JP2008144008A - Catalyst for olefin copolymerization and method for producing olefin copolymer - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a catalyst for olefin copolymerization capable of giving an olefin copolymer having high randomness in high polymerization activity and a method for producing an olefin copolymer. <P>SOLUTION: The invention provides an olefin copolymerization catalyst obtained by contacting the following components (A), (B) and (C) and a method for producing an olefin copolymer by using the olefin copolymerization catalyst. (A) A solid catalyst component produced by contacting (a) a solid component containing a titanium atom, a magnesium atom and a hydrocarbyloxy group, (b) a halide compound and (c) an electron donor and/or (d) an organic acid halide, (B) an organic aluminum compound and/or an organic aluminumoxy compound and (C) an aromatic nitrogen heterocyclic compound having a 1-3C alkyl group on one or more carbon atoms adjacent to the nitrogen atom. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to a catalyst for olefin copolymerization and a method for producing an olefin copolymer.

  Molded articles made of polypropylene are excellent in rigidity, heat resistance, surface glossiness, and the like, and thus have been used for various applications, but have a problem of insufficient impact resistance. For this reason, for example, impact resistance is improved by including an olefin copolymer such as an ethylene-propylene copolymer or an ethylene-1-butene copolymer. As a method for producing an olefin copolymer used for such a purpose, for example, Patent Document 1 discloses that a homogeneous solution obtained by contacting diethoxymagnesium and tetrabutoxytitanium with a specific electron-donating compound and tetrachloride. It is described that a copolymer rubber obtained by randomly polymerizing ethylene and propylene is obtained using a solid catalyst component obtained by contacting titanium.

JP-A-3-205406

However, in the production method using the polymerization catalyst described in Patent Document 1, an olefin copolymer having high randomness is obtained, but the polymerization activity is not sufficient.
Under such circumstances, the problem to be solved by the present invention, that is, the object of the present invention, is to provide an olefin copolymer catalyst and a method for producing an olefin copolymer that can obtain an olefin copolymer having high randomness with high polymerization activity. It is something to be offered.

The present invention relates to an olefin copolymer catalyst obtained by bringing the following components (A), (B) and (C) into contact with each other, and a method for producing an olefin copolymer using the olefin copolymer catalyst.
(A) obtained by contacting a solid component (a) containing a titanium atom, a magnesium atom and a hydrocarbyloxy group, a halogenated compound (b), an electron donor (c) and / or an organic acid halide (d). Solid catalyst component (B) Organoaluminum compound and / or organoaluminum oxycompound (C) Aromatic nitrogen heterocyclic compound having an alkyl group having 1 to 3 carbon atoms on at least one carbon atom adjacent to the nitrogen atom

  ADVANTAGE OF THE INVENTION According to this invention, the manufacturing method of the catalyst for olefin copolymer which can obtain an olefin copolymer with high randomness by high polymerization activity, and an olefin copolymer is provided.

Hereinafter, the present invention will be specifically described.
Component (C) used in the present invention is an aromatic nitrogen heterocyclic compound having a substituent having an alkyl group having 1 to 3 carbon atoms on at least one carbon atom adjacent to the nitrogen atom. A nitrogen heterocyclic compound is a cyclic compound having one or more nitrogen atoms in a ring composed of carbon atoms, and an aromatic nitrogen heterocyclic compound is a compound in which the nitrogen heterocyclic moiety is aromatic. is there. Examples of the aromatic nitrogen heterocyclic compound having one nitrogen atom in the heterocyclic ring include pyridine and pyrrole.

  The aromatic nitrogen heterocyclic compound is preferably an aromatic nitrogen heterocyclic compound in which the nitrogen heterocyclic moiety has a 6-membered ring structure, and more preferably pyridine.

  The aromatic nitrogen heterocyclic compound used in the present invention is a compound having a substituent having an alkyl group having 1 to 3 carbon atoms on at least one carbon atom adjacent to the nitrogen atom.

  Examples of the alkyl group having 1 to 3 carbon atoms include a methyl group, an ethyl group, an n-propyl group, and an isopropyl group.

  The aromatic nitrogen heterocyclic compound used in the present invention is a compound having the above alkyl group having 1 to 3 carbon atoms on at least one carbon atom adjacent to the nitrogen atom, but has higher randomness. From the viewpoint of producing an olefin copolymer, a compound having an alkyl group having 1 to 3 carbon atoms on two carbon atoms adjacent to a nitrogen atom is preferable, and a plurality of alkyl groups having 1 to 3 carbon atoms are the same. But it can be different.

  Examples of the aromatic nitrogen heterocyclic compound having an alkyl group having 1 to 3 carbon atoms on at least one carbon atom adjacent to the nitrogen atom include 2-methylpyridine, 2,3-dimethylpyridine, 2,4 -Dimethylpyridine, 2,5-dimethylpyridine, 2,6-dimethylpyridine, 2,3,4-trimethylpyridine, 2,3,5-trimethylpyridine, 2,3,5-trimethylpyridine, 2,4,5 -Trimethylpyridine, 2,4,6-trimethylpyridine, 2,3,4,5-tetramethylpyridine, 2,3,4,6-tetramethylpyridine, pentamethylpyridine, 2-ethylpyridine, 2,3- Diethylpyridine, 2,4-diethylpyridine, 2,5-diethylpyridine, 2,6-diethylpyridine, 2,3,4-triethylpyridine, 2, , 5-triethylpyridine, 2,3,5-triethylpyridine, 2,4,5-triethylpyridine, 2,4,6-triethylpyridine, 2,3,4,5-tetraethylpyridine, 2,3,4, 6-tetraethylpyridine, pentaethylpyridine, 2-propylpyridine, 2,3-dipropylpyridine, 2,4-dipropylpyridine, 2,5-dipropylpyridine, 2,6-dipropylpyridine, 2,3, 4-tripropylpyridine, 2,3,5-tripropylpyridine, 2,3,5-tripropylpyridine, 2,4,5-tripropylpyridine, 2,4,6-tripropylpyridine, 2,3, 4,5-tetrapropylpyridine, 2,3,4,6-tetrapropylpyridine, pentapropylpyridine, 2-isopropylpyridine, 2,3-di Sopropylpyridine, 2,4-diisopropylpyridine, 2,5-diisopropylpyridine, 2,6-diisopropylpyridine, 2,3,4-triisopropylpyridine, 2,3,5-triisopropylpyridine, 2,3,5 -Triisopropylpyridine, 2,4,5-triisopropylpyridine, 2,4,6-triisomethylpyridine, 2,3,4,5-tetraisopropylpyridine, 2,3,4,6-tetraisopropylpyridine, Or a pyridine compound such as pentaisopropylpyridine, 2-methylpyrrole, 2,3-dimethylpyrrole, 2,4-dimethylpyrrole, 2,5-dimethylpyrrole, 2,3,4-trimethylpyrrole, 2,3,5 -Trimethylpyrrole, 2,3,4,5-tetramethylpyrrole, 2-ethylpyrrole, 2,3-diethylpyrrole, 2,4-diethylpyrrole, 2,5-diethylpyrrole, 2,3,4-triethylpyrrole, 2,3,5-triethylpyrrole, 2,3,4,5-tetraethylpyrrole, 2-propyl pyrrole, 2,3-dipropyl pyrrole, 2,4-dipropyl pyrrole, 2,5-dipropyl pyrrole, 2,3,4-tripropyl pyrrole, 2,3,5-tripropyl pyrrole, 2 , 3,4,5-tetrapropylpyrrole, 2-isopropylpyrrole, 2,3-diisopropylpyrrole, 2,4-diisopropylpyrrole, 2,5-diisopropylpyrrole, 2,3,4-triisopropylpyrrole, 2,3 Pyrrole compounds such as, 5-triisopropylpyrrole, 2,3,4,5-tetraisopropylpyrrole, Preferably, 2-methylpyridine, 2,3-dimethylpyridine, 2,4-dimethylpyridine, 2,5-dimethylpyridine, 2,6-dimethylpyridine, 2,3,4-trimethylpyridine, 2,3, 5-trimethylpyridine, 2,3,5-trimethylpyridine, 2,4,5-trimethylpyridine, 2,4,6-trimethylpyridine, 2,3,4,5-tetramethylpyridine, 2,3,4, 6-tetramethylpyridine, pentamethylpyridine, 2-ethylpyridine, 2,3-diethylpyridine, 2,4-diethylpyridine, 2,5-diethylpyridine, 2,6-diethylpyridine, 2,3,4-triethyl Pyridine, 2,3,5-triethylpyridine, 2,3,5-triethylpyridine, 2,4,5-triethylpyridine, 2,4,6-triethyl Pyridine, 2,3,4,5-tetraethylpyridine, 2,3,4,6-tetraethylpyridine, pentaethylpyridine, 2-propylpyridine, 2,3-dipropylpyridine, 2,4-dipropylpyridine, 2 , 5-dipropylpyridine, 2,6-dipropylpyridine, 2,3,4-tripropylpyridine, 2,3,5-tripropylpyridine, 2,3,5-tripropylpyridine, 2,4,5 -Tripropylpyridine, 2,4,6-tripropylpyridine, 2,3,4,5-tetrapropylpyridine, 2,3,4,6-tetrapropylpyridine, pentapropylpyridine, 2-isopropylpyridine, 2, 3-diisopropylpyridine, 2,4-diisopropylpyridine, 2,5-diisopropylpyridine, 2,6-diisopropylpyrid 2,3,4-triisopropylpyridine, 2,3,5-triisopropylpyridine, 2,3,5-triisopropylpyridine, 2,4,5-triisopropylpyridine, 2,4,6-triiso Methylpyridine, 2,3,4,5-tetraisopropylpyridine, 2,3,4,6-tetraisopropylpyridine, or pentaisopropylpyridine,

  More preferably, 2,6-dimethylpyridine, 2,4,6-trimethylpyridine, 2,3,4,6-tetramethylpyridine, pentamethylpyridine, 2,6-diethylpyridine, 2,4,6-triethyl Pyridine, 2,3,4,6-tetraethylpyridine, pentaethylpyridine, 2,6-dipropylpyridine, 2,4,6-tripropylpyridine, 2,3,4,6-tetrapropylpyridine, pentapropylpyridine 2,6-diisopropylpyridine, 2,4,6-triisomethylpyridine, 2,3,4,6-tetraisopropylpyridine, or pentaisopropylpyridine, more preferably 2,6-dimethylpyridine, 2,6-diethylpyridine, 2,6-dipropylpyridine, or 2,6-diisopropylpyrid , And most preferably, 2,6-dimethylpyridine or 2,6-diethyl-pyridine.

  The solid catalyst component used together with the component (C) in the present invention may be appropriately selected from known ones. Typical examples of the solid catalyst component (A) include a titanium atom, a magnesium atom and a halogen atom. ).

(A) Solid catalyst component The solid catalyst component (A) may be any known solid catalyst component containing a titanium atom, a magnesium atom and a halogen atom, and the method for producing the solid catalyst component is particularly limited. Is not to be done. Examples of the solid catalyst component include, for example, JP-B-46-34092, JP-B-47-41676, JP-B-55-23561, JP-B-57-24361, JP-B-52-39431, and JP-B 52-36786, JP-B 1-28049, JP-B 3-43283, JP-A-4-80044, JP-A 55-52309, JP-A 58-21405, JP JP 61-181807, JP 63-142008, JP 5-339319, JP 54-148093, JP 4-227604, JP 64-6006, JP-A-6-179720, JP-B-7-116252, JP-A-8-134124, JP-A-9-31119, JP-A-11 No. 228628, JP-A-11-80234, JP-A-11-322833, JP-A-54-94590, JP-A-5-55405, JP-A-56-45909, JP-A JP-A-56-163102, JP-A-57-63310, JP-A-57-115408, JP-A-58-83006, JP-A-58-83016, JP-A-58-138707. JP, 59-149905, JP, 60-23404, JP, 60-32805, JP, 61-18330, JP, 61-55104, JP, 63. Solid catalyst component or solid catalyst component described in JP-303010, JP-A-1-315406, JP-A-2-77413, and JP-A-2-117905 It can be exemplified manufacturing method.

As the solid catalyst component, a solid catalyst component containing an electron donor in addition to a titanium atom, a magnesium atom and a halogen atom is preferable. The electron donor is preferably an organic acid ester or ether described below. Examples of the method for producing the solid catalyst component include the following methods (1) to (5).
(1) A method of contacting a magnesium halide compound with a titanium compound.
(2) A method of contacting a magnesium halide compound, an electron donor, and a titanium compound.
(3) A method in which a magnesium halide compound and a titanium compound are dissolved in an electron donating solvent to obtain a solution, and then the carrier material is impregnated with the solution.
(4) A method of contacting a solid component (a) containing a magnesium atom and a hydrocarbyloxy group, a halogenated compound (b), an electron donor (c) and / or an organic acid halide (d).

  Among them, the method (4) in which the solid component (a) containing a magnesium atom and a hydrocarbyloxy group, the halogenated compound (b), the electron donor (c) and / or the organic acid halide (d) is contacted is preferable.

  Examples of the magnesium halide compound include magnesium chloride, magnesium bromide, magnesium iodide, and magnesium fluoride, with magnesium chloride being preferred.

(A) Solid component containing magnesium atom and hydrocarbyloxy group The solid component (a) used in the method (4) is a solid substance containing a magnesium atom and a hydrocarbyloxy group (hereinafter simply referred to as a solid component ( a). As such a compound, for example,
1) Solid compound of dihydrocarbyloxymagnesium represented by the formula Mg (OR ¹ ) (OR ² ) (wherein R ¹ and R ² represent hydrocarbyl having 1 to 20 carbon atoms.)
2) A solid compound of hydrocarbyloxymagnesium halide represented by the formula Mg (OR ³ ) X ¹ (wherein R ³ represents a hydrocarbyl group having 1 to 20 carbon atoms, and X ¹ represents a halogen atom.)
3) A solid compound containing a trivalent titanium atom, a magnesium atom and a hydrocarbyloxy group.

1) Examples of dihydrocarbyloxymagnesium represented by the formula Mg (OR ¹ ) (OR ² ) include, for example, dimethoxymagnesium, diethoxymagnesium, dipropoxymagnesium, dibutoxymagnesium, dipentoxymagnesium, dihexyloxymagnesium, Examples include dioctoxymagnesium, diphenoxymagnesium, dicyclohexyloxymagnesium, methoxyethoxymagnesium, methoxypropoxymagnesium, methoxybutoxymagnesium, ethoxypropoxymagnesium, ethoxybutoxymagnesium, and the like. Dimethoxy magnesium, diethoxy magnesium, and dipropoxy magnesium are preferable, and diethoxy magnesium is more preferable.

1) Any preparation method may be used to obtain a solid compound of dihydrocarbyloxymagnesium represented by the formula Mg (OR ¹ ) (OR ² ), but a solid suitable for producing a catalyst component for olefin copolymerization. Examples of the method for preparing the gaseous compound include a method of reacting metal magnesium with an alcohol and a small amount of halogen and / or a halogen-containing compound, and a method of reacting a dialkylmagnesium compound with an alkoxysilicon compound.

2) Examples of the hydrocarbyloxymagnesium halide represented by the formula Mg (OR ³ ) X ¹ include methoxymagnesium chloride, ethoxymagnesium chloride, propoxymagnesium chloride, butoxymagnesium chloride, pentoxymagnesium chloride, hexyloxymagnesium chloride, octet Examples thereof include xylmagnesium chloride, phenoxymagnesium chloride, cyclohexyloxymagnesium chloride, and those obtained by replacing these chlorine atoms with fluorine atoms, bromine atoms, and iodine atoms. Preferred are methoxymagnesium chloride, ethoxymagnesium chloride and propoxymagnesium chloride, and more preferred is ethoxymagnesium chloride.

2) Any preparation method may be used to obtain a solid compound of hydrocarbyloxymagnesium halide represented by the formula Mg (OR ³ ) X ¹ , but it is suitable for the production of a catalyst component for olefin copolymerization. Examples of the preparation method include a method of reacting a Grignard compound and an alkoxysilicon compound, a method of reacting a Grignard compound and an alcohol, and the like.

（ただし、上式［Ｉ］において、ａは１〜２０の数を表し、Ｒ⁴は炭素原子数１〜２０のヒドロカルビル基を表す。Ｘ²はハロゲン原子または炭素原子数１〜２０のヒドロカルビルオキシ基を表し、Ｘ²は互いに同じであっても異なっていてもよい。） Examples of the hydrocarbyloxy group of the solid compound containing a trivalent titanium atom, magnesium atom and hydrocarbyloxy group in 3) include a hydrocarbyloxy group having 1 to 20 carbon atoms, preferably a methoxy group, An ethoxy group, a propoxy group, a butoxy group, a pentoxy group, and a hexoxy group.
Any preparation method may be used to obtain a solid compound containing a trivalent titanium atom, magnesium atom and hydrocarbyloxy group in 3), but preparation of a solid compound suitable for the production of a catalyst component for olefin polymerization As a method, for example, a method of reducing a titanium compound (ii) represented by the following formula [I] with an organomagnesium compound (iii) in the presence of an organosilicon compound (i) having a Si—O bond. Can be mentioned.

(In the above formula [I], a represents a number of 1 to 20, R ⁴ represents a hydrocarbyl group having 1 to 20 carbon atoms. X ² represents a halogen atom or a hydrocarbyloxy having 1 to 20 carbon atoms. And X ² may be the same or different from each other.

３）の固体状化合物は、Ｓｉ−Ｏ結合を有する有機ケイ素化合物（ｉ）の存在下に、下式［Ｉ］で表されるチタン化合物（ｉｉ）を、有機マグネシウム化合物（ｉｉｉ）で還元することによって得られる固体状化合物であるが、このとき、重合活性をさらに向上させる観点から、任意成分としてエステル化合物（ｉｖ）を共存させることが好ましい。

（ただし、上式［Ｉ］において、ａは１〜２０の数を表し、Ｒ⁴は炭素原子数１〜２０のヒドロカルビル基を表す。Ｘ²はハロゲン原子または炭素原子数１〜２０のヒドロカルビルオキシ基を表し、Ｘ²は互いに同じであっても異なっていてもよい。）
３価のチタン原子の含有量として好ましくは、総チタン原子の５０％以上であり、より好ましくは９０％以上である。また、ヒドロカルビルオキシ基の含有量として好ましくは２０重量％以上であり、より好ましくは２５重量％以上である。 Among these solid compounds, the solid component (a) is preferably a solid compound 3). The following 3) will be described in detail.

The solid compound 3) reduces the titanium compound (ii) represented by the following formula [I] with the organomagnesium compound (iii) in the presence of the organosilicon compound (i) having a Si—O bond. In this case, from the viewpoint of further improving the polymerization activity, it is preferable that the ester compound (iv) coexists as an optional component.

(In the above formula [I], a represents a number of 1 to 20, R ⁴ represents a hydrocarbyl group having 1 to 20 carbon atoms. X ² represents a halogen atom or a hydrocarbyloxy having 1 to 20 carbon atoms. And X ² may be the same or different from each other.
The content of trivalent titanium atoms is preferably 50% or more of the total titanium atoms, more preferably 90% or more. The content of hydrocarbyloxy groups is preferably 20% by weight or more, and more preferably 25% by weight or more.

As organosilicon compound (i) which has Si-O bond, the organosilicon compound represented by the following Formula is mentioned, for example.
Si (OR ⁵ ) _t R ⁶ _4-t ,
R ⁷ (R ⁸ ₂ SiO) _u SiR ⁹ ₃ or
(R ¹⁰ ₂ SiO) _v
Here, R ⁵ is a hydrocarbyl group having 1 to 20 carbon atoms, and R ⁶ , R ⁷ , R ⁸ , R ⁹ and R ¹⁰ are each independently a hydrocarbyl group having 1 to 20 carbon atoms or a hydrogen atom. is there. t is an integer satisfying 0 <t ≦ 4, u is an integer of 1-1000, and v is an integer of 2-1000.

  Examples of the organosilicon compound (i) having a Si—O bond include tetramethoxysilane, dimethyldimethoxysilane, tetraethoxysilane, triethoxyethylsilane, diethoxydiethylsilane, ethoxytriethylsilane, tetraisopropoxysilane, diiso Propoxy-diisopropylsilane, tetrapropoxysilane, dipropoxydipropylsilane, tetrabutoxysilane, dibutoxydibutylsilane, dicyclopentoxydiethylsilane, diethoxydiphenylsilane, cyclohexyloxytrimethylsilane, phenoxytrimethylsilane, tetraphenoxysilane, tri Ethoxyphenylsilane, hexamethyldisilohexane, hexaethyldisilohexane, hexapropyldisiloxane, octaethyltrisiloxane Dimethyl polysiloxane, diphenyl polysiloxane, methylhydropolysiloxane, phenyl hydropolysiloxane like.

The organosilicon compound (i) having a Si—O bond is preferably an alkoxysilane compound represented by the formula Si (OR ⁵ ) _t R ⁶ _4-t (t represents a number satisfying 1 ≦ t ≦ 4). More preferred is tetraalkoxysilane in which t is 4, and most preferred is tetraethoxysilane.

（ただし、上式［Ｉ］において、ａは１〜２０の数を表し、Ｒ⁴は炭素原子数１〜２０のヒドロカルビル基を表す。Ｘ²はハロゲン原子または炭素原子数１〜２０のヒドロカルビルオキシ基を表し、Ｘ²は互いに同じであっても異なっていてもよい。） The titanium compound (ii) is a titanium compound represented by the following formula [I].

(In the above formula [I], a represents a number of 1 to 20, R ⁴ represents a hydrocarbyl group having 1 to 20 carbon atoms. X ² represents a halogen atom or a hydrocarbyloxy having 1 to 20 carbon atoms. And X ² may be the same or different from each other.

R ⁴ in the formula [I] is, for example, methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, amyl group, isoamyl group, hexyl group, heptyl group, octyl group, decyl group, dodecyl group. And alkyl groups such as phenyl group, cresyl group, xylyl group and naphthyl group, cycloalkyl groups such as cyclohexyl group and cyclopentyl group, allyl groups such as propenyl group, and aralkyl groups such as benzyl group.
R ⁴ is preferably an alkyl group having 2 to 18 carbon atoms or an aryl group having 6 to 18 carbon atoms, and particularly preferably a linear alkyl group having 2 to 18 carbon atoms.

As a halogen atom in X < ² > of Formula [I], a chlorine atom, a bromine atom, and an iodine atom are mentioned, for example. Particularly preferred is a chlorine atom. The hydrocarbyloxy group having 1 to 20 carbon atoms in X ² is a hydrocarbyloxy group having a hydrocarbyl group having 1 to 20 carbon atoms similar to R ⁴ . X ² is particularly preferably an alkoxy group having a linear alkyl group having 2 to 18 carbon atoms.

  In the titanium compound (ii) represented by the formula [I], a is a number of 1 to 20, and preferably a number satisfying 1 ≦ a ≦ 5.

  Examples of the titanium compound (ii) represented by the formula [I] include tetramethoxy titanium, tetraethoxy titanium, tetra-n-propoxy titanium, tetra-iso-propoxy titanium, tetra-n-butoxy titanium, and tetra-iso. -Butoxytitanium, n-butoxytitanium trichloride, di-n-butoxytitanium dichloride, tri-n-butoxytitanium chloride, di-n-tetraisopropylpolytitanate (a mixture in the range of a = 2-10), tetra-n -Butyl polytitanate (a mixture in the range of a = 2-10), tetra-n-hexyl polytitanate (a mixture in the range of a = 2-10), tetra-n-octyl polytitanate (range of a = 2-10) For example). Moreover, the condensate of the tetraalkoxy titanium obtained by making a small amount of water react with tetraalkoxy titanium can also be mentioned.

  The titanium compound (ii) represented by the formula [I] is preferably a titanium compound in which a in the formula [I] is 1, 2 or 4, and particularly preferably tetra-n-butoxy titanium or tetra-n. -Butyl titanium dimer or tetra-n-butyl titanium tetramer. The titanium compound (ii) represented by the formula [I] may be used alone or in combination of two or more.

The organomagnesium compound (iii) is any type of organomagnesium compound having a magnesium atom-carbon atom bond. The organic magnesium compound (iii) is preferably a Grignard compound represented by the formula R ¹¹ MgX ³ (wherein R ¹¹ represents a hydrocarbyl group having 1 to 20 carbon atoms, and X ³ represents a halogen atom). or formula R ¹² R ¹³ Mg (in expression, R ^12, R ¹³ each independently represent a hydrocarbyl group having 1 to 20 carbon atoms.) is a dihydrocarbyl magnesium represented by the good form From the viewpoint of obtaining a catalyst, a Grignard compound is more preferable. Examples of R ^{11 to} R ¹³ include methyl group, ethyl group, propyl group, isopropyl group, butyl group, sec-butyl group, tert-butyl group, isoamyl group, hexyl group, octyl group, 2-ethylhexyl group, phenyl Group, an alkyl group having 1 to 20 carbon atoms such as a benzyl group, an aryl group, an aralkyl group, and an alkenyl group. Particularly preferably, a Grignard compound represented by R ¹¹ MgX ³ is used as the ether solution.

  A hydrocarbon-soluble complex of the organomagnesium compound (iii) and an organometallic compound that solubilizes the organomagnesium compound (iii) in a hydrocarbon can also be used. Examples of the organometallic compound include lithium, beryllium, boron, aluminum, or zinc compounds.

  As the ester compound (iv), for example, mono- or polyvalent carboxylic acid esters are used, and examples thereof include saturated aliphatic carboxylic acid esters, unsaturated aliphatic carboxylic acid esters, alicyclic carboxylic acid esters, and aromatic carboxylic acids. Mention may be made of esters. For example, methyl acetate, ethyl acetate, phenyl acetate, methyl propionate, ethyl propionate, ethyl butyrate, ethyl valerate, ethyl acrylate, methyl methacrylate, ethyl benzoate, butyl benzoate, methyl toluate, ethyl toluate, Ethyl anisate, diethyl succinate, dibutyl succinate, diethyl malonate, dibutyl malonate, dimethyl maleate, dibutyl maleate, diethyl itaconate, dibutyl itaconate, monoethyl phthalate, dimethyl phthalate, methyl ethyl phthalate, phthalate Diethyl acetate, di-n-propyl phthalate, diisopropyl phthalate, di-n-butyl phthalate, diisobutyl phthalate, dipentyl phthalate, di-n-hexyl phthalate, diheptyl phthalate, di-n-octyl phthalate , Diphthalate (2 Ethylhexyl), diisodecyl phthalate, dicyclohexyl phthalate, and diphenyl phthalate and the like.

  The ester compound (iv) is preferably an unsaturated aliphatic carboxylic acid ester such as methacrylic acid ester or maleic acid ester or an aromatic carboxylic acid ester such as phthalic acid ester, and particularly preferably a dialkyl ester of phthalic acid.

  The solid component (a) used in the present invention is preferably represented by the formula [I] in the presence of the organosilicon compound (i) or in the presence of the organosilicon compound (i) and the ester compound (iv). It is a solid component obtained by reducing titanium compound (ii) with organomagnesium compound (iii).

The titanium compound (ii), the organosilicon compound (i), and the ester compound (iv) are preferably used after being dissolved or diluted in an appropriate solvent.
Examples of the solvent include aliphatic hydrocarbon compounds such as hexane, heptane, octane, and decane, aromatic hydrocarbon compounds such as toluene and xylene, alicyclic hydrocarbon compounds such as cyclohexane, methylcyclohexane, and decalin, and diethyl ether. , Ether compounds such as dibutyl ether, diisoamyl ether, and tetrahydrofuran.

  The reaction temperature when reducing with the organomagnesium compound (iii) is usually −50 to 70 ° C., preferably −30 to 50 ° C., particularly preferably −25 to 35 ° C. The reaction time is not particularly limited, but is usually about 30 minutes to 6 hours. Thereafter, a post-reaction may be performed at a reaction temperature of 20 to 120 ° C.

When reducing with the organomagnesium compound (iii), for example, a porous carrier such as an inorganic oxide or an organic polymer may coexist and the porous carrier may be impregnated with the solid component (a). The porous carrier used may be a known one. For example, porous inorganic oxides represented by SiO ₂ , Al ₂ O ₃ , MgO, TiO ₂ , ZrO _2, etc., or polystyrene, styrene-divinylbenzene copolymer, styrene-ethylene glycol-methyl methacrylate copolymer Polymer, polymethyl acrylate, polyethyl acrylate, methyl acrylate-divinylbenzene copolymer, polymethyl methacrylate, methyl methacrylate-divinylbenzene copolymer, polyacrylonitrile, acrylonitrile-divinylbenzene copolymer, polychlorinated Examples thereof include organic porous polymers such as vinyl, polyethylene, and polypropylene. Among these, an organic porous polymer is preferable, and a styrene-divinylbenzene copolymer or an acrylonitrile-divinylbenzene copolymer is particularly preferable.

Preferably, the porous carrier preferably has a pore volume at a pore radius of 20 to 200 nm of 0.3 cm ³ / g or more, more preferably 0.4 cm ³ / g or more, from the viewpoint of effectively immobilizing the catalyst component. The pore volume in the range is 35% or more, more preferably 40% or more with respect to the pore volume at a pore radius of 3.5 to 7500 nm.

The amount of the organosilicon compound (i) used is the atomic ratio Si / Ti of silicon atoms to the total titanium atoms in the titanium compound (ii), usually 1 to 500, preferably 1 to 300, particularly preferably. 3 to 100.
The amount of the organomagnesium compound (iii) used is the sum of titanium and silicon atoms and the atomic ratio of magnesium atoms (Ti + Si) / Mg, usually 0.1 to 10, preferably 0.2 to 5.0. Yes, particularly preferably 0.5 to 2.0.
Further, the titanium compound (ii), the organosilicon compound (i), the organic compound so that the Mg / Ti molar ratio in the solid catalyst component (a) is 1 to 51, preferably 2 to 31, particularly preferably 4 to 26. You may determine the usage-amount of a magnesium compound (iii).
The amount of the ester compound (iv) that is an optional component is usually 0.05 to 100, preferably 0.1 to 100 in terms of the molar ratio of the ester compound to the titanium atom of the titanium compound (ii) and the ester compound / Ti. 60, particularly preferably 0.2-30.

The solid component (a) obtained by the reduction reaction is usually separated into solid and liquid and washed several times with an inert hydrocarbon solvent such as hexane, heptane, toluene.
The solid component (a) thus obtained contains a trivalent titanium atom, a magnesium atom and a hydrocarbyloxy group, and is generally amorphous or extremely weakly crystalline. Particularly preferred is an amorphous structure.

(B) Halogenated Compound The halogenated compound (b) is a compound that can substitute the hydrocarbyloxy group in the solid component (a) with a halogen atom. Preferred are Group 4 element halogen compounds, Group 13 element halogen compounds, Group 14 element halogen compounds, and more preferably Group 4 element halogen compounds, Group 14 element halogen compounds. It is. When the solid component (a) does not contain a titanium atom, a halogen compound having at least a titanium atom is used.

As the halogen compound of the Group 4 element of the periodic table, preferably the formula M ¹ (OR ¹⁴ ) _b X ⁴ _4-b (wherein M ¹ represents an atom of the Group 4 of the periodic table and R ¹⁴ represents a carbon atom A hydrocarbyl group of 1 to 20; X ⁴ represents a halogen atom; and b represents a number satisfying 0 ≦ b <4. Examples of M ¹ include a titanium atom, a zirconium atom, and a hafnium atom, and a titanium atom is preferable. Examples of R ¹⁴ include methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, tert-butyl group, amyl group, isoamyl group, tert-amyl group, hexyl group, heptyl group, octyl group, Examples thereof include alkyl groups such as decyl group and dodecyl group, aryl groups such as phenyl group, cresyl group, xylyl group and naphthyl group, allyl groups such as propenyl group, and aralkyl groups such as benzyl group. An alkyl group having 2 to 18 carbon atoms or an aryl group having 6 to 18 carbon atoms is preferable, and a linear alkyl group having 2 to 18 carbon atoms is particularly preferable. It is also possible to use halogen compounds of Group 4 elements having two or more different OR ¹⁴ groups.

Examples of the halogen atom represented by X ⁴ include a chlorine atom, a bromine atom, and an iodine atom. Particularly preferred is a chlorine atom.

In the periodic table Group 4 element halogen compound represented by the formula M ¹ (OR ¹⁴ ) _b X ⁴ _4-b , b is a number that satisfies 0 ≦ b <4, and preferably satisfies 0 ≦ b ≦ 2. It is a number, particularly preferably b = 0.

Examples of halogen compounds of Group 4 elements of the periodic table represented by the formula M ¹ (OR ¹⁴ ) _b X ⁴ _4-b include titanium tetrahalides such as titanium tetrachloride, titanium tetrabromide, and titanium tetraiodide. , Methoxy titanium trichloride, ethoxy titanium trichloride, butoxy titanium trichloride, phenoxy titanium trichloride, trihalogenated alkoxy titanium such as ethoxy titanium tribromide, dimethoxy titanium dichloride, diethoxy titanium dichloride, dibutoxy titanium dichloride, diphenoxy titanium Examples thereof include dihalogenated dialkoxytitanium such as dichloride and diethoxytitanium dibromide, and similarly include zirconium compounds and hafnium compounds corresponding to the respective compounds. Most preferred is titanium tetrachloride.

As a halogen compound of Group 13 element or Group 14 element of the periodic table, preferably the formula M ² R ¹⁵ _mc X ⁵ _c (wherein M ² represents a Group 13 or Group 14 atom, and R ¹⁵ represents A hydrocarbyl group having 1 to 20 carbon atoms, X ⁵ represents a halogen atom, m represents a number corresponding to the valence of M ² , and c represents a number satisfying 0 <c ≦ m). It is a compound represented.
Examples of the Group 13 atom include a boron atom, an aluminum atom, a gallium atom, an indium atom, and a thallium atom, preferably a boron atom or an aluminum atom, and more preferably an aluminum atom. Examples of the Group 14 atom include a carbon atom, a silicon atom, a germanium atom, a tin atom and a lead atom, preferably a silicon atom, a germanium atom or a tin atom, more preferably a silicon atom or a tin atom. It is.

m is a number corresponding to the valence of M ^2, for example, it is m = 4 when M ² is a silicon atom.
c represents a number satisfying 0 <c ≦ m. When M ² is a silicon atom, c is preferably 3 or 4.
Examples of the halogen atom represented by X ⁵ include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, and a chlorine atom is preferable.

Examples of R ¹⁵ include alkyl such as methyl group, ethyl group, normal propyl group, isopropyl group, normal butyl group, isobutyl group, amyl group, isoamyl group, hexyl group, heptyl group, octyl group, decyl group, and dodecyl group. Group, phenyl group, tolyl group, cresyl group, xylyl group, aryl group such as naphthyl group, cycloalkyl group such as cyclohexyl group and cyclopentyl group, alkenyl group such as propenyl group, and aralkyl group such as benzyl group. R ² is preferably an alkyl group or an aryl group, more preferably a methyl group, an ethyl group, a normal propyl group, a phenyl group or a paratolyl group.

  Examples of halogen compounds of Group 13 elements of the periodic table include trichloroborane, methyldichloroborane, ethyldichloroborane, phenyldichloroborane, cyclohexyldichloroborane, dimethylchloroborane, methylethylchloroborane, trichloroaluminum, methyldichloroaluminum, ethyl Dichloroaluminum, phenyldichloroaluminum, cyclohexyldichloroaluminum, dimethylchloroaluminum, diethylchloroaluminum, methylethylchloroaluminum, ethylaluminum sesquichloride, gallium chloride, gallium dichloride, trichlorogallium, methyldichlorogallium, ethyldichlorogallium, phenyldichlorogallium, Cyclohexyl dichlorogallium, dimethyl chloride Examples include gallium, methylethylchlorogallium, indium chloride, indium trichloride, methylindium dichloride, phenylindium dichloride, dimethylindium chloride, thallium chloride, thallium trichloride, methylthallium dichloride, phenylthallium dichloride, dimethylthallium chloride, and the like. Also included are compounds in which “chloro” in the compound name is replaced with “fluoro”, “bromo”, or “iodo”.

  Examples of halogen compounds of Group 14 elements of the periodic table include, for example, tetrachloromethane, trichloromethane, dichloromethane, monochloromethane, 1,1,1-trichloroethane, 1,1-dichloroethane, 1,2-dichloroethane, 1,1,2, , 2-tetrachloroethane, tetrachlorosilane, trichlorosilane, methyltrichlorosilane, ethyltrichlorosilane, normal propyltrichlorosilane, normal butyltrichlorosilane, phenyltrichlorosilane, benzyltrichlorosilane, paratolyltrichlorosilane, cyclohexyltrichlorosilane, dichlorosilane, Methyldichlorosilane, ethyldichlorosilane, dimethyldichlorosilane, diphenyldichlorosilane, methylethyldichlorosilane, monochlorosilane, trimethyl Lorosilane, triphenylchlorosilane, tetrachlorogermane, trichlorogermane, methyltrichlorogermane, ethyltrichlorogermane, phenyltrichlorogermane, dichlorogermane, dimethyldichlorogermane, diethyldichlorogermane, diphenyldichlorogermane, monocrologermane, trimethylchlorogermane, triethylchlorogermane , Trinormalbutylchlorogermane, tetrachlorotin, methyltrichlorotin, normalbutyltrichlorotin, dimethyldichlorotin, dinormalbutyldichlorotin, diisobutyldichlorotin, diphenyldichlorotin, divinyldichlorotin, methyltrichlorotin, phenyltrichlorotin, Examples include dichloro lead, methyl chloro lead, phenyl chloro lead, etc. "To" fluoro ", compounds obtained by replacing the" bromo "or" iodo "can also be mentioned. Preferred halogen compounds of Group 14 elements are tetrachlorosilane, methyltrichlorosilane, ethyltrichlorosilane, normal propyltrichlorosilane, normal butyltrichlorosilane, phenyltrichlorosilane, tetrachlorotin, methyltrichlorotin, and normalbutyltrichlorotin. .

As the halogenated compound (b), from the viewpoint of polymerization activity, titanium tetrachloride, methyldichloroaluminum, ethyldichloroaluminum, tetrachlorosilane, phenyltrichlorosilane, methyltrichlorosilane, ethyltrichlorosilane, normal propyltrichlorosilane or tetrachloro are preferable. Tin, particularly preferably titanium tetrachloride or tetrachlorosilane.
As a halogenated compound (b), 1 type of the said compound may be used, and 2 or more types may be used together.

(C) Electron Donor In the present invention, a contact treatment using the electron donor (c) can be appropriately performed in the preparation of the solid catalyst component. In some cases, high polymerization activity and copolymerization performance can be imparted by contact treatment with an electron donor. As electron donors, oxygen-containing electron donating compounds such as ethers, ketones, aldehydes, carboxylic acids, esters of organic or inorganic acids, acid amides of organic or inorganic acids, acid anhydrides, Nitrogen-containing electron donating compounds such as ammonia, amines, nitriles and isocyanates can be mentioned. Of these electron donating compounds, esters of organic acids and / or ethers are preferred, and carboxylic acid esters (c1) and / or ethers (c2) are more preferred.

（ただし、上式において、Ｒ¹⁶〜Ｒ¹⁹はそれぞれ独立に、水素原子、炭素原子からなる置換基を表し、Ｘ⁶、Ｘ⁷はそれぞれ独立に、水素原子、炭素原子または酸素原子からなる置換基を表す。）
Ｒ¹⁶〜Ｒ¹⁹として好ましくは、水素原子または炭素原子数１〜１０の炭化水素基であり、各置換基は互いに結合していてもよい。Ｘ⁶、Ｘ⁷として好ましくは、ヒドロキシ基、炭素原子数１〜２０のアルコキシ基である。また、芳香族環の一部または全部は水添されていてもよい。 Examples of the carboxylic acid esters (c1) include mono- and polyvalent carboxylic acid esters, and examples thereof include saturated aliphatic carboxylic acid esters, unsaturated aliphatic carboxylic acid esters, alicyclic carboxylic acid esters, Aromatic carboxylic acid esters can be mentioned. Specifically, for example, methyl acetate, ethyl acetate, phenyl acetate, methyl propionate, ethyl propionate, ethyl butyrate, ethyl valerate, ethyl acrylate, methyl methacrylate, ethyl benzoate, butyl benzoate, methyl toluate , Ethyl toluate, ethyl anisate, diethyl succinate, dibutyl succinate, diethyl malonate, dibutyl malonate, dimethyl maleate, dibutyl maleate, diethyl itaconate, dibutyl itaconate and phthalates represented by the following formula Can be mentioned.

(However, in the above formula, R ^{16 to} R ¹⁹ each independently represent a substituent consisting of a hydrogen atom or a carbon atom, and X ⁶ and X ⁷ are each independently a substituent consisting of a hydrogen atom, a carbon atom or an oxygen atom. Represents a group.)
R ^{16 to} R ¹⁹ are preferably a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms, and each substituent may be bonded to each other. X ⁶ and X ⁷ are preferably a hydroxy group or an alkoxy group having 1 to 20 carbon atoms. Further, part or all of the aromatic ring may be hydrogenated.

  Examples of the phthalic acid derivative represented by the above formula include phthalic acid, monoethyl phthalate, dimethyl phthalate, methyl ethyl phthalate, diethyl phthalate, di-normal phthalate, diisopropyl phthalate, di-normal butyl phthalate, and phthalate. Diisobutyl phthalate, dipentyl phthalate, dinormal hexyl phthalate, di-normal heptyl phthalate, diisoheptyl phthalate, di-normal octyl phthalate, di (2-ethylhexyl) phthalate, di-nordecyl phthalate, diisodecyl phthalate, phthalic acid Examples include dicyclohexyl, diphenyl phthalate, and dichloride phthalate. Preferred examples include diethyl phthalate, di-normal phthalate, diisopropyl phthalate, di-normal butyl phthalate, and diisobutyl phthalate. That.

Of these carboxylic acid esters, unsaturated aliphatic carboxylic acid esters such as methacrylic acid esters and maleic acid esters or aromatic carboxylic acid esters such as benzoic acid esters and phthalic acid esters are preferably used. More preferably, it is an aromatic polyvalent carboxylic acid ester, more preferably a dialkyl phthalate, and particularly preferably a dialkyl phthalate in which the total number of carbon atoms of two alkyl groups is 8 or less. .
These carboxylic acid esters may be used alone or in a single contact treatment, or may be used in a series of solid catalyst component productions.

Examples of ethers include dialkyl ether compounds, cyclic ether compounds, and 1,3-diether compounds.

  Examples of the dialkyl ether compound include dimethyl ether, diethyl ether, di-n-propyl ether, diisopropyl ether, di-n-butyl ether, diisobutyl ether, methyl-n-propyl ether, methyl-n-butyl ether, ethyl-n-propyl. Examples include ether, ethyl-n-butyl ether, and methylcyclohexyl ether, and di-n-butyl ether is preferable. Di-n-butyl ether may be simply referred to as dibutyl ether or butyl ether.

The cyclic ether compound is a heterocyclic compound having at least one —C—O—C— bond in the ring.
Examples of the cyclic ether compound include ethylene oxide, propylene oxide, trimethylene oxide, tetrahydrofuran, 2,5-dimethoxytetrahydrofuran, tetrahydropyran, hexamethylene oxide, 1,3-dioxepane, 1,3-dioxane, 1,4-dioxane. 1,3-dioxolane, 2-methyl-1,3-dioxolane, 2,2-dimethyl-1,3-dioxolane, 4-methyl-1,3-dioxolane, 2,4-dimethyl-1,3-dioxolane , Furan, 2,5-dimethylfuran, or s-trioxane. Among them, preferred is a cyclic ether having at least one —C—O—C—O—C— bond in the ring.

（ただし、上式［ＩＩＩ］において、Ｒ²⁰〜Ｒ²³はそれぞれ独立に炭素原子数１〜２０の直鎖状、分岐状または脂環式のアルキル基、アリール基またはアラルキル基であり、Ｒ²⁰およびＲ²¹はそれぞれ独立に水素原子であってもよい。また、Ｒ²⁰とＲ²¹は互いに結合していてもよい。）
具体的には、例えば、２，２−ジイソブチル−１，３−ジメトキシプロパン、２−イソプロピル−２−イソペンチル−１，３−ジメトキシプロパン、２，２−ビス（シクロヘキシルメチル）−１，３−ジメトキシプロパン、２−イソプロピル−２−３，７−ジメチルオクチル−１，３−ジメトキシプロパン、２，２−ジイソプロピル−１，３−ジメトキシプロパン、２−イソプロピル−２−シクロヘキシルメチル−１，３−ジメトキシプロパン、２，２−ジシクロヘキシル−１，３−ジメトキシプロパン、２−イソプロピル−２−イソブチル−１，３−ジメトキシプロパン、２，２−ジイソプロピル−１，３−ジメトキシプロパン、２，２−ジプロピル−１，３−ジメトキシプロパン、２−イソプロピル−２−シクロヘキシル−１，３−ジメトキシプロパン、２−イソプロピル−２−シクロペンチル−１，３−ジメトキシプロパン、２，２−ジシクロペンチル−１，３−ジメトキシプロパン、２−ヘプチル−２−ペンチル−１，３−ジメトキシプロパン等が挙げられる。
これら電子供与体は、１回の接触処理において１種類または複数種類を用いてもよいし、一連の固体触媒成分の製造において１種類または複数種類を用いてもよい。 Examples of the 1,3-diether include a diether compound represented by the following formula [III].

(However, in the above formula [III], R ²⁰ ~R ²³ independently represents a 1 to 20 carbon atoms of straight, branched or alicyclic alkyl group, an aryl group or an aralkyl group, R ²⁰ And R ²¹ may independently be a hydrogen atom, and R ²⁰ and R ²¹ may be bonded to each other.)
Specifically, for example, 2,2-diisobutyl-1,3-dimethoxypropane, 2-isopropyl-2-isopentyl-1,3-dimethoxypropane, 2,2-bis (cyclohexylmethyl) -1,3-dimethoxy Propane, 2-isopropyl-2-3,7-dimethyloctyl-1,3-dimethoxypropane, 2,2-diisopropyl-1,3-dimethoxypropane, 2-isopropyl-2-cyclohexylmethyl-1,3-dimethoxypropane 2,2-dicyclohexyl-1,3-dimethoxypropane, 2-isopropyl-2-isobutyl-1,3-dimethoxypropane, 2,2-diisopropyl-1,3-dimethoxypropane, 2,2-dipropyl-1, 3-dimethoxypropane, 2-isopropyl-2-cyclohexyl-1,3-dimethyl Kishipuropan, 2-isopropyl-2-cyclopentyl-1,3-dimethoxypropane, 2,2-dicyclopentyl-1,3-dimethoxypropane, 2-heptyl-2-pentyl-1,3-dimethoxypropane and the like.
One or a plurality of these electron donors may be used in one contact treatment, or one or a plurality of types may be used in the production of a series of solid catalyst components.

(D) Organic acid halide As the organic acid halide (d) used for the preparation of the solid catalyst component of the present invention, mono- or polyvalent carboxylic acid halides are preferably used, examples of which are aliphatic carboxylic acid halides, Examples thereof include alicyclic carboxylic acid halides and aromatic carboxylic acid halides. Specific examples include acetyl chloride, propionic acid chloride, butyric acid chloride, valeric acid chloride, acrylic acid chloride, methacrylic acid chloride, benzoic acid chloride, toluic acid chloride, anisic acid chloride, succinic acid chloride, malonic acid chloride, maleic acid chloride. Itaconic acid chloride, phthalic acid chloride and the like.

  Of these organic acid halides, preferred are aromatic carboxylic acid chlorides such as benzoic acid chloride, toluic acid chloride, and phthalic acid chloride, more preferred are aromatic dicarboxylic acid dichlorides, and particularly preferred is phthalic acid chloride. .

(A) Preparation of solid catalyst component The preferred solid catalyst component (A) includes a solid component (a) containing a titanium atom, a magnesium atom and a hydrocarbyloxy group, a halogenated compound (b) and an electron donor (c). And / or by contacting with an organic acid halide (d). All of these contact treatments are usually performed in an inert gas atmosphere such as nitrogen or argon.

As a specific method of contact treatment for obtaining a solid catalyst component,
-A method in which (b) or (c) (arbitrary order) is input to (a) and contact processing is performed,
-A method in which (b) and (d) (arrangement order is arbitrary) are input to (a) and contact processing is performed,
-A method in which the mixture of (b), (c), and (d) is charged into (a) and subjected to contact treatment,
-A method in which a mixture of (b) and (c), (d) (arbitrary order) is added to (a), and contact treatment is performed,
A method in which (c) is introduced into (a) and subjected to contact treatment, and then (b) is introduced and subjected to contact treatment,
-A method in which (c) is added to (a) and contact processing is performed, and then (b) and (c) (arbitrary order is input) and contact processing is performed,
A method in which (c) is charged into (a) and contact-treated, and then a mixture of (b) and (c) is charged and contact-treated,
A method of performing contact processing by putting (a), (c) (arbitrary order) into (b),
-A method in which (a), (d) (arrangement order is arbitrary) is input to (b) and contact processing is performed,
A method of performing contact processing by introducing (a), (c), (d) (arbitrary order) into (b),
In addition, after these contact treatments, a method in which contact treatment is further performed once or more in (b) and a method in which contact treatment is performed once or more with a mixture of (b) and (c) can be mentioned.

  Among these, (b), (d) (arrangement order is arbitrary) are charged into (a), and contact processing is performed. (A) is a mixture of (b) and (c). (D) (arrangement order is arbitrary) (A), a mixture of (b) and (c), (d) (arrangement order is arbitrary), and after contact treatment, a mixture of (b) and (c) is introduced. A method of performing contact treatment more than once, a method in which (c) is added to (a), contact treatment, and then contact treatment with a mixture of (b) and (c) at least once is preferable. And a mixture of (c), each in the order of (d), contact treatment, (a) mixture of (b) and (c), each in the order of (d), contact treatment Then, the mixture of (b) and (c) is added and the contact treatment is performed one or more times, or (c) is charged into (a) and the contact treatment is performed, and then (b) and (c) How to contact treated one or more times with a mixture is more preferable. Particularly preferably, the mixture of (b) and (c2) and the mixture of (b), (c2), and the mixture of (b), (c1), and (c2) are respectively added to (a) in the order (d). A method of performing a contact treatment and further performing a contact treatment at least once with a mixture of (b) and (c2), or (a) by adding (c1) to the contact treatment, and then (b) and (c1) In this method, the mixture of (c2) is charged, contact treatment is performed, and contact treatment is further performed once or more with the mixture of (b) and (c2).

  The contact treatment can be performed by any known method capable of bringing each component into contact, such as a mechanical grinding means such as a slurry method or a ball mill. However, when mechanical grinding is performed, generation of fine powder of the solid catalyst component is generated. From the viewpoint of suppressing and not widening the particle size distribution, the contact is preferably performed in the presence of a diluent.

  The diluent is preferably a diluent that is inert to the component to be treated, for example, aliphatic hydrocarbons such as pentane, hexane, heptane, octane, decane, and aromatics such as benzene, toluene, ethylbenzene, and xylene. Hydrocarbons, cycloaliphatic hydrocarbons such as cyclopentane and cyclopentane, halogenated hydrocarbons such as 1,2-dichloroethane and monochlorobenzene, preferably aliphatic hydrocarbons and aromatic hydrocarbons, more preferably Aromatic hydrocarbons, more preferably toluene and xylene.

  The amount of diluent used in the contact treatment is usually 0.1 ml to 1000 ml per gram of the solid component (a). It is preferably 1 ml to 100 ml per gram.

  The contact treatment time is not particularly limited, but is preferably 0.5 to 8 hours, and more preferably 1 to 6 hours. The temperature of the contact treatment is usually −50 to 150 ° C., preferably 0 to 140 ° C., more preferably 60 to 135 ° C.

  Following the [I] contact treatment of the solid catalyst component (A), [II] washing treatment is performed in which the contact product obtained in [I] is washed with an aromatic hydrocarbon solvent. Examples of the aromatic hydrocarbon solvent used for the washing treatment include aromatic hydrocarbons similar to the diluent, and among these, toluene and xylene are preferable.

The amount of the aromatic hydrocarbon solvent used for one cleaning treatment is the same as the amount of the diluent used for the contact treatment. The washing temperature in the washing treatment is usually −50 to 150 ° C., preferably 0 to 140 ° C., more preferably 60 to 135 ° C., and the number of washings is usually 1 to 5 times. If necessary, the number of washings may be further increased.
Although the washing treatment time is not particularly limited, it is preferably 1 to 120 minutes, more preferably 2 to 60 minutes, and further preferably 5 to 40 minutes.

  In the contact treatment and the washing treatment, stirring is preferably performed so that a uniform slurry state is maintained. When stirring is insufficient, each process becomes inadequate and stereoregularity and polymerization activity may not be enough. Moreover, when stirring is too strong, a particle | grain may be destroyed.

  After the contact treatment and the washing treatment, some or almost all of the liquid component is removed. If a large amount of the liquid component remains, removal of unreacted substances becomes insufficient, which is not preferable from the viewpoint of stereoregularity and polymerization activity. Examples of the method for removing the liquid component include a method in which the liquid component is filtered through a filter having an appropriate opening, a method in which the solid component is separated by settling, and then the supernatant liquid component is removed.

  The usage-amount of a halogenated compound (b) is 0.5-1000 mmol normally with respect to 1 g of solid components (a), Preferably it is 1-200 mmol, More preferably, it is 2-100 mmol. In using the halogenated compound (b), it is preferable to use the electron donor (c) together. In this case, the amount of (c) used relative to 1 mol of (b) is usually 1 to 100 mol, preferably 1.5 to 75 mol, and more preferably 2 to 50 mol.

  The usage-amount of an electron donor (c) is 0.01-100 mmol normally with respect to 1 g of solid components (a), Preferably it is 0.05-50 mmol, More preferably, it is 0.1-20 mmol.

  The usage-amount of organic acid halide (d) is 0.1-100 mmol normally with respect to 1 g of solid components (a), Preferably it is 0.3-50 mmol, More preferably, it is 0.5-20 mmol. Moreover, the usage-amount of the organic acid halide (d) per 1 mol of magnesium atoms in a solid component (a) is 0.01-1.0 mol normally, Preferably it is 0.03-0.5 mol. When the amount of (c) or (d) used is excessively large, particle collapse may occur.

  When the contact treatment is performed using each compound a plurality of times, the amount of each compound described above represents the amount of each compound used once and for each kind of compound.

  The obtained solid catalyst component may be used for polymerization in a slurry state in combination with an inert diluent, or may be used for polymerization as a fluid powder obtained by drying. Examples of the drying method include a method of removing volatile components under reduced pressure conditions, and a method of removing volatile components under the flow of an inert gas such as nitrogen and argon. The temperature at the time of drying is preferably 0 to 200 ° C, more preferably 50 to 100 ° C. The drying time is preferably 0.01 to 20 hours, and more preferably 0.5 to 10 hours.

(B) Organoaluminum compound and / or organoaluminum oxy compound The organoaluminum compound and / or organoaluminum oxy compound (B) used for forming the olefin copolymerization catalyst has at least one Al-carbon bond in the molecule. It is what has. A typical one is shown in the following general formula.
R ²⁴ _w AlX ⁸ _3-w
R ²⁵ R ²⁶ Al-O-AlR ²⁷ R ²⁸
(Wherein R ^{24 to} R ²⁸ represent a hydrocarbyl group having 1 to 20 carbon atoms, X ⁸ represents a halogen atom, a hydrogen atom or an alkoxy group, and w is a number satisfying 2 ≦ w ≦ 3.)
Specific examples of such organoaluminum compounds include trialkylaluminum such as triethylaluminum, triisobutylaluminum, and trihexylaluminum, dialkylaluminum hydride such as diethylaluminum hydride and diisobutylaluminum hydride, dialkylaluminum halide such as diethylaluminum chloride, and triethylaluminum. Examples thereof include a mixture of a trialkylaluminum and a dialkylaluminum halide such as a mixture of benzene and diethylaluminum chloride, and an alkylalumoxane such as tetraethyldialumoxane and tetrabutyldialumoxane.

  Among these organoaluminum compounds, trialkylaluminum, a mixture of trialkylaluminum and dialkylaluminum halide, or alkylalumoxane is preferable, and triethylaluminum, triisobutylaluminum, a mixture of triethylaluminum and diethylaluminum chloride or tetraethyl is particularly preferable. Dialumoxane is preferred.

In addition to the aromatic nitrogen heterocyclic compound (C) having at least one alkyl group having 1 to 3 carbon atoms adjacent to the nitrogen atom to form an olefin polymerization catalyst, an electron as necessary A donating compound (D) may be added. Examples of the electron donating compound (D) include an oxygen-containing compound, a nitrogen-containing compound, a phosphorus-containing compound, and a sulfur-containing compound, and among them, an oxygen-containing compound or a nitrogen-containing compound is preferable.
Examples of the oxygen-containing compound include alkoxy silicons, ethers, esters, ketones and the like, and among them, alkoxy silicons or ethers are preferable.

Examples of the alkoxysilicones include the general formula R ²⁹ _r Si (OR ³⁰ ) _4-r (wherein R ²⁹ represents a hydrocarbyl group having 1 to 20 carbon atoms, a hydrogen atom, or a heteroatom-containing substituent, and R ³⁰ represents Represents a hydrocarbyl group having 1 to 20 carbon atoms, and r represents a number satisfying 0 ≦ r <4. All R ²⁹ and all R ³⁰ may be the same or different. An alkoxysilicon compound is used. When R ²⁹ is a hydrocarbyl group, for example, a linear alkyl group such as methyl group, ethyl group, propyl group, butyl group, pentyl group, isopropyl group, sec-butyl group, tert-butyl group, tert-amyl group, And a branched alkyl group such as cyclopentyl group and cyclohexyl group, a cycloalkenyl group such as cyclopentenyl group, and an aryl group such as phenyl group and tolyl group. Among these, it is preferable that the carbon atom directly bonded to the silicon atom of the alkoxysilicon compound has at least one R ²⁹ which is a secondary carbon atom or a tertiary carbon atom. When R ²⁹ is a hetero atom-containing substituent, examples of the hetero atom include an oxygen atom, a nitrogen atom, a sulfur atom, and a phosphorus atom. Specifically, dimethylamino group, methylethylamino group, diethylamino group, ethyl-n-propylamino group, di-n-propylamino group, pyrrolyl group, pyridyl group, pyrrolidinyl group, piperidyl group, perhydroindolyl group, Examples include perhydroisoindolyl, perhydroquinolyl, perhydroisoquinolyl, perhydrocarbazolyl, perhydroacridinyl, furyl, pyranyl, perhydrofuryl, and thienyl groups. Among them, a substituent in which a hetero atom can be directly chemically bonded to a silicon atom of an alkoxysilicon compound is preferable.

  Examples of the alkoxysilicon compound include diisopropyldimethoxysilane, diisobutyldimethoxysilane, di-tert-butyldimethoxysilane, tert-butylmethyldimethoxysilane, tert-butylethyldimethoxysilane, tert-butyl-n-propyldimethoxysilane, tert- Butyl-n-butyldimethoxysilane, tert-amylmethyldimethoxysilane, tert-amylethyldimethoxysilane, tert-amyl-n-propyldimethoxysilane, tert-amyl-n-butyldimethoxysilane, isobutylisopropyldimethoxysilane, tert-butyl Isopropyldimethoxysilane, dicyclobutyldimethoxysilane, cyclobutylisopropyldimethoxysilane, cyclobutylisobutene Rudimethoxysilane, cyclobutyl-tert-butyldimethoxysilane, dicyclopentyldimethoxysilane, cyclopentylisopropyldimethoxysilane, cyclopentylisobutyldimethoxysilane, cyclopentyl-tert-butyldimethoxysilane, dicyclohexyldimethoxysilane, cyclohexylmethyldimethoxysilane, cyclohexylethyldimethoxysilane, cyclohexyl Isopropyldimethoxysilane, cyclohexylisobutyldimethoxysilane, cyclohexyl-tert-butyldimethoxysilane, cyclohexylcyclopentyldimethoxysilane, cyclohexylphenyldimethoxysilane, diphenyldimethoxysilane, phenylmethyldimethoxysilane, phenylisopropyldimethoxysilane , Phenylisobutyldimethoxysilane, phenyl-tert-butyldimethoxysilane, phenylcyclopentyldimethoxysilane, diisopropyldiethoxysilane, diisobutyldiethoxysilane, di-tert-butyldiethoxysilane, tert-butylmethyldiethoxysilane, tert-butylethyl Diethoxysilane, tert-butyl-n-propyldiethoxysilane, tert-butyl-n-butyldiethoxysilane, tert-amylmethyldiethoxysilane, tert-amylethyldiethoxysilane, tert-amyl-n-propyldi Ethoxysilane, tert-amyl-n-butyldiethoxysilane, dicyclopentyldiethoxysilane, dicyclohexyldiethoxysilane, cyclohexylmethyldiethoxy Sisilane, cyclohexylethyldiethoxysilane, diphenyldiethoxysilane, phenylmethyldiethoxysilane, 2-norbornanemethyldimethoxysilane, bis (perhydroquinolino) dimethoxysilane, bis (perhydroisoquinolino) dimethoxysilane, (perhydroquinolino ) (Perhydroisoquinolino) dimethoxysilane, (perhydroquinolino) methyldimethoxysilane, (perhydroisoquinolino) methyldimethoxysilane, (perhydroquinolino) ethyldimethoxysilane, (perhydroisoquinolino) ethyldimethoxysilane , (Perhydroquinolino) (n-propyl) dimethoxysilane, (perhydroisoquinolino) (n-propyl) dimethoxysilane, ((perhydroquinolino) (tert-butyl) dimethoxy Silane, (perhydroisoquinolino) (tert-butyl) dimethoxysilane, diethylamino dimethoxysilane include diethylamino diethoxy silane.

  Examples of ethers include the cyclic ether compounds and 1,3-diether compounds exemplified in the electron donor (c).

  Examples of the nitrogen-containing compound include 2,6-substituted piperidines such as 2,6-dimethylpiperidine, 2,2,6,6-tetramethylpiperidine, 2,5-substituted piperidines, N, N, N ′. , N′-tetramethylmethylenediamine, substituted methylenediamines such as N, N, N ′, N′-tetraethylmethylenediamine, and substituted imidazolidines such as 1,3-dibenzylimidazolidine. Of these, 2,6-substituted piperidines are preferable.

  The electron donating compound (D) is particularly preferably cyclohexylmethyldimethoxysilane, cyclohexylethyldimethoxysilane, diisopropyldimethoxysilane, tert-butylethyldimethoxysilane, tert-butyl-n-propyldimethoxysilane, phenyldimethoxysilane, diphenyldimethoxysilane. , Dicyclobutyldimethoxysilane, dicyclopentyldimethoxysilane, 1,3-dioxolane, 1,3-dioxane, 2,6-dimethylpiperidine, 2,2,6,6-tetramethylpiperidine, 2-isopropyl-2-isobutyl -1,3-dimethoxypropane, 2-isopropyl-2-isopentyl-1,3-dimethoxypropane, 2,2-diisobutyl-1,3-dimethoxypropane, 2,2-diisopropyl It is a 1,3-dimethoxypropane or 2,2-dicyclohexyl-1,3-dimethoxypropane.

[Olefin copolymerization]
In the production of an olefin copolymer using the olefin copolymerization catalyst obtained by the present invention, the olefin represents ethylene and an α-olefin having 3 or more carbon atoms, and specific examples of the α-olefin include propylene. 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-decene and other linear monoolefins, 3-methyl-1-butene, 3-methyl-1-pentene, 4- Examples thereof include branched monoolefins such as methyl-1-pentene, vinylcyclohexane and the like, and any two or more kinds may be used in combination. Furthermore, a compound having a polyunsaturated bond such as a conjugated diene or a non-conjugated diene can be used for the copolymerization.

  The combination of these olefins is preferably ethylene and α-olefin, more preferably ethylene and linear α-olefin, still more preferably ethylene and propylene, ethylene and 1-butene, ethylene and 1-hexene and Ethylene and 1-octene, particularly preferably ethylene and propylene and ethylene and 1-butene, most preferably ethylene and propylene.

  The olefin copolymer produced using the olefin copolymerization catalyst of the present invention is preferably an ethylene-α-olefin copolymer, more preferably an ethylene-linear α-olefin copolymer, Preferably, ethylene-propylene copolymer, ethylene-1-butene copolymer, ethylene-1-hexene copolymer, ethylene-1-octene copolymer, propylene-1-butene copolymer and propylene-1- A hexene copolymer, particularly preferably an ethylene-propylene copolymer and an ethylene-1-butene copolymer, and most preferably an ethylene-propylene copolymer.

  As a copolymerization composition of the said preferable olefin copolymer, the monomer unit derived from ethylene is 10-90 mol% normally. Preferably, the monomer unit derived from ethylene is 30 to 80 mol%, more preferably the monomer unit derived from ethylene is 40 to 75 mol%.

The highly random olefin copolymer produced using the catalyst for olefin copolymer of the present invention is an arrangement of _two olefin monomers M ₁ and M _{2 in} the olefin copolymer, that is, a monomer sequence. It is an olefin copolymer whose distribution is statistically close to random. As an index of randomness of the monomer sequence distribution, for example, the product r ₁ r ₂ of the reactivity ratio of each olefin monomer can be mentioned. Here r1 is the relative reactivity of the olefinic monomers M ₁ and M ₂ when the growing end of the olefin copolymer is a monomer unit derived from the olefin monomer M _1, r _2, the olefin copolymer The relative reactivity of M ₂ and M ₁ when the growth terminal is a monomer unit derived from the olefin monomer M ₂ . It indicates that if the monomer reactivity ratio product r ₁ r ₂ is smaller than ₁ , M ₁ and M ₂ are likely to enter the main chain of the copolymer alternately, and if it is larger than 1, it is likely to enter in a block manner. Yes. When the product of the monomer reactivity ratios r ₁ r ₂ = 1, it is particularly called ideal copolymerization, and the olefin monomers M ₁ and M ₂ are distributed at random. That is, the closer r ₁ r ₂ is to 1, the higher the randomness. The range of the product r ₁ r ₂ of the reactivity ratio in the present invention is preferably 1.0 to 3.0, more preferably 1.0 to 2.5, and still more preferably 1.0 to 2.0. And particularly preferably 1.0 to 1.5.

  The olefin copolymer of the present invention may be copolymerized only with the above-mentioned combination of olefins, or a heteroblock copolymer in which polymerization is carried out in two or more stages, such as copolymerization after homopolypropylene polymerization. You may carry out by superposition | polymerization.

  The olefin copolymerization catalyst of the present invention comprises the above-mentioned solid catalyst component (A), organoaluminum and / or organoaluminum oxy compound (B), and at least one carbon atom adjacent to the nitrogen atom having 1 to 3 carbon atoms. Is an olefin copolymerization catalyst obtained by contacting an aromatic nitrogen heterocyclic compound (C) having an alkyl group. The term “contact” as used herein may be any means as long as the catalyst components (A), (B) and (C) are brought into contact with each other to form a catalyst. The components may be diluted with a solvent in advance or not. A method in which (A), (B) and (C) are mixed and brought into contact with each other, a method in which the mixture is separately supplied to the polymerization vessel and brought into contact in the polymerization vessel, and the like can be adopted. As a method of supplying each catalyst component to the polymerization tank, it is preferable to supply the catalyst components in an inert gas such as nitrogen or argon in the absence of moisture. Each catalyst component may be supplied in contact with either two or three members in advance.

  Although it is possible to polymerize olefins in the presence of the catalyst, prepolymerization described below may be performed before such polymerization (main polymerization).

  The prepolymerization is usually carried out by supplying a small amount of olefin in the presence of the solid catalyst component (A) and the organoaluminum compound and / or the organoaluminum oxy compound (B), and is preferably carried out in a slurry state. Examples of the solvent used for slurrying include inert hydrocarbons such as propane, butane, isobutane, pentane, isopentane, hexane, heptane, octane, cyclohexane, benzene, and toluene. Further, when slurrying, a liquid olefin can be used instead of a part or all of the inert hydrocarbon solvent.

  The amount of the organoaluminum compound used in the prepolymerization can be selected in a wide range such as 0.5 to 700 mol per mol of titanium atom in the solid catalyst component, but preferably 0.8 to 500 mol. ˜200 mol is particularly preferred.

  The amount of olefin to be prepolymerized is usually 0.01 to 1000 g, preferably 0.05 to 500 g, particularly preferably 0.1 to 200 g, per 1 g of the solid catalyst component.

  The slurry concentration during the prepolymerization is preferably 1 to 500 g-solid catalyst component / liter-solvent, and more preferably 3 to 300 g-solid catalyst component / liter-solvent. The prepolymerization temperature is preferably -20 to 100 ° C, particularly preferably 0 to 80 ° C. Further, the partial pressure of the olefin in the gas phase during the prepolymerization is preferably from 1 kPa to 2 MPa, and particularly preferably from 10 kPa to 1 MPa. However, the olefin that is liquid at the prepolymerization pressure and temperature is not limited thereto. Further, the prepolymerization time is not particularly limited, but usually 2 minutes to 15 hours is preferable.

  In carrying out the prepolymerization, the solid catalyst component (A), the organoaluminum compound and / or the organoaluminum oxy compound (B), and the olefin may be supplied by a method of supplying the solid catalyst component (A), the organoaluminum compound and / or organic. Method of supplying olefin after contacting aluminum oxy compound (B), supplying organoaluminum compound and / or organoaluminum oxy compound (B) after contacting solid catalyst component (A) and olefin Any method such as a method may be used. In addition, as a method for supplying olefin, either a method of sequentially supplying olefin while maintaining the inside of the polymerization tank at a predetermined pressure, or a method of supplying all of the predetermined amount of olefin first is used. Good. It is also possible to add a chain transfer agent such as hydrogen in order to adjust the molecular weight of the resulting copolymer.

  Further, when the solid catalyst component (A) is prepolymerized with a small amount of olefin in the presence of the organoaluminum compound and / or the organoaluminum oxy compound (B), at least one or more carbons adjacent to the nitrogen atom as necessary. An aromatic nitrogen heterocyclic compound (C) or an electron donating compound (D) having an alkyl group having 1 to 3 carbon atoms in the atom may coexist. The electron donating compound (D) used is an aromatic nitrogen heterocyclic compound (C) or an electron having an alkyl group having 1 to 3 carbon atoms on at least one carbon atom adjacent to the nitrogen atom. Part or all of the donating compound (D). The amount used is usually 0.01 to 400 mol, preferably 0.02 to 200 mol, particularly preferably 0.03 to 100 mol, per 1 mol of titanium atoms contained in the solid catalyst component (A). Yes, with respect to the organoaluminum compound and / or the organoaluminum oxy compound (B), it is usually 0.003 to 5 mol, preferably 0.005 to 3 mol, particularly preferably 0.01 to 2 mol.

  Method for supplying aromatic nitrogen heterocyclic compound (C) or electron donating compound (D) having an alkyl group having 1 to 3 carbon atoms in at least one or more carbon atoms adjacent to nitrogen atom in preliminary polymerization The organic aluminum compound and / or the organic aluminum oxy compound (B) may be supplied separately or may be supplied in contact with each other. Further, the olefin used in the prepolymerization may be the same as or different from the olefin used in the main polymerization.

  After performing the prepolymerization as described above or without performing the prepolymerization, at least one adjacent to the solid catalyst component (A), the organoaluminum compound and / or the organoaluminum oxy compound (B), and the nitrogen atom. The main polymerization of olefin can be carried out in the presence of an olefin polymerization catalyst comprising an aromatic nitrogen heterocyclic compound (C) having a substituent having an alkyl group having 1 to 3 carbon atoms on one or more carbon atoms. it can.

  The amount of the organoaluminum compound used in the main polymerization can usually be selected in a wide range such as 1 to 1000 mol per 1 mol of the titanium atom in the solid catalyst component (A), particularly preferably in the range of 5 to 600 mol. It is.

  Moreover, the aromatic nitrogen heterocyclic compound (C) which has a substituent which has a C1-C3 alkyl group in the at least 1 or more carbon atom adjacent to the nitrogen atom used at the time of this superposition | polymerization is a solid catalyst. It is 0.1-2000 mol normally with respect to 1 mol of titanium atoms contained in a component (A), Preferably it is 0.3-1000 mol, Most preferably, it is 0.5-800 mol, Usually, it is 0.001 to 5 mol, preferably 0.005 to 3 mol, particularly preferably 0.01 to 1 mol.

  The polymerization temperature of the main polymerization can be carried out usually from -30 to 300 ° C, but preferably from 20 to 180 ° C. Although there is no restriction | limiting in particular about the superposition | polymerization pressure, Generally the pressure of a normal pressure-10MPa, Preferably about 200kPa-5MPa is employ | adopted by the point that it is industrial and economical. As the polymerization method, either batch type or continuous type is possible. In addition, slurry polymerization or solution polymerization using an inert hydrocarbon solvent such as propane, butane, isobutane, pentane, hexane, heptane, and octane, and bulk polymerization or gas phase polymerization using a liquid olefin as a medium at the polymerization temperature are also possible.

  In the main polymerization, a chain transfer agent such as hydrogen can be added to adjust the molecular weight of the copolymer.

  EXAMPLES Hereinafter, although an Example and a comparative example demonstrate this invention further in detail, this invention is not specifically limited by the following Examples. In the examples, the evaluation methods of various physical properties of the copolymer are as follows.

(1) 20 ° C. xylene soluble part (hereinafter abbreviated as CXS)
1 g of the copolymer was dissolved in 200 ml of boiling xylene, gradually cooled to 50 ° C., then immersed in ice water, cooled to 20 ° C. with stirring, allowed to stand at 20 ° C. for 3 hours, and the precipitated copolymer The coalescence was filtered off. The weight percentage of the copolymer remaining in the filtrate was defined as CXS (unit =%). A higher CXS value is preferable from the viewpoint of impact resistance because there are fewer crystal components and more rubbery polymer.

(2) Intrinsic viscosity (hereinafter abbreviated as [η])
The copolymer was dissolved in a tetralin solvent and measured at 135 ° C. using an Ubbelohde viscometer.

(3) Bulk density It was measured according to JIS K 6721 (1966).

(4) The composition analysis of the solid sample such as the solid catalyst component was performed as follows. That is, the titanium atom content was determined by decomposing a solid sample with dilute sulfuric acid, adding excess hydrogen peroxide water to this, and absorbing the 410 nm characteristic absorption of the obtained liquid sample by Hitachi double beam spectrophotometer U-2001 type. Was determined using a calibration curve prepared separately. The alkoxy group content was obtained by decomposing a solid sample with water, and then determining the alcohol amount corresponding to the alkoxy group in the obtained liquid sample using a gas chromatography internal standard method, and converting it to the alkoxy group content. The carboxylic acid ester content was determined by decomposing a solid sample with water, extracting a soluble component with a saturated hydrocarbon solvent, and determining the amount of carboxylic acid ester in the extract by a gas chromatography internal standard method.

(4) Propylene content in ethylene-propylene copolymer (unit: mol%)
M.M. De. M. De Pooter, “Journal of Applied Polymer Science”, Vol. 42, USA, 1991, p. 399-p. Based on the description of 408, it was measured and calculated by the ¹³ C-NMR method under the following conditions.
Apparatus: JNM-EX270 manufactured by JEOL Ltd.
Probe diameter: 10mmφ
Solvent: Orthodichlorobenzene Temperature: 135 ° C
Sample concentration: 5% by weight
Pulse width: 45
Repeat time: 10 seconds Integration count: 2500 times

(5) Reactivity ratio product of each monomer (r ₁ r ₂ )
Measured under the same conditions as in (5), Kakugogai, “Macromolecules”, Vol. 15, USA, 1982, p. 1150-p. It was calculated based on the description of 1152. The closer r ₁ r ₂ is to 1, the higher the randomness.

(6) Glass transition temperature (Tg, unit: ° C)
Using a differential scanning calorimeter (DS Instruments Q100, manufactured by TA Instruments), about 10 mg of a specimen was melted at 200 ° C. under a nitrogen atmosphere, then held at 200 ° C. for 5 minutes, and at a rate of temperature decrease of 10 ° C./min. The temperature was lowered to -90 ° C. Then, it measured from the endothermic curve at the time of heating up to 200 degreeC at 10 degreeC / min.

(7) Heat of crystallization (ΔHc, unit: J / g)
Using an apparatus similar to the glass transition temperature, about 10 mg of a specimen is melted at 200 ° C. in a nitrogen atmosphere, then held at 200 ° C. for 5 minutes, and the temperature is lowered to −90 ° C. at a temperature lowering rate of 10 ° C./min. The heat of crystallization per unit weight (ΔHc) was determined from the heat release peak at that time.

[Example 1]
(1) Synthesis of solid component (a) 200 liter cylindrical reactor shown in FIG. 1 (agitator with three pairs of stirring blades with a diameter of 0.35 m and a diameter with four baffle plates with a width of 0.05 m) 0.5 ml) was replaced with nitrogen, and 54 liters of hexane, 100 g of diisobutyl phthalate, 20.6 kg of tetraethoxysilane and 2.23 kg of tetrabutoxytitanium were added and stirred. Next, 51 liters of a dibutyl ether solution of butyl magnesium chloride (concentration 2.1 mol / liter) was added dropwise to the mixture over 4 hours while maintaining the temperature in the reactor at 7 ° C. At this time, the stirring rotation speed was 150 rpm. After completion of the dropping, the mixture was stirred at 20 ° C. for 1 hour and then filtered. The obtained solid was washed with 70 liters of toluene at room temperature three times, and toluene was added to obtain a solid catalyst component precursor slurry.
The solid catalyst component precursor contained Ti: 1.9% by weight, OEt (ethoxy group): 35.6% by weight, and OBu (butoxy group): 3.5% by weight.

(2) Synthesis of solid catalyst component (A) A 200-liter cylindrical reactor having the same shape as that used in (1) above was replaced with nitrogen, and the solid catalyst component precursor slurry obtained in (1) above was replaced with nitrogen. Transferred. After standing, the amount of toluene was withdrawn so that the volume of the slurry was 49.7 liters, stirred at 80 ° C. for 1 hour with stirring, and then the slurry was cooled to 40 ° C. or less. Thereafter, a mixed liquid of 30 liters of tetrachlorotitanium and 1.16 kg of dibutyl ether was added, and 4.23 kg of orthophthalic acid chloride was further added. The temperature in the reactor was adjusted to 110 ° C. and stirred for 3 hours, followed by filtration. The obtained solid was washed with 90 liters of toluene at 95 ° C. three times.
Toluene was added to form a slurry. After standing, the toluene was withdrawn so that the slurry volume was 49.7 liters. Under stirring, 15 liters of tetrachlorotitanium, 1.16 kg of dibutyl ether, and 0.87 kg of diisobutyl phthalate were obtained. Was added. The temperature in the reactor was set at 105 ° C. and stirred for 1 hour, followed by filtration. The obtained solid was washed twice with 90 liters of toluene at 95 ° C.
Toluene was added to form a slurry, and after standing, toluene was withdrawn so that the slurry volume was 49.7 liters, and a mixture of 15 liters of tetrachlorotitanium and 1.16 kg of dibutyl ether was added with stirring. The temperature in the reactor was set at 105 ° C. and stirred for 1 hour, followed by filtration. The obtained solid was washed twice with 90 liters of toluene at 95 ° C.
Toluene was added to form a slurry, and after standing, toluene was withdrawn so that the slurry volume was 49.7 liters, and a mixture of 15 liters of tetrachlorotitanium and 1.16 kg of dibutyl ether was added with stirring. The reactor was heated to 105 ° C. for 1 hour and then filtered, and the resulting solid was washed with 90 liters of toluene three times at 95 ° C. and twice with 90 liters of hexane. The obtained solid component was dried to obtain a solid catalyst component.
The solid catalyst component contained Ti: 2.2% by weight and phthalate ester compound component: 9.4% by weight.

(3) [Production of ethylene-propylene copolymer]
100 g of sodium chloride was added to a 1 liter mixed stainless steel autoclave and dried under reduced pressure at 80 ° C. After normal pressure with argon, the inside of the autoclave was stabilized at 60 ° C. Hydrogen was added at 0.02 MPa, then propylene was added at 0.21 MPa, and then a mixed gas of ethylene and propylene (the amount of ethylene in the mixed gas was 40.0 wt%) was added until the total pressure reached 0.71 MPa. Next, 10 mL of pentane, 1 mL of a 1.0 mmol / mL hexane solution of triethylaluminum (that is, 1.0 mmol as triethylaluminum), and 1.75 mL of a 0.057 mmol / mL heptane solution of 2,6-dimethylpyridine (that is, 2 mL). , 6-dimethylpyridine (0.10 mmol) and 8.79 mg of the solid catalyst component described in Example 1 (2) were mixed with argon under pressure to initiate polymerization. At 65 ° C., the above mixed gas of ethylene and propylene was fed so that the total pressure was adjusted to 0.71 MPa, and stirring was continued for 112 minutes. After the completion of the polymerization, the content was taken out, about 1 L of pure water was added and stirred for 1 hour, followed by filtration and vacuum drying to obtain 16 g of an ethylene-propylene copolymer. The activity per hour was 980 g-copolymer / g-catalyst / hr, the ethylene content in the ethylene-propylene copolymer was 56.3 mol%, r ₁ r ₂ was 2.01, and [η] was 1. 78 dl / g, CXS was 64.9 wt%, ΔHc was 7.6 J / g, and Tg was −48.5 ° C.

Example 2 [Production of ethylene-propylene copolymer]
A 3 L stirring type autoclave made of stainless steel was cooled to 5 ° C. or lower, and the inside of the autoclave was depressurized. In a state where the pressure was reduced, 1 L of heptane, 0.04 MPa of hydrogen, and 150 g of propylene were introduced, and then the temperature was raised to 65 ° C. in a closed system. After the internal temperature was stabilized at 65 ° C., ethylene was introduced so that the ethylene partial pressure was 0.20 MPa. After the inside of the autoclave was stabilized, 10 mL of heptane, 2.6 mL of a 1.0 mmol / mL hexane solution of triethylaluminum (that is, 2.6 mmol as triethylaluminum), and a 0.057 mmol / mL heptane solution of 2,6-dimethylpyridine were added. A mixture of 4.6 mL (that is, 0.26 mmol of 2,6-dimethylpyridine) and 3.70 mg of the solid catalyst component described in Example 1 (2) was charged with argon under pressure to initiate polymerization. At 65 ° C., ethylene was fed so that the ethylene partial pressure was adjusted to 0.20 MPa, and stirring was continued for 30 minutes. Ethanol was charged with argon and polymerized. The content solution was put in ethanol with a small amount of hydrochloric acid, and the precipitated polymer was filtered and dried in vacuo to obtain 13 g of an ethylene-propylene copolymer. The activity per hour was 6800 g-copolymer / g-catalyst / hr, the ethylene content in the ethylene-propylene copolymer was 69.3 mol%, r ₁ r ₂ was 1.50, and [η] was 2. 09 dl / g, CXS was 80.5 wt%, ΔHc was 11.5 J / g, and Tg was −53.1 ° C.

Schematic diagram of cylindrical reactor

Explanation of symbols

(A) Top view (b) Side view 1 Agitation blade 2 Baffle plate

Claims (8)

An olefin copolymerization catalyst obtained by contacting the following components (A), (B) and (C).
(A) obtained by contacting a solid component (a) containing a titanium atom, a magnesium atom and a hydrocarbyloxy group, a halogenated compound (b), an electron donor (c) and / or an organic acid halide (d). Solid catalyst component (B) Organoaluminum compound and / or organoaluminum oxycompound (C) Aromatic nitrogen heterocyclic compound having an alkyl group having 1 to 3 carbon atoms on at least one carbon atom adjacent to the nitrogen atom   The catalyst for olefin copolymerization according to claim 1, wherein component (C) is a substituted pyridine having an alkyl group having 1 to 3 carbon atoms on at least one carbon atom adjacent to the nitrogen atom.   The catalyst for olefin copolymerization according to claim 1, wherein the component (C) is a substituted pyridine having an alkyl group having 1 to 3 carbon atoms at the 2nd and 6th positions.

The solid component (a) reduces the titanium compound (ii) represented by the following formula [I] with the organomagnesium compound (iii) in the presence of the organosilicon compound (i) having a Si—O bond. The catalyst for olefin copolymerization according to any one of claims 1 to 3, which is a solid product containing a trivalent titanium atom obtained by the following process.
(In the above formula [I], a represents a number of 1 to 20, R ⁴ represents a hydrocarbyl group having 1 to 20 carbon atoms. X ² represents a halogen atom or a hydrocarbyloxy having 1 to 20 carbon atoms. And X ² may be the same or different from each other.   The manufacturing method of the olefin copolymer using the catalyst for olefin copolymer in any one of Claims 1-4.   The method for producing an olefin copolymer according to claim 5, wherein the olefin copolymer is an ethylene-α-olefin copolymer.   The method for producing an olefin copolymer according to claim 5, wherein the olefin copolymer is an ethylene-propylene copolymer. The method for producing an ethylene-propylene copolymer according to claim 7, wherein propylene is homopolymerized in the first step and then ethylene and propylene are copolymerized in the second step.

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