JP2012158640A - Method for producing solid catalytic component for olefin polymerization - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for producing a solid catalytic component for olefin polymerization, which exhibits sufficiently high polymerization activity and presents a polymer having a small content of CXS component, a solid catalyst for olefin polymerization and a method for producing an olefin polymer.SOLUTION: The method for producing a solid catalytic component (A) for olefin polymerization containing a titanium atom, a magnesium atom, a halogen atom and an internal electron donor (d) represented by general formula (I) [wherein R, R, Rand Rare each the same or different and a 1C-10C hydrocarbyl group, and may be mutually bonded or contain a heteroatom] includes performing a step (P) for bringing the internal electron donor (d) and/or an internal electron donor precursor (e) into contact with a magnesium compound (b) in a solvent and thereafter carrying out solid-liquid separations twice or more.

Description

The present invention relates to a method for producing a solid catalyst component for olefin polymerization, a method for producing a solid catalyst for olefin polymerization using a solid catalyst component for olefin polymerization, and a method for producing an olefin polymer using a solid catalyst for olefin polymerization.

Conventionally, many solid catalyst components containing a titanium atom, a magnesium atom, a halogen atom and an internal electron donor have been proposed as olefin polymerization catalyst components. The catalyst using these solid catalyst components has a high polymerization activity in the polymerization of olefins, and the content of components eluted in a low-temperature organic solvent typified by low molecular weight components and indefinitely formed components (hereinafter referred to as CXS components). It is desirable to obtain a polymer with a low content. It is known that the internal electron donor greatly affects the performance of the catalyst component for olefin polymerization, and it has been clarified that a malonic acid ester is effective as the internal electron donor.

Patent Documents 1 and 2 disclose a solid catalyst component for olefin polymerization containing titanium, magnesium, halogen, and a malonic ester compound as an internal electron donor.

Patent Document 3 discloses a solid catalyst component for olefin polymerization produced from a solid component containing a trivalent titanium atom, a magnesium atom, and a halogen atom.

Japanese Patent Laid-Open No. 10-212319 JP 2000-516987 A JP 2004-91513 A

However, the above-mentioned catalyst for olefin polymerization is not yet satisfactory from the viewpoint of the polymerization activity and the content of the CXS component of the resulting olefin polymer. An object of the present invention is to provide a method for producing a solid catalyst component for olefin polymerization, a solid catalyst for olefin polymerization, and a method for producing an olefin polymer, which exhibit a sufficiently high polymerization activity and give a polymer having a low CXS component content It is intended to do.

The present invention relates to a method for producing a solid catalyst component (A) for olefin polymerization comprising a titanium atom, a magnesium atom, a halogen atom, and an internal electron donor (d) represented by the general formula (I), comprising a magnesium compound The step (P) of solid-liquid separation after contacting the internal electron donor (d) and / or the internal electron donor precursor (e) in a solvent with respect to (b) is performed twice or more. The production method of the solid catalyst component (A) for olefin polymerization.

（Ｉ）
［Ｒ^１、Ｒ^２、Ｒ^３、Ｒ^４は同一または異なってもよく、炭素原子数１〜１０のハイドロカルビル基であり、互いに結合していてもよく、ヘテロ原子を含んでいてもよい。］

(I)
[R ¹ , R ² , R ³ , R ⁴ may be the same or different and each is a hydrocarbyl group having 1 to 10 carbon atoms, may be bonded to each other, and may contain a hetero atom. . ]

The present invention further relates to a method for producing a solid catalyst component (A) for olefin polymerization comprising a titanium atom, a magnesium atom, a halogen atom and an internal electron donor (d) represented by the above general formula (I). Contact of the internal electron donor (d) and / or the internal electron donor precursor (e) with the solid component (c) containing a valent titanium atom, magnesium atom and hydrocarbyloxy group in a solvent And the step (Q) of solid-liquid separation after the formation is carried out twice or more, which is a method for producing a solid catalyst component (A) for olefin polymerization.

The present invention still further provides a method for producing a solid catalyst for olefin polymerization comprising the step of contacting the solid catalyst component for olefin polymerization (A), the organoaluminum compound (B) and optionally an external electron donor (C). It is.

The present invention is also a method for producing an olefin polymer comprising a step of polymerizing an olefin in the presence of the solid catalyst for olefin polymerization produced by the above production method.

According to the present invention, a method for producing a solid catalyst component for olefin polymerization, a method for producing a solid catalyst for olefin polymerization, and a method for producing an olefin polymer, which give a polymer having a sufficiently high polymerization activity and a low content of CXS component A method is provided.

The solid catalyst component (A) for olefin polymerization produced by the production method of the present invention comprises an olefin polymerization comprising a titanium atom, a magnesium atom, a halogen atom, and an internal electron donor (d) represented by the general formula (I) The solid catalyst component (A) for use.

（Ｉ）
［Ｒ^１、Ｒ^２、Ｒ^３、Ｒ^４は同一または異なってもよく、炭素原子数１〜１０のハイドロカルビル基であり、互いに結合していてもよく、ヘテロ原子を含んでいてもよい。］

(I)
[R ¹ , R ² , R ³ , R ⁴ may be the same or different and each is a hydrocarbyl group having 1 to 10 carbon atoms, may be bonded to each other, and may contain a hetero atom. . ]

<Internal electron donor (d) represented by formula (I)>
Examples of the hydrocarbyl group of R ¹ , R ² , R ³ and R ^{4 in} the general formula (I) include an alkyl group, an aralkyl group, an aryl group, and an alkenyl group, and these include a halogen atom, hydrocarbyloxy It may be substituted with a group, nitro group, sulfonyl group, silyl group or the like. Specifically, linear alkyl groups such as methyl group, ethyl group, n-propyl group, n-butyl group, n-pentyl group, n-hexyl group, n-heptyl group, and n-octyl group; Branched alkyl groups such as isopropyl group, isobutyl group, tert-butyl group, isopentyl group, neopentyl group, isoamyl group, and 2-ethylhexyl group; cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, And cyclic alkyl groups such as cyclooctyl group; aralkyl groups such as benzyl group and phenethyl group; aryl groups such as phenyl group, tolyl group, and naphthyl group; vinyl group, allyl group, 3-butenyl group, and 5 A linear alkenyl group such as a hexenyl group; an isobutenyl group, and 4-methyl- - branched alkenyl groups such as pentenyl group; can be exemplified cyclic alkenyl groups such as 2-cyclohexenyl group and a 3-cyclohexenyl group.

The hydrocarbyl group of R ¹ and R ² in the general formula (I) is preferably a linear or branched alkyl group having 1 to 5 carbon atoms, more preferably an alkyl group having 1 to 2 carbon atoms. And particularly preferably an ethyl group.

The hydrocarbyl group represented by R ³ and R ⁴ in formula (I) is preferably a linear or branched alkyl group having 2 to 10 carbon atoms, more preferably a straight chain having 2 to 6 carbon atoms. A chain or branched alkyl group.

Specifically, dimethyl dimethyl malonate, diethyl dimethyl malonate, diisopropyl dimethyl malonate, dinormal dimethyl malonate, diisobutyl dimethyl malonate, ethyl methyl dimethyl malonate, dicyclohexyl dimethyl malonate, bis (2-dimethyl malonate (2- Ethyl hexyl), dimethyl diethyl malonate, diethyl diethyl malonate, diisopropyl diethyl malonate, dinormal butyl diethyl malonate, diisobutyl diethyl malonate, ethyl methyl diethyl malonate, dicyclohexyl diethyl malonate, bis (2-ethylhexyl) diethyl malonate , Dimethyl diisopropyl malonate, diethyl diisopropyl malonate, diisopropyl diisopropyl malonate, dinormal butyl diisopropyl malonate, Diisobutyl isopropylmalonate, ethyl methyl diisopropylmalonate, dicyclohexyldiisopropylmalonate, bis (2-ethylhexyl) diisopropylmalonate, dimethyl dinormalbutylmalonate, diethyldinormalbutylmalonate, diisopropyldinormalbutylmalonate, diisopropylbutyl Dinormal butyl malonate, diisobutyl butyl malonate, ethyl methyl dinormal butyl malonate, dicyclohexyl dinormal butyl malonate, bis (2-ethylhexyl) dinormal butyl malonate, dimethyl diisobutyl malonate, diethyl diisobutyl malonate, Diisobutylmalonate diisopropyl, diisobutylmalonate dinormalbutyl, diisobutylmalonate diisobutyl, diisobutylmalo Ethyl methyl, diisobutyl malonate dicyclohexyl, bis (2-ethylhexyl) diisobutyl malonate, dimethyl di-tert-butyl malonate, diethyl di-tert-butyl malonate, diisopropyl di-tert-butyl malonate, di-tert- Dinormal butyl butylmalonate, diisobutyl di-tert-butylmalonate, ethyl methyl di-tert-butylmalonate, dicyclohexyl di-tert-butylmalonate, bis (2-ethylhexyl) di-tert-butylmalonate, diamylmalon Dimethyl acid, diethyl diamyl malonate, diisopropyl diamyl malonate, dinormal butyl diamyl malonate, diisobutyl diamyl malonate, ethyl methyl diamyl malonate, dicyclohexyl diamyl malonate, Bis (2-ethylhexyl) diamylmalonate, dimethyl dicyclohexylmalonate, diethyl dicyclohexylmalonate, diisopropyldicyclohexylmalonate, dibutylmalonate dicyclohexylmalonate, diisobutylmalonate dicyclohexylmalonate, ethylmethyldicyclohexylmalonate, dicyclohexylmalonate dicyclohexylmalonate Bis (2-ethylhexyl), dimethyl ethyl normal butyl malonate, diethyl ethyl normal butyl malonate, diisopropyl ethyl normal butyl malonate, dinormal butyl ethyl normal butyl malonate, diisobutyl ethyl normal butyl malonate, ethyl ethyl normal butyl malonate Methyl, ethyl normal butylmalonate dicyclohexyl, ethyl Bis (2-ethylhexyl) lumal butylmalonate, dimethyl ethylisobutylmalonate, diethyl ethylisobutylmalonate, diisopropylethylisobutylmalonate, dinormalbutyl ethylisobutylmalonate, diisobutylethylisobutylmalonate, ethylmethyl ethylisobutylmalonate, Ethyl isobutyl malonate dicyclohexyl, ethyl isobutyl malonate bis (2-ethylhexyl), dimethyl diphenyl malonate, diethyl diphenyl malonate, diisopropyl diphenyl malonate, dinormal butyl diphenyl malonate, diisobutyl diphenyl malonate, ethyl methyl diphenyl malonate, Dicyclohexyl malonate dicyclohexyl, diphenyl malonate bis (2-ethylhexyl), methyl hexyl malonate di Cyl, diethyl methyl hexyl malonate, diisopropyl methyl texyl malonate, dinormal butyl methyl hexyl malonate, diisobutyl methyl hexyl malonate, ethyl methyl hexyl malonate, dicyclohexyl methyl hexyl malonate, methyl texyl Bis (2-ethylhexyl) malonate, dimethyl isobutylisopropylmalonate, diethyl isobutylisopropylmalonate, diisopropylisobutylisopropylmalonate, dinormalbutylisobutylisopropylmalonate, diisobutylisobutylisopropylmalonate, ethylmethylisobutylisopropylmalonate, isobutylisopropyl Dicyclohexyl malonate, bis (2-ethylhexyl) isobutylisopropylmalonate, ethylphenylmalon Dimethyl acid, diethyl ethyl phenyl malonate, diisopropyl ethyl phenyl malonate, dinormal butyl ethyl phenyl malonate, diisobutyl ethyl phenyl malonate, ethyl methyl ethyl phenyl malonate, dicyclohexyl ethyl phenyl malonate, bis ethyl phenyl malonate (2- Ethyl hexyl), benzyl methyl malonate dimethyl, benzyl methyl malonate diethyl, benzyl methyl malonate diisopropyl, benzyl methyl malonate dinormal butyl, benzyl methyl malonate diisobutyl, benzyl methyl malonate ethyl methyl, benzyl methyl malonate dicyclohexyl, benzyl methyl Bis (2-ethylhexyl) malonate, dimethyl dibenzylmalonate, diethyl dibenzylmalonate, diidibenzylmalonate Propyl, dinormal malonate dibenzylmalonate, diisobutyl dibenzylmalonate, ethyl methyl dibenzylmalonate, dicyclohexylmalonate dicyclohexyl, dibenzylmalonate bis (2-ethylhexyl), diallylmalonate dimethyl, diallylmalonate diethyl, Diisopropyl diallyl malonate, dinormal butyl diallyl malonate, diisobutyl diallyl malonate, ethyl methyl diallyl malonate, dicyclohexyl diallyl malonate, bis (2-ethylhexyl) diallyl malonate, dimethyl bis (3-butenyl) malonate, bis ( 3-butenyl) malonate diethyl, bis (3-butenyl) malonate diisopropyl, bis (3-butenyl) malonate dinormalbutyl, bis (3-butenyl) malonate diisobutyl, bis (3 Butenyl) ethyl methyl malonate, dicyclohexyl bis (3-butenyl) malonate, bis (2-ethylhexyl) bis (3-butenyl) malonate, dimethyl bis (3-chloropropyl) malonate, bis (3-chloropropyl) Diethyl malonate, diisopropyl bis (3-chloropropyl) malonate, dinormal butyl bis (3-chloropropyl) malonate, diisobutyl bis (3-chloropropyl) malonate, ethyl methyl bis (3-chloropropyl) malonate Bis (3-chloropropyl) malonate dicyclohexyl, bis (3-chloropropyl) malonate bis (2-ethylhexyl), cyclohexane-1,1-dicarboxylate dimethyl, cyclohexane-1,1-dicarboxylate diethyl, cyclohexane- 1,1-dicarboxylic acid dii Sopropyl, cyclohexane-1,1-dicarboxylate dinormal butyl, cyclohexane-1,1-dicarboxylate diisobutyl, cyclohexane-1,1-dicarboxylate ethylmethyl, cyclohexane-1,1-dicarboxylate dicyclohexyl, and cyclohexane-1, An example is bis (2-ethylhexyl) 1-dicarboxylate.

The internal electron donor (d) is preferably diethylmalonic acid ester, diisopropylmalonic acid ester, isobutylisopropylmalonic acid ester, diisobutylmalonic acid ester, and di-tert-butylmalonic acid ester, particularly preferably diethylmalonic acid. Diethyl, diethyl isobutyl isopropylmalonate, and diethyl diisobutylmalonate.

<Other internal electron donor (d ′)>
The solid catalyst component for olefin polymerization (A) obtained by the method for producing the solid catalyst component for olefin polymerization (A) provided by the present invention is added to the internal electron donor (d) represented by the general formula (I). The other internal electron donor (d ′) may further contain one or more aromatic carboxylic acid esters and / or 1,3-diethers.

The aromatic carboxylate ester as another internal electron donor (d ′) is not particularly limited as long as it is a compound in which an aromatic carboxylic acid and an alcohol are ester-bonded. Specific examples include ethyl benzoate and butyl benzoate. Aromatic monocarboxylic acid esters such as methyl toluate, ethyl toluate, ethyl anisate; monoethyl phthalate, dimethyl phthalate, methyl ethyl phthalate, diethyl phthalate, di-n-propyl phthalate, diisopropyl phthalate Di-n-butyl phthalate, diisobutyl phthalate, dipentyl phthalate, di-n-hexyl phthalate, diheptyl phthalate, di-n-octyl phthalate, di (2-ethylhexyl) phthalate, diisodecyl phthalate, Aromatic polycarboxylic acids such as dicyclohexyl phthalate and diphenyl phthalate It can be exemplified ester.

The 1,3-diether as the other internal electron donor (d ′) is not particularly limited as long as it is a compound having a C—O—C—C—C—O—C bond. , 2-diisobutyl-1,3-dimethoxypropane, 2-isopropyl-2-isopentyl-1,3-dimethoxypropane, 2,2-bis (cyclohexylmethyl) -1,3-dimethoxypropane, 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- Methoxypropane, 2,2-dipropyl-1,3-dimethoxypropane, 2-isopropyl-2-cyclohexyl-1,3-dimethoxypropane, 2-isopropyl-2-cyclopentyl-1,3-dimethoxypropane, 2,2- Illustrative are 1,3-diethers such as dicyclopentyl-1,3-dimethoxypropane and 2-heptyl-2-pentyl-1,3-dimethoxypropane.

<Ingredients used during production of solid catalyst component (A) for olefin polymerization>
In the method for producing the solid catalyst component (A) for olefin polymerization provided by the present invention, the internal electron donor (d) and / or the internal electron donor precursor (e) are brought into contact with the magnesium compound (b). Is the method.
Further, as another aspect of the present invention, an internal electron donor (d) and / or an internal electron donation with respect to a solid component (c) containing a trivalent titanium atom, a magnesium atom, and a hydrocarbyloxy group. This is a method of contacting the body precursor (e).

Arbitrary components other than the internal electron donor (d) and the internal electron donor precursor (e) may be brought into contact with the magnesium compound (b) or the solid component (c).

Specific examples of components other than the internal electron donor (d) and the internal electron donor precursor (e) that are brought into contact with the magnesium compound (b) or the solid component (c) include titanium compounds (a), etc. The internal electron donor (d ′) and the metal halide compound (g) can be exemplified.

<Magnesium compound (b)>
The magnesium compound (b) is not particularly limited as long as it is a compound containing a magnesium atom, but a compound containing a hydrocarbyl group, a hydrocarbyloxy group, and / or a halogen atom in addition to the magnesium atom. It can be illustrated.

Although there is no restriction | limiting in particular as a hydrocarbyl group contained in a magnesium compound (b), A methyl group, an ethyl group, n-propyl group, n-butyl group, n-pentyl group, n-hexyl group, n-heptyl And linear alkyl groups such as n-octyl group; branched alkyl groups such as isopropyl group, isobutyl group, tert-butyl group, isopentyl group, neopentyl group, isoamyl group, and 2-ethylhexyl group; Cyclic alkyl groups such as propyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, and cyclooctyl; aralkyl groups such as benzyl and phenethyl; phenyl, tolyl, and naphthyl Aryl group; vinyl group, allyl group, 3-butenyl group, and 5-hexe A linear alkenyl group such as an alkyl group; a branched alkenyl group such as an isobutenyl group and a 4-methyl-3-pentenyl group; a cyclic alkenyl group such as a 2-cyclohexenyl group and a 3-cyclohexenyl group. It can be illustrated.

The hydrocarbyloxy group contained in the magnesium compound (b) is not particularly limited, but is a methoxy group, ethoxy group, n-propoxy group, n-butoxy group, n-pentyloxy group, n-hexyloxy group, linear alkyloxy groups such as n-heptyloxy and n-octyloxy; isopropoxy, isobutoxy, tert-butoxy, isopentyloxy, neopentyloxy, isoamyloxy, and 2 A branched alkyloxy group such as an ethylhexyloxy group; a cyclic alkyloxy group such as a cyclopropoxy group, a cyclobutoxy group, a cyclopentyloxy group, a cyclohexyloxy group, a cycloheptyloxy group, and a cyclooctyloxy group; a benzyloxy group And like phenethyloxy group Aralkyloxy groups; aryloxy groups such as phenoxy groups, naphthyloxy groups, and tolyloxy groups; linear alkenyloxy groups such as vinyloxy groups, allyloxy groups, 3-butenyloxy groups, and 5-hexenyloxy groups; Examples thereof include a branched alkenyloxy group such as a tenenyloxy group and a 4-methyl-3-pentenyloxy group; a cyclic alkenyloxy group such as a 2-cyclohexenyloxy group and a 3-cyclohexenyloxy group. .

Any halogen atom may be used as the halogen atom contained in the magnesium compound (b).

Specifically, dialkyl magnesium compounds such as dimethyl magnesium, diethyl magnesium, diisopropyl magnesium, dibutyl magnesium, dihexyl magnesium, dioctyl magnesium, ethyl butyl magnesium, dicyclohexyl magnesium, and butyl octyl magnesium; dimethoxy magnesium, diethoxy magnesium, Dialkoxymagnesium compounds such as dipropoxymagnesium, dibutoxymagnesium, dihexyloxymagnesium, dioctoxymagnesium, and dicyclohexyloxymagnesium; methylmagnesium chloride, ethylmagnesium chloride, isopropylmagnesium chloride, isobutylmagnesium chloride, t-butylmagnesium chloride Hexyl magnesium chloride, isobutyl magnesium chloride, benzyl magnesium chloride, methyl magnesium bromide, ethyl magnesium bromide, isopropyl magnesium bromide, isobutyl magnesium bromide, t-butyl magnesium bromide, hexyl magnesium bromide, isobutyl magnesium bromide, benzyl magnesium bromide, methyl magnesium iodide Alkyl magnesium halide compounds such as ethylmagnesium iodide, isopropylmagnesium iodide, isobutylmagnesium iodide, t-butylmagnesium iodide, hexylmagnesium iodide, isobutylmagnesium iodide, benzylmagnesium iodide; methoxymagnesium chloride, ethoxy Alkoxymagnesium chlorides such as gnesium chloride, isopropoxymagnesium chloride, butoxymagnesium chloride, and hexyloxymagnesium chloride; aryloxymagnesium chlorides such as phenoxymagnesium chloride; magnesium fluoride, magnesium chloride, magnesium bromide, and magnesium iodide The following magnesium halide compounds can be exemplified.

Further, as the magnesium compound (b), in addition to the hydrocarbyl group, hydrocarbyloxy group, and halogen atom, vanadium atom, chromium atom, manganese atom, iron atom, cobalt atom, nickel atom, copper atom, zinc Also exemplified are mixtures comprising metal atoms such as atoms, gallium atoms, zirconium atoms and hafnium atoms; organic compounds such as hydrocarbons, alcohols, ethers and amines; inorganic compounds such as carbon dioxide.

The magnesium compound (b) may be dissolved in an alcohol such as methanol, ethanol, and 2-ethylhexanol or a solvent such as chlorobenzene, toluene, and hexane, or may be solid.

The magnesium compound (b) may be supported on a carrier material. There are no particular restrictions on the support material, but porous inorganic oxides such as SiO ₂ , Al ₂ O ₃ , MgO, TiO ₂ , and ZrO ₂ ; polystyrene, styrene-divinylbenzene copolymer, styrene-ethylene glycol-di Methyl methacrylate copolymer, polymethyl acrylate, polyethyl acrylate, methyl acrylate-divinylbenzene copolymer, polymethyl methacrylate, methyl methacrylate-divinylbenzene copolymer, polyacrylonitrile, acrylonitrile-divinylbenzene copolymer Examples include organic porous polymers such as polymers, polyvinyl chloride, polyethylene, and polypropylene. Of these, porous inorganic oxides are preferable, and SiO ₂ is particularly preferable.

From the viewpoint of effectively immobilizing the magnesium compound (b), the support is preferably a porous support; the pore distribution of the support is a radius 3.5 of the pore volume of the pore having a radius of 20 to 200 nm. The ratio of pores of ˜7500 nm to the pore volume is preferably 35% or more, more preferably 40% or more; and the pore volume of pores having a radius of 20 to 200 nm is preferably 0.3 cm. ³ / g or more, and more preferably 0.4 cm ³ / g or more.

The magnesium compound (b) is preferably a halogenated magnesium compound (b-1) or a dialkoxymagnesium compound (b-2).

The magnesium halide compound (b-1) is preferably magnesium chloride.

A commercially available magnesium chloride may be used as it is, or it may be produced by a method in which a commercially available product is dissolved in alcohol and then dropped into a solvent.

The dialkoxymagnesium compound (b-2) is preferably dialkoxymagnesium having 1 to 20 carbon atoms, more preferably dialkoxymagnesium having 1 to 10 carbon atoms, particularly preferably dimethoxymagnesium and diethoxymagnesium. Dipropoxymagnesium, diisopropoxymagnesium and dibutoxymagnesium.

Examples of the method for producing the dialkoxymagnesium compound (b-2) include a method in which metal magnesium and an alcohol are contacted in the presence of a catalyst. Alcohols include methanol, ethanol, propanol, butanol, and octanol. Catalysts include halogens such as iodine, chlorine and bromine; magnesium halides such as magnesium iodide and magnesium chloride; α, β-dihaloalkanes such as 1,2-dibromoethane, preferably It is iodine.

<Solid component (c)>
The solid component (c) containing a trivalent titanium atom, magnesium atom and hydrocarbyloxy group is not limited as long as it is a solid component having a trivalent titanium atom, magnesium atom and hydrocarbyloxy group. May be.

Examples of the hydrocarbyloxy group contained in the solid component (c) include the same hydrocarbyloxy groups contained in the magnesium compound (b). Preferably, it is an alkyloxy group having 1 to 20 carbon atoms or an aryloxy group having 6 to 20 carbon atoms, more preferably a linear or branched alkyloxy group having 1 to 20 carbon atoms, particularly A methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, an n-butoxy group, an isobutoxy group, and a pentyloxy group are preferable.

The solid component (c) containing a trivalent titanium atom, magnesium atom and hydrocarbyloxy group may be synthesized by any production method. For example, there is a method in which the titanium compound (c-2) is reduced with the organomagnesium compound (c-3) in the presence of the silicon compound (c-1) having a Si—O bond.

Furthermore, in the presence of the silicon compound (c-1) having a Si—O bond, the compound (c-2) having an arbitrary ester group during the reduction reaction with the organomagnesium compound (c-3) ( c-4) may coexist.

<Silicon compound having Si—O bond (c-1)>
The silicon compound (c-1) having a Si—O bond is not particularly limited as long as it is a compound containing a silicon atom, but examples thereof include compounds represented by the following formulas (i) to (iii).
Si (OR ⁵ ) _t R ⁶ _(4-t) (i)
R ⁷ (R ⁸ ₂ SiO) _u SiR ⁹ ₃ (ii)
(R ¹⁰ ₂ SiO) _v (iii)
[Wherein R ⁵ , 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, and t satisfies 0 <t ≦ 4. An integer that satisfies u is an integer from 1 to 1000; v is an integer from 2 to 1000]

Magnesium compounds as hydrocarbyl groups of R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ and R ^{10 in} the silicon compound (c-1) having a Si—O bond represented by formulas (i) to (iii) The same thing as the hydrocarbyl group contained in (b) can be illustrated.

R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ and R ¹⁰ in the silicon compound (c-1) having a Si—O bond represented by formulas (i) to (iii) are preferably 2 to 2 carbon atoms. 18 is an alkyl group or an aryl group having 6 to 18 carbon atoms, and particularly preferably a linear alkyl group having 2 to 18 carbon atoms.

Specific examples of the silicon compound (c-1) having a Si—O bond represented by formulas (i) to (iii) include tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, tetraisopropoxysilane, tetrabutoxysilane, And tetraalkoxysilanes such as tetraphenoxysilane; monoalkyltrialkoxysilanes such as ethyltriethoxysilane and phenyltriethoxysilane; dimethyldimethoxysilane, diethyldiethoxysilane, diphenyldiethoxysilane, dipropyldipropoxysilane, Dialkyldialkoxysilanes such as diisopropyldiisopropoxysilane, dibutyldibutoxysilane, and diethyldicyclopentyloxysilane; triethylethoxysilane, trimethylcyclohexane Trioxymonoalkoxysilanes such as trioxyphenoxysilane; disiloxanes such as hexamethyldisiloxane, hexaethyldisiloxane, and hexapropyldisiloxane; octaethyltrisiloxane, dimethylpolysiloxane, diphenylpolysiloxane, methyl Examples include hydropolysiloxanes and polysiloxanes such as phenylhydropolysiloxanes.

Among the silicon compounds (c-1) having a Si—O bond represented by formulas (i) to (iii), t in formula (i) is preferably a compound satisfying 1 ≦ t ≦ 4, more preferably, Tetraalkoxysilane in which t is 4, most preferably tetraethoxysilane.

<Titanium compound (c-2)>
Although there will be no restriction | limiting in particular as a titanium compound (c-2) if it is a compound containing a titanium atom, The compound represented by the following Formula (iv) can be illustrated.

（ｉｖ）
［ただし、式（ｉｖ）において、ｍは１〜２０の整数を表し、Ｒ^１１は炭素原子数１〜２０のハイドロカルビル基を表す。Ｘ^１はハロゲン原子または炭素原子数１〜２０のハイドロカルビルオキシ基を表し、Ｘ^１は互いに同じであっても異なっていてもよい］

(Iv)
[However, in Formula (iv), m represents an integer of 1 to 20, and R ¹¹ represents a hydrocarbyl group having 1 to 20 carbon atoms. X ¹ represents a halogen atom or a hydrocarbyloxy group having 1 to 20 carbon atoms, and X ¹ may be the same or different.

Specific examples of R ^{11 in} the titanium compound (c-2) represented by the formula (iv) can include the same hydrocarbyl group contained in the magnesium compound (b), preferably the number of carbon atoms It is a 2-18 alkyl group or a C6-C18 aryl group, Most preferably, it is a C2-C18 linear alkyl group.

Examples of the halogen atom for X ¹ in formula (iv) include a chlorine atom, a bromine atom and an iodine atom. Particularly preferred is a chlorine atom.

The hydrocarbyloxy group having 1 to 20 carbon atoms of X ¹ in the formula (iv) is preferably a linear alkoxy group having 2 to 18 carbon atoms, more preferably 2 to 10 carbon atoms. A straight-chain alkoxy group, particularly preferably a straight-chain alkoxy group having 2 to 6 carbon atoms.

The value of m in formula (iv) is preferably 1, 2 or 4.

Specific examples of the titanium compound (c-2) represented by the formula (iv) include tetramethoxy titanium, tetraethoxy titanium, tetra-n-propoxy titanium, tetraisopropoxy titanium, tetra-n-butoxy titanium, tetraiso Butoxytitanium, n-butoxytitanium trichloride, di-n-butoxytitanium dichloride, tri-n-butoxytitanium chloride, di-n-tetraisopropylpolytitanate (mixture in the range of m = 2 to 10), tetra-n -Butylpolytitanate (mixture in the range m = 2-10), tetra-n-hexylpolytitanate (mixture in the range m = 2-10), tetra-n-octylpolytitanate (m = 2-2) Tetraalkoxy tita obtained by reacting tetraalkoxytitanium with a small amount of water. As well as combinations of two or more thereof, more preferably tetra-n-butoxytitanium, tetra-n-butyltitanium dimer or tetra-n-butyltitanium tetramer. .

<Organic magnesium compound (c-3)>
The organomagnesium compound (c-3) is not particularly limited as long as it is a compound having a magnesium atom-C bond, but a compound represented by the following formula (v) or (vi) can be exemplified, and more preferably Is a Grignard compound represented by the formula (v).
R ¹² MgX ² (v)
R ¹³ R ¹⁴ Mg (vi)
[R ¹² , R ¹³ and R ¹⁴ represent a hydrocarbyl group having 1 to 20 carbon atoms, and X ² represents a halogen atom]

The hydrocarbyl group of R ¹² , R ¹³ and R ¹⁴ in formulas (v) and (vi) is not particularly limited, but the same hydrocarbyl group contained in the magnesium compound (b) can be exemplified. .

R ¹² , R ¹³ and R ¹⁴ in formulas (v) and (vi) are more preferably an alkyl group having 2 to 18 carbon atoms or an aryl group having 6 to 18 carbon atoms, and particularly preferably the number of carbon atoms. 2 to 18 linear alkyl groups.

X ² in the formula (v) is not particularly limited, but examples thereof include a chlorine atom, a bromine atom and an iodine atom. More preferably, it is a chlorine atom.

Specific examples of the Grignard compound represented by the formula (v) include methylmagnesium chloride, ethylmagnesium chloride, n-propylmagnesium chloride, isopropylmagnesium chloride, n-butylmagnesium chloride, isobutylmagnesium chloride, tert-butylmagnesium chloride, Examples include n-pentylmagnesium chloride, isoamylmagnesium chloride, cyclopentylmagnesium chloride, n-hexylmagnesium chloride, cyclohexylmagnesium chloride, n-octylmagnesium chloride, 2-ethylhexylmagnesium chloride, phenylmagnesium chloride, and benzylmagnesium chloride. . Preferred are ethylmagnesium chloride, n-propylmagnesium chloride, isopropylmagnesium chloride, n-butylmagnesium chloride, and isobutylmagnesium chloride, and particularly preferred is n-butylmagnesium chloride.

The Grignard compound may be as it is or may be dissolved in a solvent, and more preferably in a state in which an ether compound is used as a solvent.

The ether compound is not particularly limited as long as it is a compound having a C—O—C bond, but diethyl ether, di-n-propyl ether, diisopropyl ether, di-n-butyl ether, diisobutyl ether, ethyl n-butyl ether. And dialkyl ethers such as diisoamyl ether; cyclic ethers such as tetrahydrofuran. Dialkyl ether is preferable, and di-n-butyl ether or diisobutyl ether is more preferable.

<Compound having ester group (c-4)>
Any ester compound may be used as the compound (c-4) having an ester group. For example, mono- or polyvalent carboxylic acid esters can be mentioned, and more specifically, saturated aliphatic carboxylic acid esters, unsaturated aliphatic carboxylic acid esters, alicyclic carboxylic acid esters, and aromatic carboxylic acid esters. It can be illustrated.

Specific examples of the compound (c-4) having an ester group include saturated aliphatic monocarboxylic acid esters such as methyl acetate, ethyl acetate, phenyl acetate, methyl propionate, ethyl propionate, ethyl butyrate, and ethyl valerate. Saturated aliphatic polycarboxylic esters such as diethyl succinate, dibutyl succinate, diethyl malonate and dibutyl malonate; unsaturated aliphatic monocarboxylic esters such as ethyl acrylate and methyl methacrylate; Unsaturated aliphatic polyvalent carboxylic esters such as dimethyl acid, dibutyl maleate, diethyl itaconate, and dibutyl itaconate; such as ethyl benzoate, butyl benzoate, methyl toluate, ethyl toluate, and ethyl anisate Aromatic monocarboxylic esters; phthalates Monoethyl, dimethyl phthalate, methyl ethyl phthalate, diethyl phthalate, di-n-propyl phthalate, diisopropyl phthalate, di-n-butyl phthalate, diisobutyl phthalate, dipentyl phthalate, di-n-hexyl phthalate Aromatic polycarboxylic esters such as diheptyl phthalate, di-n-octyl phthalate, di (2-ethylhexyl) phthalate, diisodecyl phthalate, dicyclohexyl phthalate, and diphenyl phthalate . Of these, aromatic dicarboxylic acid diesters such as phthalic acid esters are preferred.

Although there is no restriction | limiting in particular as a solvent in a reductive reaction, In addition to the ether compound illustrated as a solvent of a Grignard compound, aliphatic hydrocarbon compounds like pentane, hexane, heptane, octane, and decane; cyclopentane, cyclohexane, methylcyclohexane, And alicyclic hydrocarbon compounds such as decalin; aromatic hydrocarbon compounds such as benzene, toluene, xylene, ethylbenzene, and 1,3,5-trimethylbenzene; methylene chloride, chloroform, carbon tetrachloride, 1,2 Illustrating halogenated hydrocarbon compounds such as dichloroethane and tetrachloroethane; halogenated aromatic hydrocarbon compounds such as chlorobenzene, chloromethylbenzene, and dichlorobenzene, and combinations of two or more thereof It can be.

The solvent for the reduction reaction is preferably an aliphatic hydrocarbon compound, an aromatic hydrocarbon compound, or an alicyclic hydrocarbon compound, more preferably an aliphatic hydrocarbon compound or an alicyclic hydrocarbon compound. More preferred are aliphatic hydrocarbon compounds, and particularly preferred is hexane or heptane.

In the reduction reaction, the silicon compound (c-1) having an Si—O bond is used in an amount of usually 1 to 500 mol of silicon atom per mol of total titanium atom in the titanium compound (c-2) used, preferably The amount is 1 to 300 mol, particularly preferably 3 to 100 mol.

In the reduction reaction, the amount of the organomagnesium compound (c-3) used is generally 0. The sum of the titanium atoms and the silicon atoms is usually 0.1 per mol of total magnesium atoms in the organomagnesium compound (c-3) used. The amount is 1 to 10 mol, preferably 0.2 to 5.0 mol, particularly preferably 0.5 to 2.0 mol.
The amount of titanium compound (c-2), silicon compound (c-1) having an Si—O bond, and organomagnesium compound (c-3) used in the reduction reaction is also determined by the magnesium atom in the solid component (c) obtained. May be determined empirically so as to be 1 to 51 mol, preferably 2 to 31 mol, particularly preferably 4 to 26 mol, per mol of titanium atom in the precursor.

In the reduction reaction, the amount of the compound (c-4) having an ester group is usually 0.05 to 100 mol, preferably 0.1 to 60 mol, particularly preferably, per 1 mol of total titanium atoms in the titanium compound used. 0.2 to 30 mol.

In the reduction reaction, the temperature at which the organomagnesium compound (c-3) is added to the solution containing the silicon compound (c-1) having a Si—O bond, the titanium compound (c-2) and the solvent is usually − It is 50-100 degreeC, Preferably it is -30-70 degreeC, Especially preferably, it is the range of -25-50 degreeC. The time when adding the organomagnesium compound (c-3) is not particularly limited, and is usually about 30 minutes to 6 hours. From the viewpoint of obtaining a catalyst having a good form, the organomagnesium compound (c-3) is preferably added continuously. In order to further advance the reaction, a reaction at 5 to 120 ° C. may be added.

Further, since the carrier material is supported, the carrier material may be present during the reduction reaction. Although there is no restriction | limiting in particular as a support material, The same thing as the support material of a magnesium compound (b) can be illustrated.

The resulting solid component (c) may be washed with a solvent. Although there is no restriction | limiting in particular in a solvent, Specifically, alcohol, such as methanol, ethanol, isopropanol, n-butanol, isobutanol, hexanol, and 2-ethylhexanol other than the solvent in a reductive reaction, can be illustrated. . Preferred are aliphatic hydrocarbons and aromatic hydrocarbons, more preferred are aromatic hydrocarbons, and particularly preferred is toluene or xylene.

Silicon compound (c-1) having Si—O bond, titanium compound (c-2) represented by general formula (iv), compound (c-4) optionally having an ester group, and organomagnesium compound When (c-3) is added, the reduction reaction of the titanium compound by the organomagnesium compound proceeds, so that the titanium atom of the titanium compound is reduced from tetravalent to trivalent. In the present invention, it is preferable that substantially all tetravalent titanium atoms are reduced to trivalent. The obtained solid component (c) contains a trivalent titanium atom, a magnesium atom and a hydrocarbyloxy group, generally has an amorphous or very weak crystallinity, and preferably has an amorphous structure. .

<Internal electron donor precursor (e)>
The internal electron donor precursor (e) may be a compound that can be converted into the internal electron donor (d) represented by the above general formula (I) by reacting with other components during catalyst production. Although not particularly limited, specific examples include acid halides, acid anhydrides, and perfluoroalkyl esters of the internal electron donor (d). Preferably it is an acid halide, More preferably, it is an acid chloride.

More specifically, dimethylmalonic acid difluoride, dimethylmalonic acid dichloride, dimethylmalonic acid dibromide, dimethylmalonic acid diiodide, dimethylmalonic acid anhydride, dimethylmalonic acid ditriflate, diethylmalonic acid difluoride, diethylmalonic acid dichloride, diethylmalon Acid dibromide, diethylmalonic acid diiodide, diethylmalonic acid anhydride, diethylmalonic acid ditriflate, diisopropylmalonic acid difluoride, diisopropylmalonic acid dichloride, diisopropylmalonic acid dibromide, diisopropylmalonic acid diiodide, diisopropylmalonic acid anhydride, diisopropylmalonic acid diacid Triflate, dinormal butyl malonate difluoride, di normal butyl malonate dichloride, di normal butyl malonate dibro , Dinormal butyl malonic acid diiodide, di normal butyl malonic acid anhydride, di normal butyl malonic acid ditriflate, diisobutyl malonic acid difluoride, diisobutyl malonic acid dichloride, diisobutyl malonic acid dibromide, diisobutyl malonic acid diiodide, diisobutyl malonic acid anhydride , Diisobutylmalonic acid ditriflate, di-tert-butylmalonic acid difluoride, di-tert-butylmalonic acid dichloride, di-tert-butylmalonic acid dibromide, di-tert-butylmalonic acid diiodide, di-tert-butylmalonic acid Anhydride, di-tert-butylmalonate ditriflate, diamylmalonate difluoride, diamylmalonate dichloride, diamylmalonate dibromide, diamylmalonate diiodide, di Milmalonic acid anhydride, diamylmalonic acid ditriflate, dicyclohexylmalonic acid difluoride, dicyclohexylmalonic acid dichloride, dicyclohexylmalonic acid dibromide, dicyclohexylmalonic acid diiodide, dicyclohexylmalonic acid anhydride, dicyclohexylmalonic acid ditriflate, ethylnordibutylmalonate Normal butyl malonate dichloride, ethyl normal butyl malonate dibromide, ethyl normal butyl malonate diiodide, ethyl normal butyl malonate anhydride, ethyl normal butyl malonate ditriflate, ethyl isobutyl malonate difluoride, ethyl isobutyl malonate dichloride, ethyl isobutyl Malonic acid dibromide, ethyl isobutylmalonic acid diiodide, ethyl acetate Sobutylmalonic acid anhydride, ethylisobutylmalonic acid ditriflate, diphenylmalonic acid difluoride, diphenylmalonic acid dichloride, diphenylmalonic acid dibromide, diphenylmalonic acid diiodide, diphenylmalonic acid anhydride, diphenylmalonic acid ditriflate, methyl texylmalonic acid difluoride , Methyl hexyl malonate dichloride, methyl texyl malonate dibromide, methyl texyl malonate diiodide, methyl texyl malonate anhydride, methyl texyl malonate ditriflate, isobutyl isopropyl malonate difluoride, isobutyl isopropyl malonate dichloride, Isobutyl isopropyl malonate dibromide, isobutyl isopropyl malonate diiodide, isobutyl isopropyl malonate anhydride, isobutyl Isopropylmalonic acid ditriflate, ethylphenylmalonic acid difluoride, ethylphenylmalonic acid dichloride, ethylphenylmalonic acid dibromide, ethylphenylmalonic acid diiodide, ethylphenylmalonic acid anhydride, ethylphenylmalonic acid ditriflate, benzylmethylmalonic acid difluoride , Benzylmethylmalonic acid dichloride, benzylmethylmalonic acid dibromide, benzylmethylmalonic acid diiodide, benzylmethylmalonic acid anhydride, benzylmethylmalonic acid ditriflate, dibenzylmalonic acid difluoride, dibenzylmalonic acid dichloride, dibenzylmalonic acid dibromide , Dibenzylmalonic acid diiodide, dibenzylmalonic acid anhydride, dibenzylmalonic acid ditriflate, diallylmalonic acid difluoride, di Rilmalonic acid dichloride, diallylmalonic acid dibromide, diallylmalonic acid diiodide, diallylmalonic acid anhydride, diallylmalonic acid ditriflate, bis (3-butenyl) malonic acid difluoride, bis (3-butenyl) malonic acid dichloride, bis (3- Butenyl) malonic dibromide, bis (3-butenyl) malonic diiodide, bis (3-butenyl) malonic anhydride, bis (3-butenyl) malonic ditriflate, bis (3-chloropropyl) malonic difluoride, bis (3-chloropropyl) malonic acid dichloride, bis (3-chloropropyl) malonic acid dibromide, bis (3-chloropropyl) malonic acid diiodide, bis (3-chloropropyl) malonic acid anhydride, bis (3-chloropropyl) ) Malonic acid ditriflate, cyclohex Sun-1,1-dicarboxylic acid difluoride, cyclohexane-1,1-dicarboxylic acid dichloride, cyclohexane-1,1-dicarboxylic acid dibromide, cyclohexane-1,1-dicarboxylic acid diiodide, cyclohexane-1,1-dicarboxylic acid anhydride And cyclohexane-1,1-dicarboxylic acid ditriflate.

Diethylmalonic acid dichloride, isobutylisopropylmalonic acid dichloride, and diisobutylmalonic acid dichloride are preferred.

<Titanium compound (a)>
The titanium compound (a) is not particularly limited as long as it is a compound containing a titanium atom. Specifically, titanium tetrachloride such as titanium tetrachloride, titanium tetrabromide, and titanium tetraiodide; Tetraalkoxytitanium such as methoxytitanium, tetraethoxytitanium, tetra-n-propoxytitanium, tetraisopropoxytitanium, tetra-n-butoxytitanium, tetraisobutoxytitanium, tetracyclohexyloxytitanium, and tetraphenoxytitanium; Alkoxy titanium trihalides such as chloride, ethoxy titanium trichloride, n-propoxy titanium trichloride, n-butoxy titanium trichloride, and ethoxy titanium tribromide; dimethoxy titanium dichloride, diethoxy titanium dichloride, di Dihalogenated dialkoxytitanium such as sopropoxytitanium dichloride, di-n-propoxytitanium dichloride, and diethoxytitanium dibromide; trimethoxytitanium chloride, triethoxytitanium chloride, triisopropoxytitanium chloride, tri-n-propoxytitanium Mention may be made of monohalogenated trialkoxytitanium such as chloride and tri-n-butoxytitanium chloride. Preferred are titanium tetrahalide and alkoxytitanium trichloride, more preferred is titanium tetrahalide, and still more preferred is titanium tetrachloride. These titanium compounds (a) may be used alone or in combination of two or more.

<Halogenated metal compound (g)>
The metal halide compound (g) is a halide of a Group 13 or Group 14 element, and may optionally contain a hydrocarbyl group and / or a hydrocarbyloxy group.

Specific examples of the Group 13 element include boron, aluminum, gallium, indium, and thallium. Specific examples of the Group 14 element include silicon, germanium, tin, and lead.

The group 13 or group 14 element is preferably silicon, germanium or tin, and particularly preferably silicon.

The halogen atom contained in the metal halide compound (g) is not particularly limited, but is preferably a chlorine atom.

Specific examples of the hydrocarbyl group optionally contained in the metal halide compound (g) include the same hydrocarbyl group contained in the magnesium compound (b).

Specific examples of the hydrocarbyloxy group optionally contained in the halogenated metal compound (g) include the same hydrocarbyloxy groups contained in the magnesium compound (b).

The metal halide compound (g) is preferably ethylaluminum dichloride, ethylaluminum sesquichloride, diethylaluminum chloride, trichloroaluminum, tetrachlorosilane, phenyltrichlorosilane, methyltrichlorosilane, ethyltrichlorosilane, normal propyltrichlorosilane, or p- Tolyltrichlorosilane, more preferably tetrachlorosilane and phenyltrichlorosilane.

<Method for Producing Solid Catalyst Component (A) for Olefin Polymerization>
The method for producing a solid catalyst component (A) for olefin polymerization provided by the present invention comprises the steps of using an internal electron donor (d) and / or an internal electron donor precursor (e) as a solvent for the magnesium compound (b). It is characterized in that the step (P) of solid-liquid separation after being brought into contact is performed twice or more.
In another embodiment, an internal electron donor (d) and / or an internal electron donor precursor (for the solid component (c) containing a trivalent titanium atom, a magnesium atom, and a hydrocarbyloxy group ( The step (Q) of solid-liquid separation after contacting e) in a solvent is performed twice or more.

The number of times of performing the step (P) or the step (Q) is preferably 2 times or more and 10 times or less, more preferably 2 times or more and 5 times or less.

As long as it has the said characteristic, the manufacturing method in particular of the solid catalyst component (A) for olefin polymerization used in this invention is not restrict | limited, Other arbitrary processes can be performed.

Specifically, a step (R) in which any component other than the internal electron donor (d) and the internal electron donor precursor (e) is contacted in a solution and then solid-liquid separated; and a magnesium compound (b) ) Or the step (ω) of washing the solid component (c) with a solvent.

The internal electron donor (d) and the internal electron donor precursor (e) to be brought into contact with the magnesium compound (b) or the solid component (c) may be used alone or in combination. May be.
Components other than the internal electron donor (d) and the internal electron donor precursor (e) that are brought into contact with the magnesium compound (b) or the solid component (c) may not be used, and only one type is used. You may use, and you may use multiple together.

The internal electron donor (d), the internal electron donor precursor (e), and the other components that are brought into contact with the magnesium compound (b) or the solid component (c) are sequentially separated in separate steps. ) Or the solid component (c), or two or more combinations may be contacted simultaneously in the same step.

<Contact process P and Contact process Q>
A step of bringing the internal electron donor (d) and / or the internal electron donor precursor (e) into contact with the magnesium compound (b) or the solid component (c) in a solvent, followed by solid-liquid separation (P, In Q), in addition to the internal electron donor (d) and the internal electron donor precursor (e), an optional component may coexist.

More specifically, the following steps can be exemplified as the contact steps (P, Q).
[Step (β)]
A step of bringing the internal electron donor (d) into contact with the magnesium compound (b) or the solid component (c) in a solution and then solid-liquid separation [Step (γ)]
A step of bringing the internal electron donor precursor (e) into contact with the magnesium compound (b) or the solid component (c) in a solution, followed by solid-liquid separation [Step (βγ)]
A step of bringing the internal electron donor (d) and the internal electron donor precursor (e) into contact with the magnesium compound (b) or the solid component (c) in a solution and then solid-liquid separation [Step (αβ) ]
The step of bringing the titanium compound (a) and the internal electron donor (d) into contact with the magnesium compound (b) or the solid component (c) in a solution and then solid-liquid separation [Step (αγ)]
The step of bringing the titanium compound (a) and the internal electron donor precursor (e) into contact with the magnesium compound (b) or the solid component (c) in a solution and then solid-liquid separation [Step (αβγ)]
The magnesium compound (b) or the solid component (c) is contacted with the internal electron donor (d), the internal electron donor precursor (e) and the titanium compound (a) in a solution and then solid-liquid separated. Process

<Contact process (R)>
A step of bringing the components other than the internal electron donor (d) and the internal electron donor precursor (e) into contact with the magnesium compound (b) or the solid component (c) in a solution, followed by solid-liquid separation ( R) is in any manner as long as the magnesium compound (b) or solid component (c) and the components other than the internal electron donor (d) and the internal electron donor precursor (e) are substantially in contact with each other. There may be.

More specifically, the following steps can be exemplified as the contact step (R).
[Step (α)]
A step of bringing the titanium compound (a) into contact with the magnesium compound (b) or the solid component (c) in a solution, followed by solid-liquid separation [Step (δ)]
A step of bringing the internal compound (d ′) into contact with the magnesium compound (b) or the solid component (c) in a solution, followed by solid-liquid separation [Step (ε)]
A step of bringing the metal halide (g) into contact with the magnesium compound (b) or the solid component (c) in a solution and then solid-liquid separation [Step (αε)]
Step of solid-liquid separation after contacting the titanium compound (a) and the metal halide compound (g) in the solution with the magnesium compound (b) or the solid component (c)

<Method of performing the contact step (P, Q, R)>
Although the implementation method of a contact process (P, Q, R) is not restrict | limited in particular, The following methods can be illustrated as a well-known method.
[Slurry method]
After mixing the solid magnesium compound (b) or solid component (c) dispersed in the solvent with the internal electron donor (d), the internal electron donor precursor (e), and other components, the solid liquid Separation method [Solution method]
Method of solid-liquid separation after mixing magnesium compound (b) or solid component (c) dissolved in a solvent, internal electron donor (d), internal electron donor precursor (e), and other components

<Slurry method>
Although there is no restriction | limiting in particular in the apparatus used in a slurry method, As a well-known apparatus, the reaction container which comprises a stirring blade, and a spray dryer can be illustrated.

The solvent in the slurry method is not particularly limited as long as the magnesium compound (b) or the solid component (c) is not completely dissolved. Specifically, aliphatic hydrocarbons such as pentane, hexane, heptane, octane, and decane are used. Compounds; cycloaliphatic hydrocarbon compounds such as cyclopentane, cyclohexane, methylcyclohexane, and decalin; aromatic hydrocarbon compounds such as benzene, toluene, xylene, ethylbenzene, and 1,3,5-trimethylbenzene; methylene chloride , Halogenated hydrocarbon compounds such as chloroform, carbon tetrachloride, 1,2-dichloroethane, and tetrachloroethane; halogenated aromatic hydrocarbon compounds such as chlorobenzene, chloromethylbenzene, and dichlorobenzene; diethyl ether, di- n-Pro Diether ethers such as ether, diisopropyl ether, di-n-butyl ether, diisobutyl ether, ethyl n-butyl ether, and diisoamyl ether; cyclic ethers such as tetrahydrofuran; methanol, ethanol, isopropanol, n-butanol, isobutanol, hexanol And alcohols such as 2-ethylhexanol. Preferred are aromatic hydrocarbon compounds and halogenated aromatic hydrocarbon compounds, and more preferred are toluene and chlorobenzene.

In the slurry method, when the component brought into contact with the magnesium compound (b) or the solid component (c) is a liquid, the contacting step may be performed using the component as a solvent.

The amount of the component to be brought into contact with the magnesium compound (b) or the solid component (c) in the slurry method is not particularly limited, and is determined empirically depending on the mode of the contact step. When the component to be contacted is a low molecule, in a known method, it is usually 0.1 to 1000 mmol, preferably 0.3 per mol of total magnesium atom in the magnesium compound (b) or solid component (c) used. ˜500 mmol, particularly preferably 0.5 to 300 mmol.

The contact time in the slurry method is not particularly limited, and is determined empirically depending on the mode of the contact process. In a known method, it is usually 10 minutes to 12 hours, preferably 30 minutes to 10 hours, and more preferably 1 hour to 8 hours.

The contact temperature in the slurry method is not particularly limited, and is determined empirically depending on the mode of the contact process. In a known method, it is normally −50 ° C. to 200 ° C., preferably −20 ° C. to 170 ° C., more preferably 0 ° C. to 150 ° C., and particularly preferably 50 ° C. to 130 ° C.

The method of solid-liquid separation is not particularly limited, and specifically, a method of filtering with a glass filter and a decantation method can be exemplified.

<Solution method>
Although there is no restriction | limiting in particular in the apparatus used in a solution method, As a well-known apparatus, the reaction container provided with a stirring blade and a spray dryer can be illustrated.

Although there is no restriction | limiting in particular in the solvent in which a magnesium compound (b) is dissolved in a solution method, Specifically, the same thing as the solvent in a slurry method can be illustrated. Preferred is a mixed solvent of alcohol and an aliphatic hydrocarbon compound and alcohol, and more preferred is a mixed solvent of heptane and 2-ethylhexyl alcohol.

In the solution method, the component brought into contact with the magnesium compound (b) may be used as it is, or may be used in a state where the component is dissolved in a solvent. There is no restriction | limiting in particular as a solvent, It may be the same as that of the solvent of a magnesium compound (b), or may differ. Specifically, the same thing as the solvent in a slurry method can be illustrated.

In the solvent method, a solid component mainly containing the magnesium compound (b) may be precipitated during the process. Usually, the solvent, the components to be brought into contact with, the temperature and the time are determined empirically so that a solid component mainly composed of the magnesium compound (b) is precipitated.

The method of solid-liquid separation is not particularly limited, and specifically, a method of filtering with a glass filter and a decantation method can be exemplified.

<Washing process (ω)>
The solvent in the step (ω) of washing the magnesium compound (b) or the solid component (c) with a solvent is not particularly limited as long as the magnesium compound (b) is not completely dissolved. Specifically, the solvent in the slurry method is used. The same thing can be illustrated. Preferred are aliphatic hydrocarbon compounds, aromatic hydrocarbon compounds, halogenated aliphatic hydrocarbon compounds, and aromatic hydrocarbon compounds, more preferred are hexane, heptane, toluene, methylene chloride, and chlorobenzene, and particularly preferred. Are hexane and toluene.

The washing step (ω) may be in any form as long as the magnesium compound (b) and the solvent are in contact with each other. However, from the viewpoint of effectively bringing the magnesium compound (b) into contact with the solvent, the washing step (ω) is usually performed by a slurry method. Done.

The cleaning time in the cleaning step (ω) is not particularly limited, and is determined empirically depending on the mode of the cleaning step (ω). In a known method, it is usually less than 1 minute to 1 hour, more preferably 1 minute to 30 minutes, and further preferably 5 minutes to 20 minutes.

The cleaning temperature in the cleaning step (ω) is not particularly limited, and is determined empirically depending on the mode of the cleaning step (ω). In a known method, it is usually 0 ° C to 150 ° C.

In the washing step (ω), the solvent is removed after contacting the magnesium compound (b) with the solvent. Although the removal method is not particularly limited, examples of the known method include decantation and filtration.

In the method for producing a solid catalyst component (A) for olefin polymerization provided by the present invention, an internal electron donor (d) and / or an internal electron donor precursor for the magnesium compound (b) or the solid component (c). The step (P) of solid-liquid separation after contacting the body (e) in a solvent is performed twice or more. Other steps may not be performed and may be performed only once or may be performed a plurality of times. The order in which the steps are performed is not particularly limited, and may be performed in any order.

Hereinafter, preferred modes for producing the solid catalyst component (A) for olefin polymerization in the present invention will be exemplified, but the present invention is not limited by the following examples.

One method for producing the solid catalyst component (A) for olefin polymerization is a method using dialkoxymagnesium (b-2). The dialkoxymagnesium (b-2) is subjected to a slurry process (αβ), a washing process (ω), a slurry process (αβ), and a washing process (ω) in this order, thereby producing a solid catalyst for olefin polymerization. Component (A) can be obtained.

Another method for producing the solid catalyst component (A) for olefin polymerization is a method using a solid component (c) containing a trivalent titanium atom, a magnesium atom, and a halogen atom. For the solid component (c), a slurry process (γ), a cleaning process (ω), a slurry process (αβ), a cleaning process (ω), a slurry process contact process (α), and a cleaning process (ω ), The contact step (α) by the slurry method, and the washing step (ω) are sequentially performed to obtain the solid catalyst component (A) for olefin polymerization.

The solid catalyst component (A) of the present invention is reacted with an organoaluminum compound (B) and an optional external electron donor (C) by a known method to form a solid catalyst for olefin polymerization.

Examples of the organoaluminum compound (B) used in the present invention include the compounds described in US Pat. No. 6,903,041. Among them, preferred is trialkylaluminum, a mixture of trialkylaluminum and dialkylaluminum halide, or alkylalumoxane, and more preferred is triethylaluminum, triisobutylaluminum, a mixture of triethylaluminum and diethylaluminum chloride or tetraethyldichloride. Alumoxane.

Examples of the external electron donor (C) optionally used in the present invention include the electron donation described in JP-A-7-216017, JP-A-2006-96936, JP-A-2009-173870, and JP-A-2010-168545. The body can be exemplified. Oxygen-containing compounds and nitrogen-containing compounds are preferred. Examples of the oxygen-containing compound include alkoxy silicon, ether, ester, and ketone. Among them, preferred is alkoxy silicon or ether.

The alkoxysilicon as the external electron donor (C) is preferably a compound represented by the following formula ((vii)).
R ¹⁵ _h Si (OR ¹⁶ ) _4-h (vii)
[Wherein, R ¹⁵ represents a hydrocarbyl group having 1 to 20 carbon atoms, a hydrogen atom or a heteroatom-containing substituent, and R ¹⁶ represents a hydrocarbyl group having 1 to 20 carbon atoms. h represents an integer satisfying 0 ≦ h ^{<4, if R 15} and ^{R 16} there are a plurality, each of ^{R 15} and ^{R 16} the same or different. ]

The ether as the external electron donor (C) is more preferably a cyclic ether compound. The cyclic ether compound is a heterocyclic compound having at least one C—O—C bond in the ring structure, more preferably at least one C—O—C—O—C bond in the ring structure. It is a cyclic ether compound having

The external electron donor (C) is particularly preferably cyclohexylmethyldimethoxysilane, cyclohexylethyldimethoxysilane, diisopropyldimethoxysilane, tert-butylethyldimethoxysilane, tert-butyl-n-propyldimethoxysilane, phenyltrimethoxysilane, diphenyl. Dimethoxysilane, dicyclobutyldimethoxysilane, dicyclopentyldimethoxysilane, tetraethoxysilane, methyltriethoxysilane, ethyltriethoxysilane, isobutyltriethoxysilane, vinyltriethoxysilane, sec-butyltriethoxysilane, cyclohexyltriethoxysilane, Cyclopentyltriethoxysilane, diethylaminotrimethoxysilane, diethylaminotriethoxysilane, 1,3- Oxolane, and 1,3-dioxane.

The external electron donor (C) may be used alone or in combination of two or more.

The method of contacting the solid catalyst component for olefin polymerization (A), the organoaluminum compound (B), and optionally the external electron donor (C) is not particularly limited as long as the solid catalyst for olefin polymerization is produced. Contact is performed in the presence or absence of a solvent. These contact mixtures may be supplied to the polymerization tank, may be separately supplied to the polymerization tank and contacted in the polymerization tank, or any two-component contact mixture and the remaining components may be separately supplied. You may supply to a polymerization tank.

Examples of the olefin used in the method for producing an olefin polymer of the present invention include ethylene and 1-olefin having 3 or more carbon atoms. 1-olefins include linear monoolefins such as propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, and 1-decene; 3-methyl-1-butene, 3- Illustrative examples include branched monoolefins such as methyl-1-pentene and 4-methyl-1-pentene; cyclic monoolefins such as vinylcyclohexane; and combinations of two or more thereof. Among these, ethylene or propylene homopolymerization or copolymerization of a combination of a plurality of olefins mainly composed of ethylene or propylene is preferable, and propylene homopolymerization is more preferable. The combination of a plurality of types of olefins described above may include a combination of two or more types of 1-olefins other than propylene, and a compound having a polyunsaturated bond such as a conjugated diene or a non-conjugated diene. May be included.

The olefin polymer produced by the method for producing an olefin polymer of the present invention is preferably an ethylene homopolymer, a propylene homopolymer, a 1-butene homopolymer, a 1-pentene homopolymer, or a 1-hexene homopolymer. , Ethylene-propylene copolymer, ethylene-1-butene copolymer, ethylene-1-hexene copolymer, propylene-1-butene copolymer, propylene-1-hexene copolymer, ethylene-propylene-1- It is a butene copolymer, an ethylene-propylene-1-hexene copolymer, or a copolymer obtained by multistage polymerization thereof.

The method for forming the solid catalyst for olefin polymerization according to the present invention may be preferably a method comprising the following steps:
(1) In the presence of the solid catalyst component for olefin polymerization (A) and the organoaluminum compound (B), a small amount of olefin (the same or different from the olefin used in the original polymerization (usually called main polymerization)) Polymerized (a chain transfer agent such as hydrogen may be used to control the molecular weight of the olefin polymer produced, or an external electron donor (C) may be used). A step of producing a catalyst component having a surface covered (the polymerization is usually referred to as pre-polymerization, and thus the catalyst component is usually referred to as pre-polymerization catalyst component);
(2) A step of bringing the prepolymerization catalyst component into contact with the organoaluminum compound (B) and the external electron donor (C).

The term “solid catalyst component” in the present invention means not only the above “solid catalyst component” but also “preliminary polymerization catalyst component” and “combination of both”.

The prepolymerization is preferably a slurry polymerization using an inert hydrocarbon such as propane, butane, isobutane, pentane, isopentane, hexane, heptane, octane, cyclohexane, benzene and toluene as a solvent.

The amount of the organoaluminum compound (B) used in the step (1) is usually 0.5 to 700 mol, preferably 0.8 per mol of titanium atom in the solid catalyst component (A) used in the step (1). ˜500 mol, particularly preferably 1 to 200 mol.
The amount of the prepolymerized olefin 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 for olefin polymerization (A) used in the step (1). It is.

The slurry concentration of the solid catalyst component for olefin polymerization (A) in the slurry polymerization in the above step (1) is preferably 1 to 500 g-solid catalyst component for olefin polymerization / liter-solvent, particularly preferably 3 to 300 g for olefin polymerization. Solid catalyst component / liter-solvent.
The prepolymerization temperature is preferably -20 to 100 ° C, particularly preferably 0 to 80 ° C. The partial pressure of the olefin in the gas phase in the prepolymerization is preferably 0.01 to 2 MPa, particularly preferably 0.1 to 1 MPa. However, for olefins that are liquid at the prepolymerization pressure and temperature, Absent. The prepolymerization time is not particularly limited and is preferably 2 minutes to 15 hours.

The following methods (1) and (2) can be exemplified as methods for supplying the solid catalyst component for olefin polymerization (A), the organoaluminum compound (B) and the olefin to the polymerization tank in the prepolymerization:
(1) A method of supplying an olefin after supplying the solid catalyst component (A) for olefin polymerization and the organoaluminum compound (B); and (2) supplying a solid catalyst component (A) for olefin polymerization and an olefin. Then, the method of supplying an organoaluminum compound (B).

The following methods (1) and (2) can be exemplified as methods for supplying olefin to the polymerization tank in the prepolymerization:
(1) A method of sequentially supplying olefins so that the pressure in the polymerization tank is maintained at a predetermined pressure;
The amount of the external electron donor (C) used in the prepolymerization is usually 0.01 to 400 mol, preferably 0.02 to 200 mol, relative to 1 mol of titanium atoms contained in the solid catalyst component (A) for olefin polymerization. Especially preferably, it is 0.03-100 mol, and is 0.003-5 mol normally with respect to 1 mol of organoaluminum compounds (B), Preferably it is 0.005-3 mol, Most preferably, it is 0.01-2 mol.

The following methods (1) and (2) can be exemplified as a method for supplying the external electron donor (C) to the polymerization tank in the prepolymerization:
(1) A method of supplying the external electron donor (C) alone; and (2) A method of supplying a contact product between the external electron donor (C) and the organoaluminum compound (B).
The prepolymerization is also described in JP-A-11-322833.
The usage-amount of the organoaluminum compound (B) at the time of this superposition | polymerization is 1-1000 mol normally with respect to 1 mol of titanium atoms in the solid catalyst component (A) for olefin polymerization, Most preferably, it is 5-600 mol.
The amount of the external electron donor (C) used during the main polymerization is usually 0.1 to 2000 mol, preferably 0.3 to 1000 mol, in particular, per 1 mol of titanium atoms contained in the solid catalyst component (A) for olefin polymerization. Preferably it is 0.5-800 mol, and is 0.001-5 mol normally per 1 mol of organoaluminum compounds (B), Preferably it is 0.005-3 mol, Most preferably, it is 0.01-1 mol.

The temperature of the main polymerization is usually -30 to 300 ° C, preferably 20 to 180 ° C. The polymerization pressure is not particularly limited, and is generally from atmospheric pressure to 10 MPa, preferably from about 200 kPa to 5 MPa in that it is industrial and economical. The polymerization is batch or continuous, and as a polymerization method, a slurry polymerization method or a solution polymerization method using an inert hydrocarbon such as propane, butane, isobutane, pentane, hexane, heptane and octane as a solvent, or a liquid at the polymerization temperature. Examples thereof include a bulk polymerization method using an olefin as a medium and a gas phase polymerization method.

In order to adjust the molecular weight of the polymer obtained by the main polymerization, a chain transfer agent (for example, hydrogen or alkyl zinc such as dimethyl zinc and diethyl zinc) may be used.

According to the present invention, there are obtained a method for producing a solid catalyst component for olefin polymerization, a solid catalyst for olefin polymerization, and a method for producing an olefin polymer, which give a polymer having sufficiently high polymerization activity and a low content of CXS component. I can do it.

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.

<Analysis of catalyst>
The composition analysis of the solid catalyst component was performed as follows. That is, about 20 mg of solid sample is decomposed with about 30 ml of 2N dilute sulfuric acid, and 3 ml of 3% by weight 3% hydrogen peroxide solution is added to this, and the resulting liquid sample absorbs the characteristic absorption at 410 nm. The measurement was made using a Hitachi double beam spectrophotometer U-2001 type, and it was determined by a separately prepared calibration curve. The alkoxy group content is obtained by decomposing about 2 g of a solid sample with 100 ml of water, and then determining the amount of alcohol corresponding to the alkoxy group in the obtained liquid sample using a gas chromatography internal standard method. did. The content of the internal electron donor (d) was determined by dissolving about 300 mg of the solid catalyst component in 100 ml of N, N-dimethylacetamide and then determining the amount of the internal electron donor (d) in the solution by gas chromatography internal standard method.

<Analysis of polymer>
The amount of the 20 ° C. xylene-soluble component (hereinafter abbreviated as CXS) of the olefin polymer was measured as follows. 1 g of the polymer was dissolved in 200 ml of boiled xylene, gradually cooled to 50 ° C., then immersed in ice water, cooled to 20 ° C. with stirring, and allowed to stand at 20 ° C. for 3 hours. Filtered off. The weight percentage of the polymer remaining in the filtrate was defined as CXS (unit = wt%).
The intrinsic viscosity (hereinafter abbreviated as [η]; unit = dl / g) of the olefin polymer was measured at 135 ° C. in a tetralin solvent.

[Example 1]
(1) Synthesis of solid catalyst component (A) for olefin polymerization After replacing a 200 ml flask equipped with a stirrer, a dropping funnel and a thermometer with nitrogen, spherical diethoxymagnesium (magnesium compound (b)) was added to the flask. ) 5 g and 40 ml of chlorobenzene were added. 10 ml of titanium tetrachloride (titanium compound (a)) was added, and 1.5 ml of diethylmalonic acid dichloride (internal electron donor precursor (e)) was added, and the mixture was stirred at 110 ° C. for 3 hours. Next, the stirred mixture was subjected to solid-liquid separation, and washing with 50 ml of toluene was repeated three times at 110 ° C., and 40 ml of toluene was added to the washed solid. To this, 10 ml of titanium tetrachloride and 0.5 ml of diethyl diisobutylmalonate (internal electron donor (d)) were added and stirred at 110 ° C. for 1 hour. Thereafter, the stirred mixture was separated into solid and liquid, washed with 50 ml of toluene three times at 110 ° C., and further washed three times with 50 ml of hexane at room temperature, and the washed solid was dried under reduced pressure. 5.22 g of catalyst component (A) was obtained. The solid catalyst component contained 5.4% by weight diethyl diethylmalonate (internal electron donor (d)) and 6.3% by weight diethyl diisobutylmalonate. The other analysis results are shown in Table 1.

(2) Polymerization of propylene An autoclave with a stirrer having an internal volume of 3 liters was sufficiently dried and then evacuated. Solid catalyst component for olefin polymerization (A) 5.04 mg synthesized with 2.63 mmol of triethylaluminum (organoaluminum compound (B)), 0.26 mmol of cyclohexylethyldimethoxysilane (external electron donor (C)), and (1) Was added. Next, 780 g of propylene and 0.2 MPa of hydrogen were added. The temperature of the autoclave was raised to 80 ° C., and polymerization was performed at 80 ° C. for 1 hour. After completion of the polymerization reaction, unreacted monomers were purged to obtain 246 g of a propylene polymer. The amount of polymer produced per unit amount of catalyst (polymerization activity) was 48800 g-PP / g-solid catalyst component. The obtained results are shown in Table 1.

[Example 2]
(1) Synthesis of solid catalyst component (A) for olefin polymerization A solid catalyst was obtained in the same manner as in Example 1 (1) except that diethyl diethyl malonate was used instead of diethyl malonate dichloride and diethyl diisobutyl malonate. 5.32 g of component (A) was obtained. The analysis results are shown in Table 1.
(2) Polymerization of propylene The same procedure as in Example 1 (2) was conducted except that 8.53 mg of the solid catalyst component (A) obtained in (1) was used. The polymerization activity was 47800 g-PP / g-solid catalyst component. The obtained results are shown in Table 1.

[Example 3]
(1) Synthesis of solid catalyst component (A) for olefin polymerization Solid catalyst component (A) 5 was prepared in the same manner as in Example 1 (1) except that diethyl diethyl malonate was used instead of diethyl malonate dichloride. .19 g was obtained. The analysis results are shown in Table 1.
(2) Polymerization of propylene The same procedure as in Example 1 (2) was conducted except that 4.59 mg of the solid catalyst component (A) obtained in (1) was used. The polymerization activity was 51200 g-PP / g-solid catalyst component. The obtained results are shown in Table 1.

[Comparative Example 1]
(1) Synthesis of solid catalyst component for olefin polymerization (A) The same procedure as in Example 1 (1) was conducted except that diethyl diisobutylmalonate was not used, to obtain 4.96 g of a solid catalyst component (A). The analysis results are shown in Table 1.
(2) Polymerization of propylene The same procedure as in Example 1 (2) was conducted except that 7.20 mg of the solid catalyst component (A) obtained in (1) was used. The polymerization activity was 35700 g-PP / g-solid catalyst component. The obtained results are shown in Table 1.

[Comparative Example 2]
(1) Synthesis of solid catalyst component (A) for olefin polymerization The same procedure as in Example 1 (1) except that diethyl diethyl malonate was used instead of diethyl malonate dichloride, and diethyl diisobutyl malonate was not used. Thus, 5.20 g of a solid catalyst component (A) was obtained. The analysis results are shown in Table 1.
(2) Polymerization of propylene The same procedure as in Example 1 (2) was conducted except that 5.93 mg of the solid catalyst component (A) obtained in (1) was used. The polymerization activity was 43000 g-PP / g-solid catalyst component. The obtained results are shown in Table 1.

[Example 4]
(1) Synthesis of Solid Catalyst Component (A) for Olefin Polymerization After a 100 ml flask equipped with a stirrer, a dropping funnel and a thermometer was replaced with nitrogen, Example 1 of JP 2004-182981 A was placed in the flask. The solid component (c) slurry described in (1) was added so that the solid component was 8.00 g. After standing, toluene was extracted so that the slurry concentration was 0.40 g-solid component / ml-solvent. The temperature was raised to 100 ° C., 1.6 ml of diethylmalonic dichloride (internal electron donor precursor (e)) was added, and the mixture was stirred at the same temperature for 30 minutes. Thereafter, the stirred mixture was subjected to solid-liquid separation, washed 3 times with 40 ml of toluene at 100 ° C., and 15 ml of toluene was added to the washed solid.

Thereafter, 16 ml of titanium tetrachloride (titanium compound (a)) and 1.6 ml of diethyl diethylmalonate (internal electron donor (d)) were added at 65 ° C., and the mixture was stirred at 115 ° C. for 3 hours. Thereafter, the stirred mixture was subjected to solid-liquid separation, washed 3 times with 40 ml of toluene at 100 ° C., and 15 ml of toluene was added to the washed solid. To this, 6.4 ml of titanium tetrachloride was added and stirred at 110 ° C. for 1 hour. Thereafter, the stirred mixture was subjected to solid-liquid separation and washed 3 times with 40 ml of toluene at 100 ° C. To this, 6.4 ml of titanium tetrachloride was added and stirred at 110 ° C. for 1 hour. Thereafter, the stirred mixture was separated into solid and liquid, washed with 40 ml of toluene three times at 100 ° C., and further washed with 40 ml of hexane three times at room temperature, and the washed solid was dried under reduced pressure. 6.25 g of catalyst component (A) was obtained. The solid catalyst component contained 6.9% by weight diethyl diethylmalonate. The other analysis results are shown in Table 2.

(2) Polymerization of propylene The same procedure as in Example 1 (2) was conducted except that 8.85 mg of the solid catalyst component (A) obtained in (1) was used. The polymerization activity was 21700 g-PP / g-solid catalyst component. The obtained results are shown in Table 2.

[Example 5]
(1) Synthesis of solid catalyst component (A) for olefin polymerization The solid catalyst component (A) 7 was prepared in the same manner as in Example 4 (1) except that diethyl diisobutylmalonate was used instead of diethyl diethylmalonate. .12 g was obtained. The analysis results are shown in Table 2.
(2) Polymerization of propylene The same procedure as in Example 1 (2) was conducted except that 7.00 mg of the solid catalyst component (A) obtained in (1) was used. The polymerization activity was 28000 g-PP / g-solid catalyst component. The obtained results are shown in Table 2.

[Comparative Example 3]
(1) Synthesis of solid catalyst component (A) for olefin polymerization The same procedure as in Example 4 (1) was conducted except that diethyl diethyl malonate was not used, to obtain 6.78 g of a solid catalyst component (A). The analysis results are shown in Table 2.
(2) Polymerization of propylene The same procedure as in Example 1 (2) was conducted except that 7.37 mg of the solid catalyst component (A) obtained in (1) was used. The polymerization activity was 19800 g-PP / g-solid catalyst component. The obtained results are shown in Table 2.

[Comparative Example 4]
(1) Synthesis of Solid Catalyst Component (A) for Olefin Polymerization The same procedure as in Example 4 (1) was conducted except that diethylmalonic acid dichloride was not used. As a result, 8.00 g of a solid catalyst component (A) was obtained. The analysis results are shown in Table 2.
(2) Polymerization of propylene The same procedure as in Example 1 (2) was conducted except that 6.32 mg of the solid catalyst component (A) obtained in (1) was used. The polymerization activity was 20500 g-PP / g-solid catalyst component. The obtained results are shown in Table 2.

[Comparative Example 5]
(1) Synthesis of Solid Catalyst Component (A) for Olefin Polymerization Other than using diethyl malonate dichloride instead of diethyl malonate dichloride, using diethyl n-butyl malonate instead of diethyl malonate, and not using chlorobenzene When it carried out like Example 4 (1), 8.37g of solid catalyst components (A) were obtained. The analysis results are shown in Table 2.
(2) Polymerization of propylene The same procedure as in Example 1 (2) was conducted except that 8.72 mg of the solid catalyst component (A) obtained in (1) was used, but almost no polymer was obtained.

[Comparative Example 6]
(1) Synthesis of Solid Catalyst Component (A) for Olefin Polymerization Same as Example 4 (1) except that phthalic acid chloride was used instead of diethylmalonic acid dichloride and diisobutyl phthalate was used instead of diethyl diethylmalonate. Was conducted to obtain 6.38 g of a solid catalyst component (A). The analysis results are shown in Table 2.
(2) Polymerization of propylene The same procedure as in Example 1 (2) was conducted except that 9.81 mg of the solid catalyst component (A) obtained in (1) was used. The polymerization activity was 13200 g-PP / g-solid catalyst component. The obtained results are shown in Table 2.

−： 得られた重合体量が少なく、分析できなかった。

−: The amount of the obtained polymer was small and could not be analyzed.

Claims (13)

A method for producing a solid catalyst component (A) for olefin polymerization comprising a titanium atom, a magnesium atom, a halogen atom, and an internal electron donor (d) represented by the general formula (I), wherein the magnesium compound (b) On the other hand, the step (P) of solid-liquid separation of the internal electron donor (d) and / or the internal electron donor precursor (e) after contacting them in a solvent is carried out twice or more. For producing a solid catalyst component (A) for use.

(I)
[R ¹ , R ² , R ³ , R ⁴ may be the same or different and each is a hydrocarbyl group having 1 to 10 carbon atoms, may be bonded to each other, and may contain a hetero atom. . ] The method for producing a solid catalyst component (A) for olefin polymerization according to claim 1, wherein the magnesium compound (b) is magnesium halide (b-1). The method for producing a solid catalyst component (A) for olefin polymerization according to claim 1, wherein the magnesium compound (b) is dialkoxymagnesium (b-2). A method for producing a solid catalyst component (A) for olefin polymerization comprising a titanium atom, a magnesium atom, a halogen atom and an internal electron donor (d) represented by the above general formula (I), comprising a trivalent titanium atom, A solid liquid after contacting an internal electron donor (d) and / or an internal electron donor precursor (e) with a solid component (c) containing a magnesium atom and a hydrocarbyloxy group in a solvent. The method for producing a solid catalyst component (A) for olefin polymerization, wherein the step (Q) of separation is performed twice or more. In the presence of the silicon compound (c-1) in which the solid component (c) has a Si—O bond, the titanium compound (c-2) represented by the general formula (iv) is converted into the organomagnesium compound (c-3). The manufacturing method of the solid catalyst component (A) for olefin polymerization of Claim 4 obtained by reduce | restoring by.

(Iv)
[Wherein, m represents an integer of 1 to 20; R ¹¹ represents a hydrocarbyl group having 1 to 20 carbon atoms; X ¹ represents a halogen atom or a hydrocarbyloxy group having 1 to 20 carbon atoms] Each represents a plurality of X ¹ may be the same or different. ] The step (P) in which the internal electron donor (d) and / or the internal electron donor precursor (e) is brought into contact with the magnesium compound (b) in a solvent and then solid-liquid separated is performed. The method for producing a solid catalyst component (A) for olefin polymerization according to any one of claims 1 to 3, which is carried out in the presence of The step (Q) of solid-liquid separation after contacting the internal electron donor precursor (e) with the solid component (c) is carried out in the absence of the titanium compound (a), and then the internal electron donor is performed. The method for producing a solid catalyst component (A) for olefin polymerization according to claim 4 or 5, wherein the step (Q) of solid-liquid separation after contacting (d) is carried out in the presence of the titanium compound (a). R ¹ and R ^{2 in} the general formula (I) may be the same or different and are a methyl group or an ethyl group, and R ³ and R ⁴ are each independently a straight chain having 2 to 6 carbon atoms or It is a branched alkyl group, The manufacturing method of the solid catalyst component (A) for olefin polymerization in any one of Claims 1-7. The method for producing a solid catalyst component (A) for olefin polymerization according to any one of claims 1 to 8, wherein the internal electron donor precursor (e) is an acid halide of the internal electron donor (d). The manufacturing method of the solid catalyst for olefin polymerization which consists of the process which the solid catalyst component for olefin polymerization (A) manufactured by the manufacturing method in any one of Claims 1-9 and an organoaluminum compound (B) are made to contact. It consists of the process which the solid catalyst component for olefin polymerization (A) manufactured by the manufacturing method in any one of Claims 1-9, an organoaluminum compound (B), and an external electron donor (C) are made to contact. A method for producing a solid catalyst for olefin polymerization. The manufacturing method of the olefin polymer which consists of the process of superposing | polymerizing an olefin in presence of the solid catalyst for olefin polymerization manufactured by the manufacturing method of Claim 10 or 11. The method for producing an olefin polymer according to claim 12, wherein the olefin is an α-olefin having 3 to 20 carbon atoms.