 2,3-dibromosuccinic acid. Examples include dipropyl, dipropyl 2,3-diiodosuccinate, dibutyl 2,3-dichlorosuccinate, dibutyl 2,3-dibromosuccinate, dibutyl 2,3-diiodosuccinate, and halogenated succinic diesters include 2-chloro Diethyl 3-methyl succinate, diethyl 2-chloro-3-ethyl succinate, diethyl 2-chloro-3-propyl succinate, diethyl 2-chloro-3-isopropyl succinate, diethyl 2-chloro-3-butyl succinate, 2 -Dichloro-3-tert-butyl succinate, 2-chloro -3-methyl succinate dipropyl, 2-chloro-3-ethyl succinate dipropyl, 2-chloro-3-propyl succinate dipropyl, 2-chloro-3-isopropyl succinate dipropyl, 2-chloro-3-butyl succinate dipropyl, 2 -Chloro-3-tert-butyl succinate dipropyl, 2-bromo-3-methyl succinate dibutyl, 2-bromo-3-ethyl succinate dibutyl, 2-bromo-3-propyl succinate dibutyl, 2-bromo i-3-sopropyl Dibutyl succinate, dibutyl 2-bromo-3-butyl succinate, dibutyl 2-bromo-tert-butyl succinate, diethyl 2-bromomethyl succinate, diethyl 2-bromo-3-ethyl succinate, 2-bromo-3-propyl succinate Diethyl acid, 2-bromo-3-isopropylsuccinate Diethyl, 2-bromo-3-butyl succinate, 2-bromo-3-tert-butyl succinate, 2-iodo-3-methyl succinate dipropyl, 2-iodo-3-ethyl succinate dipropyl, 2-iodo-3- Propyl succinate dipropyl, 2-iodo-3-isopropyl succinate dipropyl, 2-iodo-3-butyl succinate dipropyl, 2-iodo-3-tert-butyl succinate dipropyl, 2-iodo-3-methyl succinate dibutyl, 2- Dibutyl iodo-3-ethyl succinate, dibutyl 2-iodo-3-propyl succinate, dibutyl 2-iodo-3-isopropyl succinate, dibutyl 2-iodo-3-butyl succinate, 2-iodo-3-tert-butyl succinic acid Examples include dibutyl.

  Of these, diethyl 2,3-dipropyl succinate, diethyl 2,3-diisopropyl succinate, diethyl 2,3-dibutyl succinate, diethyl 2,3-di-tert-butyl succinate, 2,3-di Dibutyl propyl succinate, dibutyl 2,3-diisopropyl succinate, dibutyl 2,3-dibutyl succinate, dibutyl 2,3-di-tert-butyl succinate, diethyl 2,3-dibromosuccinate, 2,3-dibromosuccinate Dibutyl acid and the like are preferable. Moreover, the said component (c) can be used individually or in combination of 2 or more types.

  In combination with the succinic acid diester derivative of the component (c), the solid catalyst component (A) can also be prepared using another electron donating compound. Examples of such electron donating compounds include organic compounds containing oxygen or nitrogen, such as alcohols, phenols, ethers, esters, ketones, acid halides, aldehydes, amines, amides, and nitriles. , Isocyanates, organosilicon compounds containing Si—O—C bonds, and the like.

  Specifically, alcohols such as methanol, ethanol, n-propanol and 2-ethylhexanol, phenols such as phenol and cresol, methyl ether, ethyl ether, propyl ether, butyl ether, amyl ether, diphenyl ether, 9,9- Ethers such as bis (methoxymethyl) fluorene and 2-isopropyl-2-isopentyl-1,3-dimethoxypropane, methyl formate, ethyl acetate, vinyl acetate, propyl acetate, octyl acetate, cyclohexyl acetate, ethyl propionate, ethyl butyrate , Methyl benzoate, ethyl benzoate, propyl benzoate, butyl benzoate, octyl benzoate, cyclohexyl benzoate, phenyl benzoate, methyl p-toluate, ethyl p-toluate, methyl anisate, anisic acid Monocarboxylic acid esters such as chill, diethyl malonate, dibutyl malonate, diethyl maleate, dibutyl maleate, dimethyl adipate, diethyl adipate, dipropyl adipate, dibutyl adipate, diisodecyl adipate, dioctyl adipate, phthalate Dicarboxylic acid esters such as dimethyl acid, diethyl phthalate, dipropyl phthalate, dibutyl phthalate, dipentyl phthalate, dihexyl phthalate, diheptyl phthalate, dioctyl phthalate, dinonyl phthalate, didecyl phthalate, acetone, methyl ethyl ketone, methyl Ketones such as butyl ketone, acetophenone, benzophenone, acid halides such as phthalic dichloride, terephthalic dichloride, acetaldehyde, propionaldehyde, octylal Aldehydes such as hydride and benzaldehyde, amines such as methylamine, ethylamine, tributylamine, piperidine, aniline and pyridine, amides such as oleic acid amide and stearic acid amide, nitriles such as acetonitrile, benzonitrile and tolunitrile, isocyanic acid Isocyanates such as methyl acid and ethyl isocyanate.

  In addition, examples of the organosilicon compound containing a Si—O—C bond include phenylalkoxysilane, alkylalkoxysilane, phenylalkylalkoxysilane, cycloalkylalkoxysilane, and cycloalkylalkylalkoxysilane.

  As the aromatic hydrocarbon compound (d) in the present invention (hereinafter sometimes simply referred to as “component (d)”), those which are liquid at room temperature and have a boiling point in the range of 50 to 150 ° C. are preferred. , Toluene, xylene, ethylbenzene, chlorobenzene, dichlorobenzene, chlorotoluene, dichlorotoluene and the like. Of these, toluene, xylene and ethylbenzene are preferred.

  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 silicon halides such as silicon tetrachloride, silicon tetrabromide and silicon tetraiodide Alternatively, a polysiloxane such as a liquid or viscous chain, partially hydrogenated, cyclic or modified polysiloxane at room temperature 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) described above in the aromatic hydrocarbon compound (d). .

  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.

  In the preparation of the solid catalyst component (A), as a method of contacting each component, the magnesium compound (a) is suspended in the aromatic hydrocarbon compound (d) to form a suspension, and then the suspension and the titanium It is preferable to contact the compound (b). At this time, the magnesium compound (a) may be suspended in the aromatic hydrocarbon compound (d) to form a suspension, and the titanium compound (b) may be added to and brought into contact with the suspension. The compound (a) may be suspended in the aromatic hydrocarbon compound (d) to form a suspension, and this suspension may be added to the titanium compound (b) and contacted.

  Also, the succinic acid diester derivative (c) is brought into contact at any point in the above preparation, but when suspended in the magnesium compound (a) and the aromatic hydrocarbon compound (d) to form a suspension, It is preferable to add a succinic acid diester derivative (c).

  Further, the magnesium compound (a) and the succinic acid diester derivative (c) are suspended in the aromatic hydrocarbon compound (d) to form a suspension, and then the suspension and the titanium compound (b) are combined. It can also be set as the preparation method which contacts and prepares.

  In the preparation of the solid catalyst component (A), the magnesium compound (a) is suspended in the aromatic hydrocarbon compound (d) to form a suspension, and then the suspension and the titanium compound (b) are contacted. After obtaining a solid product reacted with the succinic acid diester derivative (c) at any point of time, the solid product is washed with an aromatic hydrocarbon (d), and further a titanium compound ( By contacting b), the catalytic activity can be further improved.

  Furthermore, when dialkoxymagnesium is used as the magnesium compound (a) and a titanium halide such as titanium tetrachloride is used as the titanium compound (b), the dialkoxymagnesium is halogenated by the titanium halide and the reaction heat is generated. If the temperature of the reaction system rises too much due to this heat of reaction, the performance of the resulting solid catalyst component will deteriorate. Therefore, it is desirable to halogenate dialkoxymagnesium while removing the reaction heat generated at this time. The temperature of the reaction system is in the range of -20 to 50 ° C, preferably in the range of -20 to 30 ° C, particularly preferably in the range of -20 to 20 ° C, with titanium halides such as dialkoxymagnesium and titanium tetrachloride. It is desirable to contact in the presence of an aromatic hydrocarbon to halogenate at least a part or all of dialkoxymagnesium (in the case of titanium tetrachloride, chlorinate to produce magnesium chloride). The halogenation time is 30 to 150 minutes, preferably 30 to 120 minutes, and particularly preferably 30 to 90 minutes. After the halogenation of dialkoxymagnesium through the halogenation step in such a low temperature region, the reaction is performed at a high temperature, for example, 40 to 130 ° C, preferably 60 to 120 ° C, particularly preferably 70 to 120 ° C. It is desirable to process.

  Further, dialkoxymagnesium is suspended in the aromatic hydrocarbon compound (d) to form a suspension, and then the suspension is brought into contact with the titanium halide compound. It is particularly preferable that at least a part of dialkoxymagnesium is halogenated in the range of −20 to 30 ° C. for 30 to 150 minutes and then heated to 70 to 120 ° C. for reaction treatment.

Below, the preferable preparation method of the solid catalyst component (A) for olefin polymerization is illustrated.
(1) After dialkoxymagnesium is suspended in an aromatic hydrocarbon compound solvent, it is brought into contact with titanium tetrachloride, and then heated to contact with component (c) to obtain a solid product. A method of preparing a solid catalyst component (A) for olefin polymerization by washing a product with an aromatic hydrocarbon compound and then again contacting with titanium tetrachloride in the presence of the aromatic hydrocarbon compound. In this case, the solid component can be heat-treated in the presence or absence of a hydrocarbon compound solvent to obtain the solid catalyst component (A) for olefin polymerization.

  (2) After dialkoxymagnesium is suspended in an aromatic hydrocarbon compound, it is contacted with titanium tetrachloride (b) and component (c) to obtain a solid product, and the solid product is aromatic carbonized. A method of obtaining a solid catalyst component (A) for olefin polymerization by washing with a hydrogen compound and then contacting with titanium tetrachloride again in the presence of an aromatic hydrocarbon compound. At this time, the solid component and titanium tetrachloride can be contacted twice or more to obtain a solid catalyst component (A) for olefin polymerization.

(3) Dialkoxymagnesium, calcium chloride and Si (OR ¹⁵ ) ₄ (wherein R ¹⁵ represents an alkyl group or an aryl group) A method of preparing a solid catalyst component (A) for olefin polymerization by suspending in an aromatic hydrocarbon compound, contacting with titanium tetrachloride and component (c), and then further contacting with titanium tetrachloride.

  (4) Dialkoxymagnesium and component (c) are suspended in an aromatic hydrocarbon compound, and the suspension is added to titanium tetrachloride and reacted to obtain a solid product. A method in which after washing with an aromatic hydrocarbon compound, titanium tetrachloride is contacted again in the presence of the aromatic hydrocarbon compound to obtain a solid catalyst component (A) for olefin polymerization.

  (5) After dialkoxymagnesium is suspended in an aromatic hydrocarbon compound solvent, it is brought into contact with titanium tetrachloride, and then heated to contact with component (c) to obtain a solid product. A method for preparing a solid catalyst component (A) for olefin polymerization by washing a product with an aromatic hydrocarbon compound solution and then contacting with titanium tetrachloride again in the presence of the aromatic hydrocarbon compound, A method of preparing a solid catalyst component (A) for olefin polymerization by contacting aluminum chloride at any stage of suspension / contact and contact reaction.

  (6) Dialkoxymagnesium, 2-ethylhexyl alcohol and carbon dioxide are contact-reacted in the presence of an aromatic hydrocarbon compound to form a homogeneous solution, and this solution is contacted with titanium tetrachloride and component (c) to form a solid. A product is obtained, and the solid product is further dissolved in tetrahydrofuran, and then further solid product is precipitated. The solid product is contacted with titanium tetrachloride, and optionally, contact reaction with titanium tetrachloride is repeated. , A method for preparing 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.

  (7) Contact reaction of dialkoxymagnesium, titanium compound and components in the presence of an aromatic hydrocarbon compound, contact reaction of the resulting reaction product with a silicon compound such as polysiloxane, and further contact reaction with titanium tetrachloride And then bringing the metal salt of the organic acid into contact and then contacting with titanium tetrachloride again to obtain the solid catalyst component (A) for olefin polymerization.

  (8) After dialkoxymagnesium and component (c) are suspended in an aromatic hydrocarbon compound solvent, the temperature is raised and brought into contact with silicon tetrachloride, and then brought into contact with titanium tetrachloride to obtain a solid product. The solid product is washed with an aromatic hydrocarbon compound solution and then contacted with titanium tetrachloride again in the presence of the aromatic hydrocarbon compound to prepare the solid catalyst component (A) for olefin polymerization. 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.

  (9) Dialkoxymagnesium is suspended in an aromatic hydrocarbon compound solvent, then contacted with silicon tetrachloride, then heated to contact with component (c), and further contacted with titanium tetrachloride to form a solid. A product is obtained, and the solid product is washed with an aromatic hydrocarbon compound solution, and then contacted with titanium tetrachloride again in the presence of the aromatic hydrocarbon compound to prepare a solid catalyst component (A) for olefin polymerization. how to. 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.

  (10) Magnesium dichloride is dissolved in an alcohol such as 2-ethylhexyl alcohol to form a homogeneous solution, and then phthalic anhydride and titanium tetrachloride are added to precipitate a solid. The component (c) and titanium tetrachloride are contacted in the presence of a hydrocarbon compound, and titanium tetrachloride is contacted again in the presence of an aromatic hydrocarbon compound to prepare a solid catalyst component (A) for olefin polymerization. Method.

  Furthermore, as a more preferable preparation method of the solid catalyst component (A) for olefin polymerization of the present invention, the following methods may be mentioned: For example, dialkoxymagnesium is suspended in a liquid aromatic hydrocarbon compound at room temperature. To form a suspension, and then titanium tetrachloride is added to the suspension at -20 to 50 ° C, preferably -20 to 30 ° C, more preferably -20 to 20 ° C for 30 to 150 minutes, preferably After contact for 30 to 120 minutes, particularly preferably 30 to 90 minutes to chlorinate dialkoxymagnesium, the reaction is carried out at 40 to 130 ° C, more preferably 70 to 120 ° C. 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.

  The solid catalyst component (A) for olefin polymerization prepared as described above contains magnesium, titanium, component (c), and a halogen atom. The content of each component is not particularly specified, but preferably 10 to 30% by weight of magnesium, 1 to 5% by weight of titanium, 1 to 30% by weight of component (c), and 45 to 70% by weight of halogen atoms. .

  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 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 donating compounds that can be used are used, among which ethers such as 9,9-bis (methoxymethyl) fluorene, 2-isopropyl-2-isopentyl-1,3-dimethoxypropane, methyl benzoate and benzoic acid Esters such as ethyl acid or organosilicon compounds are used.

As said organosilicon compound, following General formula (2);
R ⁸ _q Si (OR ⁹ ) _4-q (2)
(In the formula, R ⁸ 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 ⁹ has 1 to 4 carbon atoms. And a straight chain or branched alkyl group, which may be the same or different, and q is an integer of 0 ≦ q ≦ 3). Examples of such an organosilicon compound include phenylalkoxysilane, alkylalkoxysilane, phenylalkylalkoxysilane, cycloalkylalkoxysilane, and cycloalkylalkylalkoxysilane.

  Specific examples of the organosilicon compound include trimethylmethoxysilane, trimethylethoxysilane, tri-n-propylmethoxysilane, tri-n-propylethoxysilane, tri-n-butylmethoxysilane, triisobutylmethoxysilane, tri -T-butylmethoxysilane, tri-n-butylethoxysilane, tricyclohexylmethoxysilane, tricyclohexylethoxysilane, cyclohexyldimethylmethoxysilane, cyclohexyldiethylmethoxysilane, cyclohexyldiethylethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, di -N-propyldimethoxysilane, diisopropyldimethoxysilane, di-n-propyldiethoxysilane, diisopropyldiethoxysilane, di-n-butyl Rudimethoxysilane, diisobutyldimethoxysilane, di-t-butyldimethoxysilane, di-n-butyldiethoxysilane, n-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, cyclohexylcyclopentyldiethoxysilane, cyclohexylcyclopentyldipropoxysilane, 3-methyl Rucyclohexylcyclopentyldimethoxysilane, 4-methylcyclohexylcyclopentyldimethoxysilane, 3,5-dimethylcyclohexylcyclopentyldimethoxysilane, 3-methylcyclohexylcyclohexyldimethoxysilane, 4-methylcyclohexylcyclohexyldimethoxysilane, 3,5-dimethylcyclohexylcyclohexyldimethoxysilane, Cyclopentylmethyldimethoxysilane, cyclopentylmethyldiethoxysilane, cyclopentylethyldiethoxysilane, cyclopentyl (isopropyl) dimethoxysilane, cyclopentyl (isobutyl) dimethoxysilane, cyclohexylmethyldimethoxysilane, cyclohexylmethyldiethoxysilane, cyclohexylethyldimethoxysilane, cyclohexyle Diethoxysilane, cyclohexyl (n-propyl) dimethoxysilane, cyclohexyl (isopropyl) dimethoxysilane, cyclohexyl (n-propyl) diethoxysilane, cyclohexyl (isobutyl) dimethoxysilane, cyclohexyl (n-butyl) diethoxysilane, cyclohexyl (n -Pentyl) dimethoxysilane, cyclohexyl (n-pentyl) diethoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, phenylmethyldimethoxysilane, phenylmethyldiethoxysilane, phenylethyldimethoxysilane, phenylethyldiethoxysilane, methyltrimethoxy Silane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, n-propyltrimethoxy Lan, isopropyltrimethoxysilane, n-propyltriethoxysilane, isopropyltriethoxysilane, n-butyltrimethoxysilane, isobutyltrimethoxysilane, t-butyltrimethoxysilane, n-butyltriethoxysilane, 2-ethylhexyltrimethoxy Silane, 2-ethylhexyltriethoxysilane, cyclopentyltrimethoxysilane, cyclopentyltriethoxysilane, cyclohexyltrimethoxysilane, cyclohexyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, tetra Examples include methoxysilane, tetraethoxysilane, tetrapropoxysilane, and tetrabutoxysilane. Among the above, di-n-propyldimethoxysilane, diisopropyldimethoxysilane, di-n-butyldimethoxysilane, diisobutyldimethoxysilane, di-t-butyldimethoxysilane, di-n-butyldiethoxysilane, t-butyltrimethoxy Silane, dicyclohexyldimethoxysilane, dicyclohexyldiethoxysilane, cyclohexylmethyldimethoxysilane, cyclohexylmethyldiethoxysilane, cyclohexylethyldimethoxysilane, cyclohexylethyldiethoxysilane, dicyclopentyldimethoxysilane, dicyclopentyldiethoxysilane, cyclopentylmethyldimethoxysilane, cyclopentyl Methyldiethoxysilane, cyclopentylethyldiethoxysilane, cyclohexylcyclopentyl Methoxysilane, cyclohexylcyclopentyldiethoxysilane, 3-methylcyclohexylcyclopentyldimethoxysilane, 4-methylcyclohexylcyclopentyldimethoxysilane, and 3,5-dimethylcyclohexylcyclopentyldimethoxysilane are preferably used, and the organosilicon compound (C) may be one kind or Two or more types can be used in combination.

  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 by the present invention, a high hydrogen response is maintained while maintaining a high yield and high stereoregularity compared to the case of using a conventional catalyst. An olefin polymer having a broad molecular weight distribution can be obtained.

  Hereinafter, examples of the present invention will be described in detail while comparing with comparative examples.

[Preparation of solid catalyst component (A)]
A 500 ml round-bottom flask fully substituted with nitrogen gas and equipped with a stirrer was charged with 10 g of diethoxymagnesium, 2.8 g of diethyl 2,3-dipropylsuccinate and 80 ml of toluene to form a suspension. The temperature was kept at 10 ° C. Next, 20 ml of titanium tetrachloride was added to the suspension while cooling the flask so that the temperature of the suspension was maintained at 10 ° C., followed by stirring at 10 ° C. for 1 hour. Thereafter, the temperature was raised to 90 ° C. Thereafter, the reaction was carried out with stirring for 1 hour while maintaining a temperature of 90 ° C. After completion of the reaction, the mixture was washed 4 times with 100 ml of toluene at 80 ° C., 20 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 1 hour. After completion of the reaction, the solid catalyst component was obtained by washing 7 times with 100 ml of n-heptane at 40 ° C. In addition, when the solid-liquid in this solid catalyst component was isolate | separated and the titanium content rate in solid content was measured, it was 3.1 weight%.

[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 dicyclopentyldimethoxysilane and 0.0026 mmol of the solid catalyst component as titanium atoms were charged. A polymerization catalyst was formed. Thereafter, 1.5 liters of hydrogen gas and 1.4 liters of liquefied propylene were charged, preliminarily polymerized at 20 ° C. for 5 minutes, then heated up, and polymerized at 70 ° C. for 1 hour. Table 1 shows the polymerization activity per 1 g of the solid catalyst component, the xylene-soluble component (XS), the melt index value (MI) of the produced polymer, and the polydispersity index (PI).

The polymerization activity per solid catalyst component used here was calculated by the following equation.
Polymerization activity = produced polymer (g) / solid catalyst component (g)
The xylene-soluble component (XS) was measured by the following method.
Method for measuring xylene-soluble component: 4.0 g of polymer was charged into 200 ml of para-xylene, and the polymer was dissolved at a boiling point (138 ° C.) over 2 hours. Thereafter, the mixture was cooled to 23 ° C., and the dissolved component and the insoluble component were separated by filtration. The dissolved component was dried by heating, and the resulting polymer was defined as xylene-soluble component (XS) (% by weight).
The value of the polydispersity index (PI) was measured with a dynamic stress rheometer manufactured by Rheometrics using a disk having a thickness of 1.0 mm.
Further, 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 g of diethyl 2,3-diisopropyl succinate was used instead of 2.8 g of diethyl 2,3-dipropyl succinate. Polymerization was performed. As a result, the titanium content in the obtained solid catalyst component was 3.2% by weight. The polymerization results are shown in Table 1.

  A solid component was prepared in the same manner as in Example 1 except that 3.4 g of dibutyl 2,3-dipropyl succinate was used instead of 2.8 g of diethyl 2,3-dipropyl succinate. And polymerization was carried out. As a result, the titanium content in the obtained solid catalyst component was 3.5% by weight. The polymerization results are shown in Table 1.

  A solid component was prepared in the same manner as in Example 1 except that 2.5 g of diethyl t-butyl succinate was used instead of 2.8 g of diethyl 2,3-dipropyl succinate, and a polymerization catalyst was formed and polymerized. It was. As a result, the titanium content in the obtained solid catalyst component was 3.1% by weight. The polymerization results are shown in Table 1.

  A solid component was prepared in the same manner as in Example 1 except that 3.6 g of diethyl 2,3-dibromosuccinate was used instead of 2.8 g of diethyl 2,3-dipropyl succinate. Polymerization was performed. As a result, the titanium content in the obtained solid catalyst component was 3.1% by weight. The polymerization results are shown in Table 1.

Comparative Example 1
A solid component was prepared in the same manner as in Example 1 except that 1.9 g of diethyl succinate was used instead of 2.8 g of diethyl 2,3-dipropyl succinate, and a polymerization catalyst was formed and polymerized. As a result, the titanium content in the solid catalyst component was 2.2% by weight. The polymerization results are shown in Table 1.

Comparative Example 2
A solid component was prepared in the same manner as in Example 1 except that 3.0 g of dibutyl phthalate was used instead of 2.8 g of diethyl 2,3-dipropyl succinate, and a polymerization catalyst was formed and polymerized. As a result, the titanium content in the solid catalyst component was 3.4% by weight. The polymerization results are shown in Table 1.

Comparative Example 3
8.3 g of anhydrous magnesium chloride, 50 ml of decane and 40.8 ml of 2-ethylhexyl alcohol were mixed and reacted at 130 ° C. for 2 hours to obtain a homogeneous solution. To this solution, 1.9 g of phthalic anhydride was added and stirred at 130 ° C. for 1 hour to obtain a uniform solution. The homogeneous solution was cooled to room temperature and added to 350 ml of titanium tetrachloride cooled to −20 ° C. over 1 hour. Thereafter, the temperature was raised to 110 ° C. over 4 hours. When the temperature reached 110 ° C., 4.7 ml of isobutyl phthalate was added and stirred while maintaining the temperature at 110 ° C. The solid and liquid were separated after the reaction. To the solid part, 350 ml of titanium tetrachloride was added and reacted at 110 ° C. for 2 hours. After completion of the reaction, the solid and liquid were separated to obtain a solid part. This solid part was washed with heptane at 60 ° C. until no free titanium compound was observed in the solution. The titanium content in the obtained solid catalyst component was 3.7%. The polymerization results are shown in Table 1.

  From the results of Table 1, by performing polymerization of olefins using the solid catalyst component and catalyst of the present invention, high hydrogen response is exhibited while maintaining high stereoregularity at a high yield, and the molecular weight distribution is wide. It turns out that an olefin polymer is obtained.

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

Claims (15)

It is prepared by contacting a magnesium compound (a), a titanium compound (b), and a succinic acid diester derivative (c) represented by the following chemical formula (1) in an aromatic hydrocarbon compound (d). Solid catalyst component for olefin polymerization.

(Wherein R ^{3 to} R ⁶ represent a hydrogen atom, a halogen atom or an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group, an aryl group, a vinyl group, an allyl group, an aralkyl group, and may be the same or different; At least one is a substituent other than a hydrogen atom, and R ¹ and R ^{2 each} represent an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group, an aryl group, a vinyl group, an allyl group, or an aralkyl group, May be different.) The solid catalyst component for olefin polymerization according to claim 1, wherein at least one group of R ^{3 to} R ⁶ is a halogen atom. The solid for olefin polymerization according to claim 1 or 2, wherein the two groups of R ^{3 to} R ⁶ are two halogen atoms, and the two halogen atoms are bonded to different carbon atoms. Catalyst component.   The magnesium compound (a) is suspended in the aromatic hydrocarbon compound (d) to form a suspension, and then the suspension and the titanium compound (b) are contacted at any point in time. The solid catalyst component for olefin polymerization according to any one of claims 1 to 3, which is prepared by contacting the succinic acid diester derivative (c).   The magnesium compound (a) and the succinic diester derivative (c) are suspended in the aromatic hydrocarbon compound (d) to form a suspension, and then the suspension and the titanium compound (b) are contacted The solid catalyst component for olefin polymerization according to any one of claims 1 to 3, wherein the solid catalyst component is prepared.   The magnesium compound (a) is suspended in the aromatic hydrocarbon compound (d) to form a suspension, and then the suspension and the titanium compound (b) are contacted at any point in time. After obtaining a solid product reacted with the succinic diester derivative (c), the solid product was washed with the aromatic hydrocarbon (d), and further contacted with the titanium compound (b). The solid catalyst component for olefin polymerization according to any one of claims 1 to 3, wherein the solid catalyst component is prepared.   The solid catalyst component for olefin polymerization according to any one of claims 1 to 6, wherein the component (a) magnesium compound is dialkoxymagnesium.  The solid catalyst component for olefin polymerization according to any one of claims 1 to 6, wherein the component (a) magnesium compound is diethoxymagnesium.   The component (a) magnesium compound is dialkoxymagnesium, and the component (b) titanium compound is a titanium halide for olefin polymerization according to any one of claims 1 to 6. Solid catalyst component.   The solid catalyst component for olefin polymerization according to any one of claims 1 to 9, wherein the aromatic hydrocarbon compound (d) is any one of toluene, xylene, and ethylbenzene.   Dialkoxymagnesium is suspended in the aromatic hydrocarbon compound (d) to form a suspension, and then the suspension and titanium halide are brought into contact with each other. The solid catalyst component for olefin polymerization according to claim 9, wherein at least a part of the catalyst is halogenated.   The dialkoxymagnesium is suspended in the aromatic hydrocarbon compound (d) to form a suspension, and then the suspension and titanium halide are contacted. The solid catalyst component for olefin polymerization according to claim 9, wherein at least a part of dialkoxymagnesium is halogenated in a range of 30 ° C for 30 to 150 minutes.   The dialkoxymagnesium is suspended in the aromatic hydrocarbon compound (d) to form a suspension, and then the suspension and titanium halide are contacted. 10. The solid for olefin polymerization according to claim 9, wherein at least a part of dialkoxymagnesium is halogenated in a range of 30 ° C. for 30 to 150 minutes, and then heated to 70 to 120 ° C. for reaction treatment. Catalyst component. (A) Solid catalyst component for olefin polymerization according to any one of claims 1 to 13, (B) the following general formula (1); R ⁷ _p AlQ _3-p (1)
(Wherein R ⁷ 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 electron donating compound. The (C) electron donating compound is represented by the following general formula (2);
R ⁸ _q Si (OR ⁹ ) _4-q (2)
(In the formula, R ⁸ 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 ⁹ has 1 to 4 carbon atoms. An alkyl group, a cycloalkyl group, a phenyl group, a vinyl group, or an allyl group or an aralkyl group, which may be the same or different, and q is an integer of 0 ≦ q ≦ 3. The catalyst for olefin polymerization according to claim 14, which is a compound.

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