JP2001139621A - Solid catalyst component for polymerizing olefin, catalyst for polymerizing olefin and method for producing polyolefin - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a highly active mixed catalyst for polymerizing an olefin which efficiently gives a polyolefin having broad molecular weight distribution and to provide a method for producing the polyolefin. SOLUTION: A catalyst for polymerizing an olefin comprises (1) a solid catalyst component composed of magnesium, titanium, halogen and an electron- donating compound (D1) as essential components, (2) a solid catalyst component composed of at least one transition metal selected from manganese, iron, cobalt, nickel and zinc, titanium, halogen and a specific electron-donating compound (D2) as essential components and (3) an organoaluminum compound.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

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

[0002]

BACKGROUND OF THE INVENTION The use of transition metal compounds as supported Ziegler catalyst components is known. For example, use of an iron halide crystal coated with a titanium compound in a molecular thin layer (Japanese Patent Publication No. 39-12105), use of a reaction product of titanium with a metal vapor such as iron (Japanese Patent Publication No. Sho.
0-50806), and preparing a solid catalyst by co-milling an adduct of iron chloride and an electron-donating compound by a ball mill and then reacting with a titanium compound (US Pat. No. 4,439,538). However, the activity of the catalysts produced by these techniques is significantly lower,
It is far from meeting current industrial requirements.

Further, a solid component obtained by contacting a metal halide such as iron pretreated with an electron donor with a silicon halide and a transition metal is used as a catalyst (JP-B-53-46799, JP-B-54). -3479,
JP-B-56-45486, JP-B-58-5201, etc.),
As a solid catalyst component, a magnesium chloride-supported catalyst or a TiCl ₃ catalyst is used in combination with a halide of a transition metal such as iron (JP-A-5-43626), and a transition metal halide such as iron chloride is added to a magnesium chloride-based catalyst. (Japanese Patent Application Laid-Open No. 56-22302,
1-1151785, JP-A-52-878, JP-A-3-5-5
0207, JP-A-4-178406, JP-A-59-11
2007, JP-A-58-147410, JP-A-59-1
13007, JP-A-9-208615) and the like.

The above approach results in catalyst disproportionation,
In turn, this leads to disproportionation of the resulting polymer (a slightly broader molecular weight distribution compared to the unadded catalyst system). Catalysts obtained by these techniques may be effective for specific purposes, but are generally not industrially desirable, such as complicating the control of catalyst production, and improving molding and processing efficiency. Molecular weight distribution (polydispersity index (P
It was not possible to obtain efficiently (with high catalytic activity) a polymer exhibiting I)> 5.0).

Further, a transition metal such as iron is added at the time of polymerization (JP-A-58-101104, JP-A-5-194).
636, JP-A-10-287708, JP-A-10-28
7709), however, these methods have many problems such that the catalyst activity is reduced by addition, and as a result, the produced polymer is colored by the remaining catalyst. Recently, it has also been disclosed that a transition metal halide such as iron chloride is added to a catalyst system using a diether compound as an electron-donating compound of a supported Ziegler catalyst (Japanese Patent Application Laid-Open No. 9-208615). None of them have solved the above-mentioned problems.

[0006]

SUMMARY OF THE INVENTION An object of the present invention is to solve the above-mentioned problems in the prior art in a method for producing a polyolefin, and to obtain a polyolefin having a wide molecular weight distribution (polydispersity index (PI)> 5.0). An object of the present invention is to provide a highly active mixed catalyst for olefin polymerization and a method for producing a polyolefin, which can be obtained well.

[0007]

Means for Solving the Problems The inventors of the present invention have conducted intensive studies on the composition of olefin polymerization catalysts in order to solve the above-mentioned problems. As a result, if olefin polymerization is carried out using a catalyst having the following composition, The present inventors have found that a high molecular weight polyolefin excellent in molding processability can be obtained at a high rate, and have reached the present invention.

That is, the present invention provides a mixed solid catalyst component for olefin polymerization comprising the following components (A) and (B). (A) A solid catalyst component comprising magnesium, titanium, halogen and an electron-donating compound (D1) different from the following compound (D2) as essential components. (B) a solid containing, as essential components, at least one transition metal atom selected from manganese, iron, cobalt, nickel, and zinc; titanium; a halogen; and an electron-donating compound (D2) represented by the following general formula (1). Catalyst component.

[0009]

Embedded image

(In the above formula, X and Y may be the same or different, and each represents —CH ₂ OR, —COO
R, -CR = O, -CHO, -CH 2 OH or -CH
₂ OSi (R) ₃ group, wherein Z is a carbon atom, a silicon atom,
Represents a methylene chain or a substituted methylene chain, and R, R ¹ and R ² may be the same or different and each has a linear or branched alkyl, alicyclic or aryl having 1 to 18 carbon atoms; , R ¹ or R ² may be hydrogen.) The present invention also provides an olefin polymerization catalyst comprising the mixed solid catalyst component for olefin polymerization and an organoaluminum compound. .

The present invention further provides a method for producing an olefin polymer, which comprises polymerizing an olefin using the olefin polymerization catalyst.

[0012]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be specifically described below. Magnesium in the solid catalyst component (A) constituting the mixed solid catalyst component of the present invention is preferably used as a magnesium compound. Examples of such a compound include magnesium halides such as magnesium chloride and magnesium bromide; ethoxymagnesium; Examples thereof include alkoxy magnesium such as isopropoxy magnesium; carboxylic acid salts of magnesium such as magnesium laurate and magnesium stearate; and alkyl magnesium such as butyl ethyl magnesium. Also, a mixture of two or more of these compounds may be used. Preferably, it is a magnesium halide or one which forms a magnesium halide when a solid catalyst is formed, and more preferably, the halogen is chlorine.

The electron donating compound (D1) in the solid catalyst component (A) has a stereoregularity of 95 when the solid catalyst component (A) alone is used as the solid catalyst component for polymerization.
% Is preferable. Specifically, (1) carbons such as methanol, ethanol, propanol, butanol, heptanol, hexanol, octanol, dodecanol, octadecyl alcohol, 2-ethyl-hexyl alcohol, benzyl alcohol, cumyl alcohol, diphenyl methanol, triphenyl methanol, etc. (2) alcohols having an alkyl group such as phenol, cresol, ethylphenol, propylphenol, cumylphenol, nonylphenol and naphthol having 6 to 25 carbon atoms;
(3) ketones having 3 to 15 carbon atoms such as acetone, methyl ethyl ketone, methyl isobutyl ketone, acetophenone and cyclohexanone; and (4) ketones having 2 to 15 carbon atoms such as acetaldehyde, propionaldehyde, tolualdehyde and naphthaldehyde. Aldehydes; (5) methyl formate, ethyl formate, methyl acetate, ethyl acetate, propyl acetate, octyl acetate, cyclohexyl acetate, methyl cellosolve acetate, cellosolve acetate, ethyl propionate, methyl n-butyrate, methyl isobutyrate, ethyl isobutyrate Isopropyl isobutyrate, ethyl valerate, butyl valerate, ethyl stearate, methyl chloroacetate, ethyl dichloroacetate, methyl methacrylate, ethyl methacrylate, ethyl crotonate, ethyl cyclohexanecarboxylate, phenylacetic acid Butyl, methyl phenylbutyrate, propyl phenylbutyrate, methyl benzoate, ethyl benzoate, propyl benzoate, butyl benzoate, octyl benzoate, cyclohexyl benzoate, phenyl benzoate, benzyl benzoate, cellosolve benzoate, methyl toluate, Ethyl toluate, amyl toluate, ethyl ethyl benzoate, methyl anisate, ethyl anisate, ethyl ethoxy benzoate, diethyl phthalate, diisobutyl phthalate, diheptyl phthalate, dinepentyl phthalate, γ-butyrolactone, γ-valerolactone Organic acid esters having 2 to 20 carbon atoms such as, coumarin, phthalide, diethyl carbonate, methyl orthoformate, ethyl orthoformate;
(6) Methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, phenyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, butyl ethoxyacetate, phenyl ethoxyacetate, ethyl n-propoxyacetate, ethyl iso-propoxyacetate, n-butoxy Methyl acetate, ethyl iso-butoxyacetate, ethyl n-hexyloxyacetate, octyl sec-hexyloxyacetate, methyl 2-methylcyclohexyloxyacetate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, 3-methoxypropionic acid Butyl, ethyl 3-ethoxypropionate, butyl 3-ethoxypropionate, n-octyl 3-ethoxypropionate,
Dodecyl 3-ethoxypropionate, pentamethylphenyl 3-ethoxypropionate, ethyl 3- (iso-propoxy) propionate, butyl 3- (iso-propoxy) propionate, allyl 3- (n-propoxy) propionate, 3 -(N-
Butoxy) cyclohexyl propionate, ethyl 3-neopentyloxypropionate, 3- (n-octyloxy)
Butyl propionate, 3- (2,6-dimethyldecyloxy)
Octyl propionate, ethyl 4-ethoxyacetate, cyclohexyl 4-ethoxybutyrate, octyl 5- (n-propoxy) valerate, ethyl 12-ethoxylaurate, ethyl 3- (1-indenoxy) propionate, 3-methoxyacrylic acid Methyl, methyl 2-ethoxyacrylate, ethyl 3-phenoxyacrylate, ethyl 2-methoxypropionate, 2- (is
o-Propoxy) n-butyl butyrate, methyl 2-ethoxyisobutyrate, phenyl 2-cyclohexyloxyisovalerate, butyl 2-ethoxy-2-phenylacetate, allyl 3-neopentyloxybutyrate, 3-ethoxy-3- (o -Methylphenyl) methyl propionate, ethyl 3-ethoxy-2- (o-methylphenyl) propionate, ethyl 4-ethoxy-2-methyl-1-naphthyl nonanoate, ethyl 2-methoxycyclopentanecarboxylate, 2- Ethoxycyclohexanecarboxylic acid butyl ester, 3- (ethoxymethyl) tetralin-2-acetic acid isopropyl ester, 8-butoxydecalin-1-carboxylic acid ethyl ester, 3-ethoxynorbornane-2-carboxylic acid methyl ester, 2- (phenoxy) Methyl acetate, ethyl 3- (p-cresoxy) propionate, 4- (2,4-
Methyl naphthoxy) butyrate, butyl 5-carbaloxyvalerate, methyl 2-phenoxypropionate, ethyl 3- (4-methylphenoxy) -2-phenylpropionate, ethyl 2-phenoxycyclohexanecarboxylate, thiophen-3-oxyacetic acid Ethyl, 2- (2-picolinoxymethyl)-
Alkoxy esters such as ethyl cyclohexanecarboxylate and ethyl 3-furfuryloxypropionate; (7)
Methyl acetyl acetate, ethyl acetyl acetate, butyl acetyl acetate, methyl propionyl acetate, phenyl acetyl acetate, ethyl propionyl acetate, ethyl propionyl acetate, phenyl propionyl acetate, butyl propionyl acetate, ethyl butyryl acetate, ethyl iso-butanoyl acetate,
Ethyl pentanoyl acetate, methyl 3-acetylpropionate, ethyl 3-acetylpropionate, butyl 3-acetylpropionate, ethyl 3-propionylpropionate, 3-
Butyl propionylpropionate, n-octyl 3-propionylpropionate, dodecyl 3-propionylpropionate, pentamethylphenyl 3-propionylpropionate, ethyl 3- (iso-propionyl) propionate, 3-
Butyl (iso-propionyl) propionate, allyl 3- (iso-propionyl) propionate, cyclohexyl 3- (iso-propionyl) propionate, ethyl 3-neopentanoylpropionate, butyl 3-n-laurylpropionate, 3 Methyl-(2,6-dimethylhexanoyl) propionate, ethyl 4-propionyl butyrate, cyclohexyl 4-propionyl butyrate, octyl 5-butyrylvalerate, ethyl 12-butyryl laurate, methyl 3-acetyl acrylate, 2-
Methyl acetyl acrylate, ethyl 3-benzoylpropionate, methyl 3-benzoylpropionate, ethyl 3-methylbenzoylpropionate, butyl 3-toluylbutyrate,
Ethyl o-benzoyl benzoate, ethyl m-benzoyl benzoate, ethyl p-benzoyl benzoate, butyl o-toluyl benzoate, ethyl o-toluyl benzoate, ethyl m-toluyl benzoate, ethyl p-toluyl benzoate, o -(2,4,6-o-
Ethyl trimethylbenzoyl) benzoate, ethyl m- (2,4,6-trimethylbenzoyl) benzoate, ethyl p- (2,4,6-trimethylbenzoyl) benzoate, ethyl o-ethylbenzoylbenzoate, o-acetyl Ethyl benzoate, ethyl o-propionyl benzoate, ethyl o-lauryl benzoate,
ketoesters such as ethyl o-cyclohexanoylbenzoate and ethyl o-dodecylbenzoate; (8) methyl borate;
Butyl titanate, butyl phosphate, diethyl phosphite, di
Inorganic acid esters such as-(2-phenylphenyl) phosphorochloridate; (9) methyl ether, ethyl ether, isopropyl ether, butyl ether, amyl ether, tetrahydrofuran, anisole, diphenyl ether, ethylene glycol diethyl ether, ethylene glycol diphenyl ether; Ethers having 2 to 25 carbon atoms such as 2,2-dimethoxypropane; (10) 2
-(2-ethylhexyl) -1,3-dimethoxypropane, 2-isopropyl-1,3-dimethoxypropane, 2-butyl-1,3-dimethoxypropane, 2-sec-butyl-1,3-dimethoxypropane, 2 -Cyclohexyl-1,3-dimethoxypropane, 2-
Phenyl-1,3-dimethoxypropane, 2-cumyl-1,3-dimethoxypropane, 2- (2-phenylethyl) -1,3-dimethoxypropane, 2- (2-cyclohexylethyl) -1,3-dimethoxy Propane, 2- (p-chlorophenyl) -1,3-dimethoxypropane, 2- (diphenylmethyl) -1,3-dimethoxypropane, 2- (1-naphthyl) -1,3-dimethoxypropane, 2-
(2-fluorophenyl) -1,3-dimethoxypropane, 2-
(1-decahydronaphthyl) -1,3-dimethoxypropane, 2-
(p-tert-butylphenyl) -1,3-dimethoxypropane, 2,
2-dicyclohexyl-1,3-dimethoxypropane, 2,2-diethyl-1,3-dimethoxypropane, 2,2-dipropyl-1,3
-Dimethoxypropane, 2,2-dibutyl-1,3-dimethoxypropane, 2-methyl-2-propyl-1,3-dimethoxypropane, 2-methyl-2-benzyl-1,3-dimethoxypropane, 2-methyl 2-ethyl-1,3-dimethoxypropane, 2-
Methyl-2-isopropyl-1,3-dimethoxypropane, 2-
Methyl-2-phenyl-1,3-dimethoxypropane, 2-methyl-2-cyclohexyl-1,3-dimethoxypropane, 2,2-
Bis (p-chlorophenyl) -1,3-dimethoxypropane, 2,
2-bis (2-cyclohexylethyl) -1,3-dimethoxypropane, 2-methyl-2-iso-butyl-1,3-dimethoxypropane, 2-methyl-2- (2-ethylhexyl) -1,3- Dimethoxypropane, 2,2-diisobutyl-1,3-dimethoxypropane,
2,2-diphenyl-1,3-dimethoxypropane, 2,2-dibenzyl-1,3-dimethoxypropane, 2,2-bis (cyclohexylmethyl) -1,3-dimethoxypropane, 2,2-diisobutyl-1 , 3-Diethoxypropane, 2,2-diisobutyl-1,3-
Dibutoxypropane, 2-isobutyl-2-isopropyl-
1,3-dimethoxypropane, 2,2-di-sec-butyl-1,3-
Dimethoxypropane, 2,2-di-tert-butyl-1,3-dimethoxypropane, 2,2-dineopentyl-1,3-dimethoxypropane, 2-isopropyl-2-isopentyl-1,3-dimethoxypropane, 2- Phenyl-2-benzyl-1,3-dimethoxypropane, 2-cyclohexyl-2-cyclohexylmethyl-1,3-dimethoxypropane, 2,3-diphenyl-1,4-diethoxybutane, 2,3-dicyclohexyl-1 , 4-Diethoxybutane, 2,2-dibenzyl-1,4-diethoxybutane, 2,
3-dicyclohexyl-1,4-diethoxybutane, 2,3-diisopropyl-1,4-diethoxybutane, 2,2-bis (p-methylphenyl) -1,4-dimethoxybutane, 2,3-bis (P-chlorophenyl) -1,4-dimethoxybutane, 2,3-bis (p-fluorophenyl) -1,4-dimethoxybutane, 2,4-diphenyl
-1,5-dimethoxypentane, 2,5-diphenyl-1,5-dimethoxyhexane, 2,4-diisopropyl-1,5-dimethoxypentane, 2,4-diisobutyl-1,5-dimethoxypentane, 2,4 -Diisoamyl-1,5-dimethoxypentane, 3-methoxymethyltetrahydrofuran, 3-methoxymethyldioxane, 1,2-diisobutoxypropane, 1,2-diisobutoxyethane, 1,3-diisoamyloxyethane, 1, 3-diisoamyloxypropane, 1,3-diisoneopentyloxyethane, 1,3-dineopentyloxypropane, 2,2-tetramethylene-1,3-dimethoxypropane, 2,2-pentamethylene
-1,3-dimethoxypropane, 2,2-hexamethylene-1,3-
Dimethoxypropane, 1,2-bis (methoxymethyl) cyclohexane, 2,8-dioxaspiro-5,5-undecane,
7-dioxabicyclo [3,3,1] nonane, 3,7-dioxabicyclo [3,3,0] octane, 3,3-diisobutyl-1,5-oxononane, 6,6-diisobutyldioxyheptane 1,1,1-dimethoxymethylcyclopentane, 1,1-bis (dimethoxymethyl) cyclohexane, 1,1-bis (methoxymethyl) bicyclo-2,2,1-heptane, 1,1-dimethoxymethylcyclopentane, 2 -Methyl-2-methoxymethyl-1,3-dimethoxypropane, 2-cyclohexyl-2-ethoxymethyl-1,3
-Diethoxypropane, 2-cyclohexyl-2-methoxymethyl-1,3-dimethoxypropane, 2,2-diisobutyl-
1,3-dimethoxycyclohexane, 2-isopropyl-2-
Isoamyl-1,3-dimethoxycyclohexane, 2-cyclohexyl-2-methoxymethyl-1,3-dimethoxycyclohexane, 2-isopropyl-2-methoxymethyl-1,3-dimethoxycyclohexane, 2-isobutyl-2-methoxymethyl- 1,3-dimethoxycyclohexane, 2-cyclohexyl
-2-ethoxymethyl-1,3-diethoxycyclohexane,
2-cyclohexyl-2-ethoxymethyl-1,3-dimethoxycyclohexane, 2-isopropyl-2-ethoxymethyl-
1,3-diethoxycyclohexane, 2-isopropyl-2-
Polyethers such as ethoxymethyl-1,3-dimethoxycyclohexane, 2-isobutyl-2-ethoxymethyl-1,3-diethoxycyclohexane, 2-isobutyl-2-ethoxymethyl-1,3-dimethoxycyclohexane; (11 ) Acid amides having 2 to 20 carbon atoms such as acetic acid amide, benzoic acid amide, and toluic acid amide; (13) acid anhydrides having 2 to 20 carbon atoms such as acetic anhydride and phthalic anhydride; (14) monomethylamine, monoethylamine, diethylamine, tributylamine, piperidine, tribenzylamine, C1-C20 alcohols such as aniline, pyridine, picoline and tetramethylethylenediamine; Down like; (15) acetonitrile, benzonitrile, 2 carbon atoms, such as trinitriles
20 nitriles; (16) C2-C2 such as ethylthioalcohol, butylthioalcohol, phenylthiol, etc.
20 thiols; (17) thioethers having 4 to 25 carbon atoms such as diethyl thioether and diphenyl thioether; (18) sulphates having 2 to 20 carbon atoms such as dimethyl sulfate and diethyl sulfate; (19) phenylmethyl sulfone And sulfonic acids having 2 to 20 carbon atoms such as diphenylsulfone; (20) phenyltrimethoxysilane, phenyltriethoxysilane, phenyltributoxysilane, vinyltriethoxysilane, diphenyldiethoxysilane, phenyldimethylmethoxysilane, phenyldimethylethoxy Silane, triphenylmethoxysilane,
Silicon-containing compounds having 2 to 24 carbon atoms such as hexamethyldisiloxane, octamethyltrisiloxane, trimethylsilanol, phenyldimethylsilanol, triphenylsilanol, diphenylsilanediol, lower alkyl silicate (especially ethyl silicate), and the like. Can be. Two or more of these electron donating compounds may be used. Of these, preferred are organic acid esters, alkoxy esters, keto esters, and polyethers.

The method for preparing the solid catalyst component (A) includes:
Although not particularly limited, for example, the following examples can be given. By co-milling a magnesium compound, a titanium halide and an electron donating compound (D1),
Alternatively, a method of obtaining a catalyst component by contacting by dispersion or dissolution in a solvent.

A complex of a magnesium compound and an organic or inorganic compound (which may contain an electron donating compound (D1)) is formed, and a titanium halide or a complex of the titanium halide and the electron donating compound (D1) is formed thereon. A method of obtaining a catalyst component by contacting. A complex of a magnesium compound and an organic or inorganic compound (which may include the above-described electron donating compound (D1)) is formed, and the electron donating compound (D1) and the titanium compound are sequentially contacted with the composite (order of contact). May be replaced) to obtain a catalyst component.

A method for obtaining a catalyst component by contacting an electron-donating compound (D1) with a magnesium compound (or further containing a titanium compound) and simultaneously or subsequently contacting with a titanium compound and / or subjecting to a halogenation treatment ( Including the use of titanium compounds at any stage). The production of the above-mentioned catalyst component may be carried out by a method of carrying or impregnating on a substance generally used as a catalyst carrier, for example, silica or alumina.

The quantitative relationship among the components in the solid catalyst component (A) is arbitrary as long as the effects of the present invention are recognized, but generally it is preferably in the following range. The content of magnesium is 0.1 to 100 in molar ratio to titanium.
0, preferably in the range of 2 to 200, the content of halogen may be in the range of 1 to 100 in molar ratio to titanium, and the content of the electron donating compound (D1) may be 10 in molar ratio to titanium. Within the following range, preferably 0.0
It may be in the range of 1 to 5.

The transition metal atoms in the solid catalyst component (B) constituting the mixed solid catalyst component of the present invention are manganese, iron,
An atom selected from cobalt, nickel and zinc,
These transition metal atoms are preferably used as halides. More preferred are transition metal halides having a CdCl ₂ type crystal form, specifically manganese chloride, iron (II) chloride, cobalt chloride, nickel chloride, zinc chloride, particularly manganese chloride, iron chloride (I
I) and cobalt chloride can be exemplified, and iron (II) chloride is particularly preferred. Further, a mixture of two or more of these transition metal halide compounds may be used.

Titanium in the solid catalyst component of the present invention is preferably used as a titanium compound. Examples of such a compound include titanium halides such as titanium tetrachloride, titanium trichloride and titanium tetrabromide; titanium butoxide, titanium ethoxy. And titanium alkoxides such as phenoxytitanium chloride. Also, a mixture of two or more of these compounds may be used. Among these titanium compounds, tetravalent titanium compounds containing halogen are preferable, and titanium tetrachloride is particularly preferable.

The halogen in the solid catalyst component of the present invention is fluorine, chlorine, bromine or iodine, and is preferably used as a halogen-containing compound. As halogen, chlorine is particularly preferred. Representative halogen-containing compounds include titanium halides such as titanium tetrachloride and titanium tetrabromide, silicon halides such as silicon tetrachloride and silicon tetrabromide, and phosphorus halides such as phosphorus trichloride and phosphorus pentachloride. However, a hydrohalic acid such as HCl, HBr, or HI may be used depending on the preparation method. These halogen-containing compounds may be commonly used as the above-mentioned transition metal halogen compounds and titanium halide compounds.

The electron donating compound (D2) is a solid catalyst component.
When the component (B) is used alone as a solid catalyst component for polymerization
Has a stereoregularity of 80% or more, particularly 90% or more in XI;
In particular, it constitutes a catalyst system expressing 95% or more.
Preferably, the specific formula is represented by the general formula (1).
Compound. Electron donation represented by general formula (1)
In the active compound (D2), Z has 1 to 10 carbon atoms and is preferably
Or a methylene chain having 1 to 6 carbon atoms or substituted methylene
And the substituent on the substituted methylene chain may be charcoal.
Primed 1 to 20, preferably C1 to C10 linear, branched
Branched or cyclic hydrocarbon group or aromatic having 6 or more carbon atoms
It may be a group hydrocarbon group. Z is preferably a carbon atom
Good. R is an alkyl group having 1 to 10 carbon atoms.
Is preferred, in which case R¹Is methyl, ethyl, pro
When pill or isopropyl, R^TwoIs Echi
Propyl, isopropyl, butyl, isobutyl, te
rt-butyl, 2-ethylhexyl, cyclohexylmethyl
R, phenyl or benzyl;¹Is hydrogen
, Then R ^TwoIs ethyl, butyl, sec-butyl,
tert-butyl, 2-ethylhexyl, cyclohexylethyl
, Diphenylmethyl, p-chlorophenyl, 1-naphthy
Or 1-decahydronaphthyl;
¹And R^TwoMay be the same, ethyl, propyl,
Isopropyl, butyl, isobutyl, tert-butyl,
Opentyl, isopentyl, phenyl, benzyl or
It may be cyclohexyl.

In such compounds, X and Y are
Also -CH_TwoA diether compound which is an OR group, X and Y
Are diester compounds in which both are -COOR groups, X and
Diketone compounds wherein Y is both —CR−O groups, X and
A dinal compound wherein Y is both a -CHO group, X and Y
Are both -CH_TwoA diol compound which is an OH group, X and
Y is both -CH_TwoOSi (R)_ThreeThe disiloxy group
Compound, X is -CH_TwoAn OR group, and Y is a -COOR group
Wherein X is -CH _TwoOR group
A ketoether compound wherein Y is a —CR ＝ O group;
And X is a —COOR group, and Y is a —CR ＝ O group.
Toester compounds, among which
Are diether compounds, diester compounds, alkoxy
Stele compounds and ketoester compounds are preferred.

Specific examples of the above diether compound include:
2- (2-ethylhexyl) -1,3-dimethoxypropane, 2-isopropyl-1,3-dimethoxypropane, 2-butyl-1,3-
Dimethoxypropane, 2-sec-butyl-1,3-dimethoxypropane, 2-cyclohexyl-1,3-dimethoxypropane,
2-phenyl-1,3-diethoxypropane, 2-cumyl-1,3-
Diethoxypropane, 2- (2-phenylethyl) -1,3-dimethoxypropane, 2- (2-cyclohexylethyl) -1,3-dimethoxypropane, 2- (diphenylmethyl) -1,3-dimethoxypropane, 2- (2-fluorophenyl) -1,3-dimethoxypropane, 2- (1-decahydronaphthyl) -1,3-dimethoxypropane, 2- (p-tert-butylphenyl) -1,3-dimethoxypropane , 2,2-dicyclohexyl-1,3-dimethoxypropane, 2,2-diethyl-1,3-dimethoxypropane, 2,2-
Dipropyl-1,3-dimethoxypropane, 2,2-dibutyl-
1,3-dimethoxypropane, 2-methyl-2-propyl-1,3-
Dimethoxypropane, 2-methyl-2-benzyl-1,3-dimethoxypropane, 2-methyl-2-ethyl-1,3-dimethoxypropane, 2-methyl-2-phenyl-1,3-dimethoxypropane, 2- Methyl 2-cyclohexyl-1,3-dimethoxypropane, 2,2-bis (p-chlorophenyl) -1,3-dimethoxypropane, 2,2-bis (2-cyclohexylethyl) -1,3-dimethoxypropane, 2 -Methyl-2-isobutyl-1,3-dimethoxypropane, 2-methyl-2- (2-ethylhexyl) -1,
3-dimethoxypropane, 2-methyl-2-isopropyl-1,3
-Dimethoxypropane, 2,2-diisopropyl-1,3-dimethoxypropane, 2,2-diphenyl-1,3-dimethoxypropane, 2,2-dibenzyl-1,3-dimethoxypropane, 2,2-
Bis (cyclohexylmethyl) -1,3-dimethoxypropane, 2,2-diisobutyl-1,3-diethoxypropane, 2,2-
Diisobutyl-1,3-dibutoxypropane, 2-isobutyl
-2-isopropyl-1,3-dimethoxypropane, 2,2-di-s
ec-butyl-1,3-dimethoxypropane, 2,2-di-tert-butyl-1,3-dimethoxypropane, 2-di-neopentyl-
1,3-dimethoxypropane, 2-isopropyl-2-isopentyl-1,3-dimethoxypropane, 2-phenyl-2-benzyl-1,3-dimethoxypropane, 2-cyclohexyl-2-cyclohexylmethyl-1,3- Dimethoxypropane, 2-isopropyl-3,7-dimethyloctyl-1,3-dimethoxypropane, 2,2-diisopropyl-1,3-dimethoxypropane,
2-isopropyl-2-cyclohexyl-1,3-dimethoxypropane, 2-isopropyl-2-cyclopentyl-1,3-dimethoxypropane, 2,2-dicyclopentyl-1,3-dimethoxypropane, 2-heptyl-2- Pentyl-1,3-dimethoxypropane and the like can be mentioned.

Specific examples of the diester compound include 2,2-
Diisopropylmalonic acid diethyl ester, 2,2-diisobutymalonic acid diethyl ester, 2,2-diisopentylmalonic acid diethyl ester, 2,2-diisohexylmalonic acid diethyl ester, 2,2-diisoheptylmalonic acid Diethyl ester, 2,2-di (2-cyclopentylethyl) malonic acid diethyl ester, 2,2-di (2-cyclohexylethyl) malonic acid diethyl ester, 2-isopropyl-2-isobutylmalonic acid diethyl ester, 2-isopropyl -2
-Diethyl isopentylmalonate, diethyl 2-isopropyl-2-isohexylmalonate, diethyl 2-isopropyl-2-isoheptylmalonate, diethyl 2-isopropyl-2- (2-cyclopentylethyl) malonate 2-isopropyl-2- (2-cyclopentylethyl) malonic acid diethyl ester, 2-isopropyl-2- (2-cyclohexylethyl) malonic acid diethyl ester, 2-isobutyl-2-isopentylmalonic acid diethyl ester, 2- Isobutyl-2-isohexylmalonic acid diethyl ester, 2-isobutyl-2-isoheptylmalonic acid diethyl ester, 2-isobutyl-2-cyclopentylmalonic acid diethyl ester, 2-isobutyl-2-cyclohexylmalonic acid diethyl ester, 2- Isobutyl-2-
(2-cyclopropylethyl) malonic acid diethyl ester, 2-isopentyl-2-isohexylmalonic acid diethyl ester, 2-isopentyl-2-isoheptylmalonic acid diethyl ester, 2-isopentyl-2-cyclopentylmalonic acid diethyl ester, 2-isopentyl-2- (2-cyclopentylethyl) malonic acid diethyl ester, 2-isohexyl-2-isoheptylmalonic acid diethyl ester,
2-isohexyl-2-cyclopentylmalonic acid diethyl ester, 2-isohexyl-2- (2-cyclopentylethyl)
Malonic acid diethyl ester, 2-cyclopentyl-2-cyclohexylmalonic acid diethyl ester, 2-cyclopentyl-2- (2-cyclopentylethyl) malonic acid diethyl ester, 2- (2-cyclopentylethyl) -2- (2-cyclohexane Xylethyl) malonic acid diethyl ester and the like.

Specific examples of the alkoxy ester compound include ethyl 3-ethoxy-2-phenylpropionate, ethyl 3-ethoxypropionate, ethyl 3-ethoxy-2-mesitylpropionate, and 3-butoxy-2- (methoxy Ethyl phenyl) propionate, methyl 3-i-propoxy-3-phenylpropionate, ethyl 3-ethoxy-3-phenylpropionate, ethyl 3-ethoxy-3-tert-butylpropionate, 3-ethoxy-3-adamantyl Ethyl propionate, ethyl 3-ethoxy-2-tert-butylpropionate, 3-
Ethyl ethoxy-2-tert-amylpropionate, ethyl 3-ethoxy-2-adamantylpropionate, 3-ethoxy-2
-Ethyl bicyclo [2,2,1] heptylpropionate, ethyl 2-ethoxy-cyclohexanecarboxylate, methyl 3- (ethoxymethyl) -cyclohexanecarboxylate, methyl 3-ethoxy-norbornane-2-carboxylate, 2-methyl -2-
Isopropyl-3-ethoxy-butyl propionate, 2,2-
Ethyl diisopropyl-3-methoxy-propionate, 2,
Ethyl 2-diisopropyl-3-methoxy-propionate,
Methyl 2-isopropyl-2-isobutyl-3-methoxy-propionate, ethyl 2-isopropyl-2-isobutyl-3-methoxy-propionate, methyl 2-isopropyl-2-isopentyl-3-methoxy-propionate, 2- Ethyl isopropyl-2-isopentyl-3-methoxy-propionate, ethyl 2,2-disobutyl-3-methoxy-propionate, 2-cyclopentyl-2-isopentyl-3-methoxy-
Examples thereof include methyl propionate and ethyl 2,2-dicyclopentyl-3-methoxy-propionate.

Specific examples of the ketoester compound include 3-
Methyl acetylpropionate, ethyl 3-acetylpropionate, butyl 3-acetylpropionate, ethyl 3-propionylpropionate, butyl 3-propionylpropionate, normal octyl 3-propionylpropionate,
Dodecyl 3-propionylpropionate, pentamethylphenyl 3-propionylpropionate, ethyl 3- (isopropionyl) propionate, butyl 3- (isopropionyl) propionate, allyl 3- (isopropionyl) propionate, 3- (iso Propionyl) cyclohexyl propionate, ethyl 3-neopentanoyl propionate,
Butyl normal lauryl propionate; methyl 3- (2,6-dimethylhexanoyl) propionate;
The solid catalyst component (B) of the present invention can be prepared, for example, by the following method, but the method of preparing the solid catalyst component (B) of the present invention is not limited to these methods. .

A method of obtaining a catalyst component by bringing a transition metal halide, a titanium halide and an electron-donating compound (D2) into contact with each other by co-grinding or by dispersing or dissolving in a solvent. A complex of a transition metal halogen compound and an organic or inorganic compound (which may contain an electron donating compound (D2)) is formed, and a titanium halide or a complex of the titanium halide and the electron donating compound (D2) is formed on the complex. To obtain a catalyst component by contacting the catalyst.

A complex of a transition metal halogen compound and an organic or inorganic compound (which may contain an electron donating compound (D2)) is formed, and an electron donating compound (D
2) A method of sequentially contacting the titanium compound with the titanium compound (the order of contact may be changed) to obtain a catalyst component. Transition metal halogen compounds (or additionally containing titanium compounds)
To obtain a catalyst component by contacting and / or halogenating treatment with a titanium compound at the same time or at a subsequent stage (including the use of a titanium compound at any stage). It is necessary).

The preparation of the above catalyst component may be carried out by a method of carrying or impregnating on a substance generally used as a catalyst carrier, for example, silica or alumina. The quantitative relationship of each component in the solid catalyst component (B) is arbitrary as long as the effects of the present invention are recognized, but generally it is preferably in the following range. That is, the content of the transition metal may be in the range of 0.1 to 1000, preferably in the range of 2 to 200 in terms of the molar ratio to titanium, and the content of the halogen may be in the range of 1 to 100 in terms of the molar ratio to titanium, The content of the electron donating compound (D2) may be in the range of 10 or less, preferably in the range of 0.01 to 5 in molar ratio to titanium.

In the present invention, as a solid catalyst component for olefin polymerization, F
Only a compound containing a transition metal selected from e, Mn, Co, Ni, and Zn is substantially used, and a Mg compound conventionally used as a carrier is not substantially used. The mixing ratio of the solid catalyst component (A) and the solid catalyst component (B) in the mixed solid catalyst component of the present invention is not particularly limited, but is generally 0.001 <([A] / ([A ] +
[B])) <0.999, preferably 0.01 <
([A] / ([A] + [B])) <0.99, more preferably 0.1 <([A] / ([A] + [B])) <0.
9 (where [A] and [B] are the amounts of the respective solid catalyst components (A) and (B)).

The solid catalyst component (A) and the solid catalyst component (B) may be mixed in advance before being inserted into the polymerization reactor, or may be separately inserted into the polymerization reactor, May be mixed. The amount of each of the solid catalyst components (A) and (B) in the polymerization system is usually 0.005 to 0.5 mmol / L, preferably 0.01 to 0.5 mmol / L in terms of Ti atoms. It is good.

As typical examples of the organoaluminum compound used in the olefin polymerization catalyst of the present invention, there are compounds represented by the following general formulas (2) to (4). AlR ³ R ⁴ R ⁵ (2) R ⁶ R ⁷ Al—O—AlR ⁸ R ⁹ (3)

[0033]

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In the above general formulas (2), (3) and (4), R ³ , R ⁴ and R ⁵ may be the same or different and each represents a hydrocarbon group having 12 or less carbon atoms, Represents a halogen atom or a hydrogen atom (provided that at least one of them is a hydrocarbon group);
⁶ , R ⁷ , R ⁸ and R ⁹ may be the same or different and each represent a hydrocarbon group having 12 or less carbon atoms, R ¹⁰ represents a hydrocarbon group having 12 or less carbon atoms, k is 1
Is an integer greater than or equal to.

Typical examples of the organoaluminum compounds represented by the general formula (2) include trialkylaluminum, tripropylaluminum, tributylaluminum, triisobutylaluminum, trihexylaluminum and trioctylaluminum. Examples thereof include alkyl aluminum hydrides such as aluminum, diethyl aluminum hydride and diisobutyl aluminum hydride, and alkyl aluminum halides such as diethyl aluminum chloride, diethyl aluminum bromide and ethyl aluminum sesquichloride.

Representative examples of the organoaluminum compounds represented by the general formula (3) include alkyldialuminoxanes such as tetraethyldialuminoxane and tetrabutyldialuminoxane. General formula (4)
Represents an aluminoxane, which is a polymer of an aluminum compound. In the general formula (4), R ¹⁰ includes a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group and the like, and is preferably a methyl group or an ethyl group. The value of k is preferably 1 to 10.

Of these organoaluminum compounds, trialkylaluminums, alkylaluminum halides and alkylaluminoxanes are preferred.
Particularly, trialkylaluminums are preferable because they give preferable results. In the production of the olefin polymer, the amount of the organoaluminum compound used in the polymerization system is generally ^10-4 mmol / L or more, and preferably ^10-2 mmol / L or more. Further, the molar ratio to the titanium atom in the solid catalyst component for olefin polymerization is generally 0.5 or more, preferably 2 or more.
Above, especially 10 or more are preferred. When the amount of the organoaluminum compound is too small, the polymerization activity is greatly reduced. When the amount of the organoaluminum compound used in the polymerization system is 20 mmol / L and the ratio to the titanium atom is 1000 or more in molar ratio, the catalyst performance is further improved even if these values are further increased. Never.

The electron-donating compound (D3) used as the third component in the present invention is a compound selected from an organosilicon compound having an alkoxy group, a nitrogen-containing compound, a phosphorus-containing compound and an oxygen-containing compound. It is preferable to use at least one or more of these. Among these, it is particularly preferable to use an organic silicon compound having an alkoxy group.

The amount of the third component to be used is preferably in the range of 0.001 to 5, more preferably 0.01 to 1, in terms of molar ratio to the organoaluminum compound. As the organosilicon compound having an alkoxy group, specifically, tetramethoxysilane, tetraethoxysilane, tetrabutoxysilane, tetraisobutoxysilane, trimethylmethoxysilane, trimethylethoxysilane, triethylmethoxysilane, triethylethoxysilane, ethylisopropyl Dimethoxysilane, propylisopropyldimethoxysilane, diisopropyldimethoxysilane, diisobutyldimethoxysilane, isopropylisobutyldimethoxysilane, di-tert-butyldimethoxysilane, te
rt-butylmethyldimethoxysilane, tert-butylethyldimethoxysilane, tert-butylnormalpropyldimethoxysilane, tert-butylisopropyldimethoxysilane, tert-butylnormalbutyldimethoxysilane, tert-butylisobutyldimethoxysilane, tert-butyl
Butyl- (sec-butyl) dimethoxysilane, tert-butylamyldimethoxysilane, tert-butylhexyldimethoxysilane, tert-butylheptyldimethoxysilane,
tert-butyloctyldimethoxysilane, tert-butylnonyldimethoxysilane, tert-butyldecyldimethoxysilane, tert-butyl (3,3,3-trifluoromethylpropyl) dimethoxysilane, tert-butyl (cyclopentyl) dimethoxysilane, tert-butyl Butyl (cyclohexyl) dimethoxysilane, dicyclopentyldimethoxysilane, bis (2-methylcyclopentyl) dimethoxysilane, bis (2,3-dimethylcyclopentyl) dimethoxysilane, diphenyldimethoxysilane, phenyltriethoxysilane, mesityltrimethoxysilane, ethyl Trimethoxysilane, normal propyltrimethoxysilane, isopropyltrimethoxysilane, butyltrimethoxysilane, isobutyltrimethoxysilane, tert-butyltrimethoxysilane, sec-butyltrimethoxysilane Methoxysilane, amyltrimethoxysilane, isoamyltrimethoxysilane, cyclopentyltrimethoxysilane, cyclohexyltrimethoxysilane, norbornanetrimethoxysilane, indenyltrimethoxysilane, 2-methylcyclopentyltrimethoxysilane, cyclopentyl (ter
t-butoxy) dimethoxysilane, isopropyl (tert-butoxy) dimethoxysilane, tert-butyl (isobutoxy) dimethoxysilane, tert-butyl (tert-butoxy)
Dimethoxysilane, tert-butyl (2,6-dimethylpiperidyl) dimethoxysilane, tert-butyl (3,3,3-trifluoropropyl) dimethoxysilane, texyltrimethoxysilane, texyl (isopropoxy) dimethoxysilane, texil ( tert-butoxy) dimethoxysilane,
Texyl (pyrrolidyl) dimethoxysilane, texil (2,6-dimethylpiperidyl) dimethoxysilane, and the like.

As the nitrogen-containing compound, specifically, 2.
6-diisopropylpiperidine, 2.6-diisopropyl-4-
2,6-substituted piperidines such as methylpiperidine, N-methyl-2,2,6,6-tetramethylpiperidine, 2,5-diisopropylazolidine, N-methyl-2,2,5,5-tetramethyl 2,5-substituted azolidines such as azolidine, N, N, N ', N'-tetramethylmethylenediamine, N, N, N', substituted methylenediamines such as N'-tetraethylmethylenediamine, 1,3 And substituted imidazolines such as -dibenzylimidazolidin and 1,3-dibenzyl-2-phenylimidazolidin.

Examples of the phosphorus-containing compound include triethyl phosphite, trinormal propyl phosphite, triisopropyl phosphite, trinormal butyl phosphite, triisobutyl phosphite, diethyl normal butyl phosphite, and diethyl phenyl phosphite. And the like. As the oxygen-containing compound, specifically, 2,2-substituted tetrahydrofurans such as 2,2,6,6-tetramethyltetrahydrofuran, 2,2,6,6-tetraethyltetrahydrofuran, and 1,1-dimethoxy-2 , 3,4,5-tetrachlorocyclopentadiene, 9,9-
Dimethoxymethane derivatives such as dimethoxyfluorene and diphenyldimethoxymethane; Alternatively, the electron donating compound (D1) or (D
Compounds similar to 2) can also be used.

The olefin used in the present invention is generally an olefin having at most 12 carbon atoms, and typical examples thereof include ethylene, propylene, butene-1, 4-methylpentene-1, and hexene- 1, octene-1
And the like. In carrying out the polymerization, two or more olefins may be copolymerized (for example, copolymerization of ethylene and propylene).

In carrying out the polymerization, the solid catalyst component of the present invention, the organoaluminum compound,
The components may be introduced individually into the polymerization vessel, or two or all of them may be premixed. The polymerization can be carried out in an inert solvent, in a liquid monomer (olefin) or in the gas phase. In order to obtain a polymer having a practical melt flow, a molecular weight modifier (generally, hydrogen) may be coexisted.

The value of the polydispersity (PI) of the polymer produced by the above-mentioned catalyst system shows PI> 5.0, and more preferably in the range of 5.0 <PI <30. More preferably, the value is in the range of 5.0 <PI <20. The polymerization temperature is generally from -10 to 180C, and practically from 20C to 130C.

In addition, the presence or absence of the prepolymerization, the configuration of the polymerization reactor, the method of controlling the polymerization, the method of post-treatment, and the like are not specifically limited to the present catalyst system, and all known methods can be applied.

[0046]

The present invention will be described in more detail with reference to the following examples. In each of the examples, each compound (organic solvent, olefin, hydrogen, titanium compound, transition metal halide, silicon compound, etc.) used in the production and polymerization of the solid catalyst component is substantially water-free.

The production and polymerization of the solid catalyst component are as follows:
The test was performed substantially without moisture and under an atmosphere of nitrogen. The stereoregularity of the polymer was evaluated by the amount of xylene-insoluble matter (XI%) at 25 ° C of the polymer. That is, 2.5 g of polymer in 250 mL of xylene at 135 ° C.
After dissolving, the amount of polymer (% by weight) precipitated by cooling the solution to 25 ° C. was measured and defined as the amount of xylene-insoluble matter (XI%). In addition, the melt flow rate (MFR) under a load of 2.16 kg was determined according to JIS-7210-
Measured according to 1995.

The value of the polydispersity index (PI) as an index for evaluating the molecular weight distribution of the polymer was determined by the following method. 2
Press molding at 30 ° C. for 5 minutes, thickness 1.5mm,
A disk-shaped measurement sample having a diameter of 25 mm was used. The measurement is
Performed using a Rheometer RMS80 from Rhometrics, Zeichner, GR, P
atel, PD: 2nd World Congr. of Chem. Eng., Montreal,
Can., 1981.

Example 1 (Preparation of solid catalyst component (A)) Anhydrous magnesium chloride 2
0 g and 5.9 g of di-n-butyl phthalate (electron-donating compound / Mg molar ratio = 0.1) were placed in a 1 L cylindrical container filled with magnetic balls having a diameter of 10 mm and an apparent volume of 50%.
Co-milling was performed for 12 hours using a vibration mill having an amplitude of 9 mm.

Separately, 120 mL of toluene and 120 mL of titanium tetrachloride were added to a flask having an internal volume of 500 mL to cause a reaction, and heated to 60 ° C. The co-ground solid was added to this solution, and the mixture was stirred at 110 ° C. for 2 hours. The contents of the flask were washed three times with 200 mL of toluene and dried at 30 ° C. under reduced pressure. (Preparation of solid catalyst component (B)) 30 g of anhydrous iron (II) chloride (manufactured by Aldrich) and 5.1 g of 2-isopropyl-2-isopentyl-1,3-dimethoxypropane (electron-donating compound / Fe molar ratio = 0.1) was placed in a 1 L cylindrical container filled with 50% apparent volume of a magnetic ball having a diameter of 10 mm, and co-milled for 12 hours using a vibration mill having an amplitude of 9 mm.

Separately, 120 mL of toluene and 120 mL of titanium tetrachloride were added to a flask having an internal volume of 500 mL to cause a reaction, and heated to 60 ° C. The co-ground solid was added to this solution, and the mixture was stirred at 110 ° C. for 2 hours. The contents of the flask were washed three times with 200 mL of toluene and dried at 30 ° C. under reduced pressure. (Polymerization) Into a 1.5 L stainless steel autoclave, 5 mg of the solid catalyst component (A), 5 mg of the solid catalyst component (B), 91 mg of triethylaluminum, and 16 mg of texyltrimethoxysilane were placed, and then 340
g of propylene and 0.03 g of hydrogen. The temperature of the autoclave was raised, and the internal temperature was kept at 70 ° C. One hour later,
The polymerization was terminated by releasing the content gas. As a result, 30g
Was obtained.

The XI of this polypropylene powder was 97.1.
%Met. The value of MFR was 5.6 and the value of PI was 8.6. Comparative Example 1 In a 1.5 L stainless steel autoclave, 15 mg of the solid catalyst component (A) obtained in Example 1, 91 mg of triethylaluminum, 16 m of texyltrimethoxysilane
g, then 340 g of propylene and 0.03 g
Of hydrogen. Raise the temperature of the autoclave and raise the internal temperature to 70
C. One hour later, the content gas was released to terminate the polymerization. As a result, 63 g of polypropylene powder was obtained.

The XI of this polypropylene powder was 97.0.
%Met. The value of MFR was 15.0 and the value of PI was 4.0. Comparative Example 2 (Preparation of solid catalyst component) Anhydrous magnesium chloride 9.4
g, anhydrous iron (II) chloride (Aldrich) 12.8
g and 5.6 g of di-n-butyl phthalate (electron-donating compound / (Mg + Fe) molar ratio = 0.1) were placed in a 1 L cylindrical container filled with 50% by apparent volume of a magnetic ball having a diameter of 10 mm. Co-milling was performed for 12 hours on a vibrating mill with amplitude.

Separately, 120 mL of toluene and 120 mL of titanium tetrachloride were added to a flask having an internal volume of 500 mL to cause a reaction, and heated to 60 ° C. The co-ground solid was added to this solution, and the mixture was stirred at 110 ° C. for 2 hours. The contents of the flask were washed three times with 200 mL of toluene and dried at 30 ° C. under reduced pressure. (Polymerization) In a 1.5 L stainless steel autoclave, 15 mg of the solid catalyst component obtained above, 91 mg of triethylaluminum, 16 mg of texyltrimethoxysilane.
And then 340 g of propylene and 0.03 g of hydrogen. Raise the temperature of the autoclave and raise the internal temperature to 70 ° C.
Kept. One hour later, the content gas was released to terminate the polymerization. As a result, 54.0 g of polypropylene powder was obtained.

The XI of this polypropylene powder was 96.2.
%Met. The value of MFR was 4.0 and the value of PI was 4.7. Comparative Example 3 (Preparation of solid catalyst component) 20 g of anhydrous magnesium chloride,
3.1 g of di-n-butyl phthalate and 3.0 g of 2-isopropyl-2-isopentyl-1,3-dimethoxypropane (electron-donating compound / Mg molar ratio = 0.1) were found on a magnetic ball having a diameter of 10 mm. The mixture was placed in a 1 L cylindrical container filled with 50% by volume, and co-milled for 12 hours using a vibration mill having an amplitude of 9 mm.

Separately, 120 mL of toluene and 120 mL of titanium tetrachloride were added to a flask having an inner volume of 500 mL to cause a reaction, and heated to 60 ° C. The co-ground solid was added to this solution, and the mixture was stirred at 110 ° C. for 2 hours. The contents of the flask were washed three times with 200 mL of toluene and dried at 30 ° C. under reduced pressure. (Polymerization) 13 mg of the solid catalyst component obtained above, 5 mg of the solid catalyst component (B), 91 mg of triethylaluminum, and 16 mg of texyltrimethoxysilane were placed in a 1.5 L stainless steel autoclave.
g of propylene and 0.03 g of hydrogen. The temperature of the autoclave was raised, and the internal temperature was kept at 70 ° C. One hour later,
The polymerization was terminated by releasing the content gas. As a result, 66.
3 g of polypropylene powder were obtained.

The XI of this polypropylene powder was 96.4.
%Met. The value of MFR was 7.0 and the value of PI was 3.5. Comparative Example 4 (Preparation of solid catalyst component) Anhydrous magnesium chloride 9.4
g, anhydrous iron (II) chloride (Aldrich) 12.8
g, 2.8 g of di-n-butyl phthalate and 2-isopropyl-2
-2.7 g of isopentyl-1,3-dimethoxypropane (electron-donating compound / (Mg + Fe) molar ratio = 0.1) is placed in a 1 L cylindrical container filled with magnetic balls having a diameter of 10 mm and an apparent volume of 50%, and then 9 mm 12 with a vibration mill of amplitude
Co-milling was performed for hours.

Separately, 120 mL of toluene and 120 mL of titanium tetrachloride were added to a flask having an internal volume of 500 mL to cause a reaction, and heated to 60 ° C. The co-ground solid was added to this solution, and the mixture was stirred at 110 ° C. for 2 hours. The contents of the flask were washed three times with 200 mL of toluene and dried at 30 ° C. under reduced pressure. (Polymerization) In a 1.5 L stainless steel autoclave, 14 mg of the solid catalyst component obtained above, 91 mg of triethylaluminum, and 16 mg of texyltrimethoxysilane.
And then 340 g of propylene and 0.03 g of hydrogen. Raise the temperature of the autoclave and raise the internal temperature to 70 ° C.
Kept. One hour later, the content gas was released to terminate the polymerization. As a result, 33.6 g of polypropylene powder was obtained.

The XI of this polypropylene powder was 93.4.
%Met. The value of MFR was 24.0 and the value of PI was 3.7. Example 2 In a 1.5 L stainless steel autoclave, 7 mg of the solid catalyst component (A), 4 mg of the solid catalyst component (B), 91 mg of triethylaluminum, and 16 mg of texyltrimethoxysilane obtained in Example 1, and then 340
g of propylene and 0.03 g of hydrogen. The temperature of the autoclave was raised, and the internal temperature was kept at 70 ° C. One hour later,
The polymerization was terminated by releasing the content gas. As a result, 26g
Was obtained.

The XI of this polypropylene powder was 97.1.
%Met. The value of MFR was 8.3 and the value of PI was 6.6. Example 3 5 mg of the solid catalyst component (A), 5 mg of the solid catalyst component (B), 91 mg of triethylaluminum and 22 mg of dicyclopentyldimethoxysilane obtained in Example 1 were placed in a 1.5 L stainless steel autoclave, and then 340 g of the same. Propylene and 0.03 g of hydrogen were charged.
The temperature of the autoclave was raised, and the internal temperature was kept at 70 ° C. One hour later, the content gas was released to terminate the polymerization. as a result,
31 g of polypropylene powder were obtained.

The XI of this polypropylene powder was 97.4.
%Met. The value of MFR was 7.0 and the value of PI was 6.9. Example 4 (Preparation of solid catalyst component (B)) 30 g of anhydrous iron (II) chloride (manufactured by Aldrich) and 3.6 g of ethyl 3-methoxy-3-tert-butylpropionate (electron-donating compound / Fe molar ratio) = 0.1) was placed in a 1 L cylindrical container filled with 50% apparent volume of a magnetic ball having a diameter of 10 mm, and co-milled for 12 hours with a vibration mill having an amplitude of 9 mm.

Separately, 120 mL of toluene and 120 mL of titanium tetrachloride were added to a flask having an inner volume of 500 mL to cause a reaction, and heated to 60 ° C. The co-ground solid was added to this solution, and the mixture was stirred at 110 ° C. for 2 hours. The contents of the flask were washed three times with 200 mL of toluene and dried at 30 ° C. under reduced pressure. (Polymerization) In a 1.5 L stainless steel autoclave, 5 mg of the solid catalyst component (A) obtained in Example 1, 5 mg of the solid catalyst component (B) obtained above, 91 mg of triethylaluminum, 16 mg of texyltrimethoxysilane And then 340 g of propylene and 0.03 g of hydrogen. The temperature of the autoclave was raised, and the internal temperature was kept at 70 ° C. One hour later, the content gas was released to terminate the polymerization. As a result, 34 g of polypropylene powder was obtained.

The XI of this polypropylene powder was 97.2.
%Met. The value of MFR was 9.1 and the value of PI was 8.6. Example 5 (Preparation of solid catalyst component (B)) 30 g of anhydrous iron (II) chloride (manufactured by Aldrich) and 7.1 g of diethyl 2,2-diisopentylmalonate (electron-donating compound / Fe molar ratio =
0.1) was placed in a 1 L cylindrical container filled with 50% apparent volume of a magnetic ball having a diameter of 10 mm, and co-milled for 12 hours using a vibration mill having an amplitude of 9 mm.

Separately, 120 mL of toluene and 120 mL of titanium tetrachloride were added to a flask having an internal volume of 500 mL to cause a reaction, and heated to 60 ° C. The co-ground solid was added to this solution, and the mixture was stirred at 110 ° C. for 2 hours. The contents of the flask were washed three times with 200 mL of toluene and dried at 30 ° C. under reduced pressure. (Polymerization) In a 1.5 L stainless steel autoclave, 5 mg of the solid catalyst component (A) obtained in Example 1, 5 mg of the solid catalyst component (B) obtained above, 91 mg of triethylaluminum, 16 mg of texyltrimethoxysilane And then 340 g of propylene and 0.03 g of hydrogen. The temperature of the autoclave was raised, and the internal temperature was kept at 70 ° C. One hour later, the content gas was released to terminate the polymerization. As a result, 33 g of a polypropylene powder was obtained.

The XI of this polypropylene powder was 96.9.
%Met. The value of MFR was 8.0 and the value of PI was 8.1. Example 6 (Preparation of solid catalyst component (B)) 30 g of anhydrous iron (II) chloride (manufactured by Aldrich) and 4.4 g of butyl 3-propionylpropionate (electron-donating compound / Fe molar ratio = 0.
1) and 50 in the apparent volume of a magnetic ball having a diameter of 10 mm.
% And filled in a 1 L cylindrical container, and co-milled for 12 hours using a vibration mill having an amplitude of 9 mm.

Separately, 120 mL of toluene and 120 mL of titanium tetrachloride were added to a flask having an internal volume of 500 mL to cause a reaction, and heated to 60 ° C. The co-ground solid was added to this solution, and the mixture was stirred at 110 ° C. for 2 hours. The contents of the flask were washed three times with 200 mL of toluene and dried at 30 ° C. under reduced pressure. (Polymerization) In a 1.5 L stainless steel autoclave, 5 mg of the solid catalyst component (A) obtained in Example 1, 5 mg of the solid catalyst component (B) obtained above, 91 mg of triethylaluminum, 16 mg of texyltrimethoxysilane And then 340 g of propylene and 0.03 g of hydrogen. The temperature of the autoclave was raised, and the internal temperature was kept at 70 ° C. One hour later, the content gas was released to terminate the polymerization. As a result, 27 g of polypropylene powder was obtained.

The XI of this polypropylene powder was 97.0.
%Met. The value of MFR was 7.6 and the value of PI was 9.2. Example 7 (Preparation of solid catalyst component (A)) Anhydrous magnesium chloride 2
0 g and 2,2-isobutyl-1,3-dimethoxypropane 5.1
g (electron-donating compound / Mg molar ratio = 0.1) and a magnetic ball having a diameter of 10 mm was filled at 50% by apparent volume.
The resultant was placed in a cylindrical container of L and co-ground with a vibration mill having an amplitude of 9 mm for 12 hours.

Separately, 120 mL of toluene and 120 mL of titanium tetrachloride were added to a flask having an internal volume of 500 mL to cause a reaction, and heated to 60 ° C. The co-ground solid was added to this solution, and the mixture was stirred at 110 ° C. for 2 hours. The contents of the flask were washed three times with 200 mL of toluene and dried at 30 ° C. under reduced pressure. (Polymerization) In a 1.5 L stainless steel autoclave, 5 mg of the solid catalyst component (A) obtained above, 5 mg of the solid catalyst component (B) obtained in Example 1, 91 mg of triethylaluminum, 16 mg of texyltrimethoxysilane And then 340 g of propylene and 0.03 g of hydrogen. The temperature of the autoclave was raised, and the internal temperature was kept at 70 ° C. One hour later, the content gas was released to terminate the polymerization. As a result, 34 g of polypropylene powder was obtained.

The XI of this polypropylene powder was 97.3.
%Met. The value of MFR was 8.4 and the value of PI was 8.5. Example 8 (Preparation of solid catalyst component (A)) An anhydrous magnesium chloride (7.14 g), decane (37.5 mL) and 2-ethylhexyl alcohol (35.1 mL) were mixed and heated at 130 ° C. for 2 hours to form a homogeneous solution. 1.4 g of 2,2-dipropyl-1,3-dimethoxypropane was added to this homogeneous solution,
The mixture was further heated and stirred at ℃ for 1 hour to be dissolved.

After cooling the obtained homogeneous solution to room temperature,
The whole amount was dropped into 200 mL of titanium tetrachloride kept at -20 ° C in one hour. After the dropwise addition, the temperature of the resulting solution was reduced to 4
After the temperature was raised to 110 ° C. over time, the mixture was stirred at 110 ° C. for 2 hours. After completion of the reaction for 2 hours, a solid portion was recovered by hot filtration,
This solid portion was resuspended in 275 mL of titanium tetrachloride and then heated again at 110 ° C. for 2 hours. After completion of the reaction, a solid portion was recovered by hot filtration and washed at 110 ° C. using decane and hexane. This washing was performed until no titanium compound was detected in the washing solution, and then dried at 30 ° C. under reduced pressure. (Preparation of solid catalyst component (B)) Anhydrous iron chloride (II)
3 g and 50 mL of decane were mixed and heated at 130 ° C. for 2 hours to obtain a slurry solution. 2,2-
1.4 g of diisopropyl-1,3-dimethoxypropane was added, and the mixture was further heated and stirred at 130 ° C. for 1 hour.

After the obtained slurry solution was cooled to room temperature, the whole amount was dropped into 200 mL of titanium tetrachloride kept at -20 ° C. in one hour. After the dropwise addition, the temperature of the resulting solution was raised to 110 ° C. over 4 hours, and then stirred at 110 ° C. for 2 hours. After completion of the reaction for 2 hours, a solid portion was recovered by hot filtration, and the solid portion was resuspended in 275 mL of titanium tetrachloride, and then heated again at 110 ° C. for 2 hours. After completion of the reaction, a solid portion was recovered by hot filtration and washed at 110 ° C. using decane and hexane. This washing was performed until no titanium compound was detected in the washing solution, and then dried at 30 ° C. under reduced pressure. (Polymerization) Into a 1.5 L stainless steel autoclave, 5 mg of the solid catalyst component (A), 5 mg of the solid catalyst component (B), 91 mg of triethylaluminum, and 16 mg of texyltrimethoxysilane were placed, and then 340
g of propylene and 0.03 g of hydrogen. The temperature of the autoclave was raised, and the internal temperature was kept at 70 ° C. One hour later,
The polymerization was terminated by releasing the content gas. As a result, 79 g
Was obtained.

The XI of this polypropylene powder was 97.0.
%Met. The value of MFR was 5.4 and the value of PI was 8.7.

[0073]

As described above, according to the present invention,
In the polymerization of olefin, it becomes possible to obtain a polyolefin having a wide molecular weight distribution with a high yield.

[Brief description of the drawings]

FIG. 1 is a flowchart showing a method for preparing a catalyst according to the present invention.

 ──────────────────────────────────────────────────の Continued on the front page F-term (reference) 4J028 AA02A AA03A AB02A AC02A AC04A AC05A AC06A AC07A AC14A AC15A AC17A AC45A AC46A AC47A AC48A BA00A BA01B BA02B BB00A BB01B BC05A BC14B BC15B BC16BCABCABBCCAB BC19A CB30A CB35A CB42A CB45A CB47C CB52A CB53A CB56A CB57A CB58A CB62A CB63C CB66A CB68A CB72C CB74C CB77C CB81A CB82 FA CB01A 07 EB01 EB01 EB01 EB01 EB01 EB01

Claims (7)

[Claims] 1. A mixed solid catalyst component for olefin polymerization comprising the following components (A) and (B). (A) A solid catalyst component comprising magnesium, titanium, halogen and an electron-donating compound (D1) different from the following compound (D2) as essential components. (B) a solid containing, as essential components, at least one transition metal atom selected from manganese, iron, cobalt, nickel, and zinc; titanium; a halogen; and an electron-donating compound (D2) represented by the following general formula (1). Catalyst component. Embedded image (In the formula, X and Y may be different mutually be the same, each -CH ₂ OR, -COOR, -CR =
O, -CHO, -CH ₂ OH or -CH ₂ OSi
(R) ₃ represents a group, Z represents a carbon atom, a silicon atom, a methylene chain or a substituted methylene chain, and R, R ¹ and R ² may be the same or different, and each has 1 to 1 carbon atoms. Represents 18 linear or branched alkyl, alicyclic, aryl, alkylaryl or arylalkyl groups, wherein R ¹ or R ² may be hydrogen. 2. An olefin polymerization catalyst comprising the mixed solid catalyst component for olefin polymerization according to claim 1 and an organoaluminum compound. 3. The olefin polymerization catalyst according to claim 2, further comprising an electron-donating compound (D3) as the third component. 4. The electron-donating compound (D3) used as the third component is a compound having an alkoxy group.
The olefin polymerization catalyst according to the above. 5. The catalyst for olefin polymerization according to claim 3, wherein the electron donating compound (D3) used as the third component is an organosilicon compound having an alkoxy group. 6. A method for producing an olefin polymer, comprising polymerizing an olefin using the olefin polymerization catalyst according to claim 2. Description: 7. The obtained olefin polymer is MFR>
The method for producing an olefin polymer according to claim 6, wherein the olefin polymer is 5.0.