JP2003137919A - Solid catalyst component for polymerization of olefin, catalyst for polymerization of olefin and method of production for olefin polymer - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a solid catalyst component for polymerization of olefins with high polymerization activity, imparting an olefin polymer excellent in tacticity and shape of powder with low residual chlorine. SOLUTION: The solid catalyst component for polymerization of olefin is obtained by reacting a compound (a) with (b-1) and then reacting those with compound (c) and (d) at 120-150 deg.C, washing the reaction product with an inert solvent, again reacting the compound (d) at the same temperature, washing with the inert solvent to obtain the solid catalyst component having molar ratio of remaining alkoxy group (RO)/supported amount of titanium (Ti) <=0.70. Details of compounds (a) to (d) are as follows: (a) a magnesium compound including an alkoxy group or an oxide of II-IV group elements of the periodic system supporting an alcohol complex of a magnesium compound including a halogen; (b-1) a silicon compound including halogens in an amount of >=0.2 of halogen/magnesium molar ratio to the oxide (a); (c) an electron donor; and (d) the titanium compound including halogens.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a solid catalyst component for olefin polymerization, a catalyst for olefin polymerization and a method for producing an olefin polymer for producing a homopolymer or a copolymer of α-olefin.

[0002]

2. Description of the Related Art Generally, an olefin polymer is polymerized by a Ziegler-Natta catalyst composed of a titanium compound and an organic aluminum compound. For example, in the production of polypropylene which is one of olefin polymers, a solid catalyst component mainly composed of titanium, magnesium, chlorine and an electron donating compound, an organoaluminum compound as a co-catalyst component, and a stereoregularity improving agent are used. By using a catalyst containing an organosilicon compound having an alkoxy group of
We have obtained isotactic polypropylene,
Attempts have been made to improve catalytic activity during polymerization, improve stereoregularity of olefin polymers, improve polymer powder form for stable production of olefin polymers, and reduce residual Cl in the polymers.

Here, if the amount of residual Cl in the polymer is large,
For example, it causes corrosion of the mold in injection molding, absorbs moisture and foams during biaxially stretched film and spinning, and causes foreign substances containing additives to make high-speed molding difficult. It is a big problem to reduce the residual Cl.

Further, as a method for solving the problem of residual Cl in the polymer, firstly, the method of improving the activity of the catalyst, and secondly, the magnesium chloride composition in the catalyst by supporting a magnesium compound on an inorganic substance such as silica, That is, a method of substantially reducing the Cl composition is generally performed.

For example, silica, butylethylmagnesium, and ethanol are brought into contact with each other to form a silica carrier carrying magnesium ethoxide, and this is reacted with silicon tetrachloride, followed by heptane washing, and further at 50 ° C. as an electron donor. Compound, a method of reacting with titanium tetrachloride only once at 90 ° C. (JP-A-61-174206), and a silica carrier carrying a butanol complex of magnesium chloride by impregnating silica with a mixture of magnesium chloride and butanol. Method of generating and supporting titanium tetrachloride and an electron donor compound (JP-A-63-168413)
Alternatively, a method of supporting diethoxymagnesium on silica previously treated with trimethylchlorosilane, and supporting titanium tetrachloride and an electron donor compound (Japanese Patent Publication No. 7-17695).
No. publication) is known.

[0006]

However, although the olefin polymers obtained by these methods have a certain level of performance, they are particularly satisfactory in terms of polymerization activity, stereoregularity, residual Cl, etc. It wasn't profitable.

The present invention provides a solid catalyst component for olefin polymerization, a catalyst for olefin polymerization, and an olefin polymer having high polymerization activity, which gives an olefin polymer excellent in stereoregularity, residual Cl, and powder form of the resulting polymer. It is an object to provide a method for producing a coalescence.

As a result of intensive studies to achieve the above object, the present inventors have found that a solid catalyst component for olefin polymerization in which the residual amount of alkoxy groups in the solid catalyst component is remarkably reduced by a specific preparation method. The present invention was completed by finding out that the above-mentioned problems can be solved by the above.

[0009]

According to the present invention, the following compounds (a) and (b-1) are reacted with each other and the following compounds (c) and (d) are reacted at a temperature of 120 ° C or higher and 150 ° C or lower. And a solid catalyst component for olefin polymerization obtained by reacting the following compound (d) at a temperature of 120 ° C. or higher and 150 ° C. or lower and washing with an inert solvent. It (A) an oxide of an alkoxy group-containing magnesium compound or one or more elements selected from Group II to IV elements carrying an alcohol complex of a halogen-containing magnesium compound (b-1) in the oxide (a) On the other hand, halogen-containing magnesium compound having a halogen / magnesium molar ratio of 0.20 or more (c) electron-donating compound (d) halogen-containing titanium compound

By preparing the solid catalyst component as described above, the residual amount of alkoxy groups can be reduced, the polymerization activity is high, the amount of residual Cl is small, and the olefin polymer is excellent in stereoregularity and powder form. Can be obtained.

Particularly, in the compound (b-1), the alkoxy or alcohol in the alkoxy group-containing magnesium compound or the alcohol complex of the halogen-containing magnesium compound is adjusted to (a) by setting the halogen / magnesium molar ratio to 0.20 or more. ) Component can be efficiently extracted from the solid surface.

By such a preparation method, the compound (a)
And the reaction of the compound (d) with the alkoxy group or alcohol contained in the reaction product of the compound (b-1),
It is considered that the alkoxy group contained in the magnesium compound or the complexed alcohol is reduced and the by-produced alkoxytitanium or the like is easily extracted from the solid surface. Here, “again” means once or more. That is, after reacting the compounds (a) to (d), the reaction product and the compound (d) may be further reacted once or more (for example, once or twice).

The washing temperature with an inert solvent after the first reaction of the compounds (a) to (d) is 100 ° C. or higher and 150 ° C. or higher.
It is preferably at most ° C.

Further, the molar ratio (RO / Ti) of the amount of remaining alkoxy groups (RO) to the amount of titanium supported (Ti) is 0.7.
It is preferably 0 or less.

Another embodiment of the present invention is (a) an oxide of one or more elements selected from Group II to IV elements carrying an alkoxy group-containing magnesium compound or an alcohol complex of a halogen-containing magnesium compound, The molar ratio (RO) of the residual amount of alkoxy groups (RO) to the amount of supported titanium (Ti), which is obtained by reacting (b) a halogen-containing silicon compound, (c) an electron-donating compound, and (d) a halogen-containing titanium compound. / Ti) is a solid catalyst component for olefin polymerization having 0.70 or less. Molar ratio (RO /
By setting the Ti) to 0.70 or less, a solid catalyst component having a high polymerization activity, a small amount of residual Cl, and an olefin polymer excellent in stereoregularity and powder form can be prepared.

The halogen-containing silicon compound (b),
It is preferable that (b-1) is silicon tetrachloride. It is considered that by using silicon tetrachloride, the rate and reaction rate of the halogenation / dealkoxylation reaction of component (a) with silicon tetrachloride can be sufficiently controlled.

Further, the molar ratio (RO / Ti) is 0.50.
The following is preferable. Remaining amount of alkoxy group (RO)
Is preferably 0.5 mmol / g or less. The amount of titanium supported is preferably 1.0% by weight or more.

Yet another embodiment of the present invention is an olefin polymerization catalyst containing the following components [A], [B] or the following components [A], [B], [C]. [A] Solid catalyst component for olefin polymerization [B] Organoaluminum compound [C] Electron-donating compound By constituting the catalyst in this way, polymerization activity is high, residual Cl is small, stereoregularity and powder form. It is possible to obtain an excellent olefin polymer. The electron-donating compound [C] is optionally contained, but the inclusion of this compound may improve the stereoregularity and the polymerization activity of the olefin polymer.

Yet another aspect of the present invention is a method for producing an olefin polymer in which an olefin is polymerized using the above-mentioned olefin polymerization catalyst.

[0020]

BEST MODE FOR CARRYING OUT THE INVENTION Each catalyst component, production method, polymerization method and the like of the present invention will be described below. The following are preferred examples, and the present invention is not limited thereto as long as the requirements of the claims are satisfied. 1. Catalyst component [A] Solid catalyst component for olefin polymerization

(A) Oxides of Group II-IV Group Elements Carrying Alcohol Complexes of Alkoxy Group-Containing Magnesium Compounds or Halogen-Containing Magnesium Compounds As oxides of Group II-IV elements, at least one of these elements is used. Solid oxides and solid composite inorganic oxides including the above can be mentioned. Group II-IV elements include Mg, Ca,
B, Al, Si and Sn are preferable, Al and Si are more preferable, and Si is particularly preferable. As a solid oxide,
For example, MgO, CaO, B ₂ O ₃ , SiO ₂ , SnO ₂ ,
Examples include Al ₂ O _{3 and the} like. Further, as the solid complex inorganic oxide, for example, SiO ₂ —Al ₂ O ₃ , SiO ₂ —Mg
_{O, SiO 2 -TiO 2, SiO} 2 -V 2 O 5, SiO 2 -C
Examples include r ₂ O ₃ and SiO ₂ —TiO ₂ —MgO. These various solid oxides and solid composite inorganic oxides,
Each may be used alone, or two or more solid oxides or solid composite inorganic oxides may be used together. Further, the solid oxide and the solid composite inorganic oxide may be used together.

Since these solid oxide components are basic elements of the catalyst carrier, the average particle diameter D ₅₀ is 0.1 to 1000 μm, particularly ₅ to 100 μm, if specified from the viewpoint of characteristics as a carrier. Specific surface area of 10 to 1000 m ² /
g, especially 100 to 800 m ² / g, pore volume of 0.1 to
It is preferably in the range of 5 cm ³ / g, particularly 1 to 2.5 cm ³ / g. Here, the average particle size (D ₅₀ ) is defined as the particle size corresponding to a weight cumulative fraction of 50%. That is, D
The total weight of the smaller particles than the particle size represented by ₅₀ is shown to be 50 percent of total grain total weight sum. Among the solid oxide components, S that can have the above characteristics
iO ₂ is particularly preferred.

As the alkoxy group-containing magnesium compound, dialkoxy magnesium such as dimethoxy magnesium, diethoxy magnesium, dipropoxy magnesium, dibutoxy magnesium, dihexyloxy magnesium, dioctoxy magnesium, diphenoxy magnesium and dicyclohexyloxy magnesium, Diallyloxy magnesium; ethoxyethyl magnesium,
Alkoxyalkyl magnesium such as phenoxymethyl magnesium, ethoxyphenyl magnesium, and cyclohexyloxyphenyl magnesium, allyloxyalkyl magnesium, alkoxyallyl magnesium, allyloxy allyl magnesium; butoxy magnesium chloride, cyclohexyloxy magnesium chloride, phenoxy magnesium chloride, ethoxy magnesium chloride, ethoxy Alkoxy magnesium halides such as magnesium bromide, butoxy magnesium bromide and ethoxy magnesium iodide, and allyloxy magnesium halides are mentioned. Among these alkoxy group-containing magnesium compounds, dialkoxy magnesium is preferable from the viewpoint of catalytic performance, and diethoxy magnesium is preferable. Especially preferred magnesium There.

Examples of the halogen-containing magnesium compound include magnesium dihalides such as magnesium chloride, magnesium bromide and magnesium iodide, butoxy magnesium chloride, cyclohexyloxy magnesium chloride, phenoxy magnesium chloride, ethoxy magnesium chloride, ethoxy magnesium bromide, butoxy magnesium bromide. Alkoxy magnesium halides such as ethoxy magnesium iodide, and allyloxy magnesium halides. Among these halogen-containing magnesium compounds, magnesium chloride is particularly preferable from the viewpoint of catalytic performance.

As the alcohol, it is preferable to use a lower alcohol having 1 to 8 carbon atoms such as methanol, ethanol, propanol and butanol. Of these, ethanol is particularly preferable.

The composition of the alcohol complex of the alkoxy group-containing magnesium compound or the halogen-containing magnesium compound is not particularly limited, but the weight ratio of magnesium / oxide (a) is usually 0.1 to 20 wt%, preferably 1 -15 wt%, particularly preferably 2-12 wt%
Is desirable in terms of activity and the like.

As a method of supporting the above-mentioned oxide with a magnesium compound containing an alkoxy group, dialkoxymagnesium, diaryloxymagnesium, alkoxyalkylmagnesium, aryloxyalkylmagnesium, alkoxymagnesium halide and allyloxy are directly applied to the solid oxide. A magnesium halide may be brought into contact, or a method in which a solid oxide and a dialkylmagnesium are once brought into contact with alcohol and then partially or completely alkoxylated may be used.

As a method of supporting the alcohol complex of the halogen-containing magnesium compound on the above oxide, a solid oxide, a magnesium dihalide alcohol complex, an alkoxy magnesium halide alcohol complex, and an allyloxy magnesium halide alcohol complex are directly added. The solid oxide may be brought into contact, or the solid oxide may be brought into contact with magnesium dihalide, alkoxymagnesium halide or allyloxymagnesium halide, and then alcohol may be brought into contact therewith to form a corresponding alcohol complex.

(B) Halogen-Containing Silicon Compound The halogen-containing silicon compound is represented by the following general formula (I)
The compound represented by can be used. Si (OR ¹ ) _r X ¹ _4-r ... (I)

By using the halogen-containing silicon compound (b), it may be possible to improve the catalytic activity during polymerization, stereoregularity, and reduce the amount of fine powder contained in the olefin polymer.

In the above general formula (I), X ¹ represents a halogen atom, of which a chlorine atom and a bromine atom are preferable, and a chlorine atom is particularly preferable. R ¹ is a hydrocarbon group, which may be a saturated group or an unsaturated group, may be a linear or branched one, or a cyclic one, and may be sulfur, nitrogen, It may contain a hetero atom such as oxygen, silicon, or phosphorus. Among these, a hydrocarbon group having 1 to 10 carbon atoms, particularly an alkyl group, an alkenyl group, a cycloalkenyl group, an aryl group, an aralkyl group and the like are preferable. When a plurality of OR ^1's are present, they may be the same or different from each other. Specific examples of R ¹ include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, isobutyl group, n-pentyl group, n-hexyl group, n-heptyl group, Examples thereof include n-octyl group, n-decyl group, allyl group, butenyl group, cyclopentyl group, cyclohexyl group, cyclohexenyl group, phenyl group, tolyl group, benzyl group and phenethyl group. r represents an integer of 0 to 3.

Specific examples of the halogen-containing silicon compound represented by the above general formula (I) include silicon tetrachloride, methoxytrichlorosilane, dimethoxydichlorosilane, trimethoxychlorosilane, ethoxytrichlorosilane, diethoxydichlorosilane and triethoxychlorosilane. ,
Examples thereof include propoxytrichlorosilane, dipropoxydichlorosilane, and tripropoxychlorosilane. Of these, silicon tetrachloride is particularly preferable. These halogen-containing silicon compounds may be used alone or in combination of two or more.

(C) Electron-donating compound As the electron-donating compound, alcohols, phenols, ketones, aldehydes, carboxylic acids, malonic acid,
Examples thereof include oxygen-containing compounds such as esters of organic acids or inorganic acids, ethers such as monoethers, diethers and polyethers, and nitrogen-containing compounds such as ammonia, amines, nitriles and isocyanates. Among these, polycarboxylic acid esters are preferable, and more preferably,
Esters of aromatic polycarboxylic acids. this house,
From the viewpoint of catalytic activity during polymerization, monoesters and / or diesters of aromatic dicarboxylic acids are particularly preferable. Also,
The ester group organic group is preferably a linear, branched or cyclic aliphatic hydrocarbon group.

Specifically, phthalic acid, naphthalene-1,
2-dicarboxylic acid, naphthalene-2,3-dicarboxylic acid, 5,6,7,8-tetrahydronaphthalene-1,2
-Methyl, ethyl, n- of dicarboxylic acids such as dicarboxylic acid, 5,6,7,8-tetrahydronaphthalene-2,3-dicarboxylic acid, indane-4,5-dicarboxylic acid and indane-5,6-dicarboxylic acid Propyl, isopropyl, n-butyl, isobutyl, t-butyl, n-pentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 1,1-dimethylpropyl, 1-methylpentyl, 2-methylpentyl, 3-methyl Pentyl, 4-methylpentyl, 1-ethylbutyl, 2-ethylbutyl,
n-hexyl, cyclohexyl, n-heptyl, n-octyl, n-nonyl, 2-methylhexyl, 3-methylhexyl, 4-methylhexyl, 2-ethylhexyl,
Dialkyl esters such as 3-ethylhexyl, 4-ethylhexyl, 2-ethylpentyl, 3-ethylpentyl and the like can be mentioned. Among these, phthalic acid diesters are preferable, and those in which the organic group of the ester portion is a linear or branched aliphatic hydrocarbon group having 4 or more carbon atoms are particularly preferable. Specific examples thereof include di-n-butyl phthalate, diisobutyl phthalate, di-n-heptyl phthalate and diethyl phthalate. Further, these compounds may be used alone or in combination of two or more kinds.

(D) Halogen-containing titanium compound As the halogen-containing titanium compound, the following general formula (II)
The compound represented by can be preferably used. TiX ² _p (OR ² ) _4-p ... (II)

In the above general formula (II), X ² represents a halogen atom, of which a chlorine atom and a bromine atom are preferable, and a chlorine atom is particularly preferable. R ² is a hydrocarbon group, which may be a saturated group or an unsaturated group, may be a linear group, a branched group, or a cyclic group, and further may be sulfur, nitrogen, It may contain a hetero atom such as oxygen, silicon, or phosphorus. Of these, a hydrocarbon group having 1 to 10 carbon atoms, particularly an alkyl group, an alkenyl group, a cycloalkenyl group, an aryl group and an aralkyl group are preferable, and a linear or branched alkyl group is particularly preferable. When there are a plurality of OR ^2's , they may be the same or different from each other. Specific examples of R ² include methyl group, ethyl group, n-propyl group, isopropyl group, n
-Butyl group, sec-butyl group, isobutyl group, n-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, n-decyl group, allyl group, butenyl group, cyclopentyl group, cyclohexyl group, cyclo A hexenyl group,
Examples thereof include a phenyl group, a tolyl group, a benzyl group and a phenethyl group. p shows the integer of 1-4.

Specific examples of the halogen-containing titanium compound represented by the above general formula (II) include titanium tetrahalide such as titanium tetrachloride, titanium tetrabromide and titanium tetraiodide;
Trihalogenated alkoxytitanium such as methoxytitanium trichloride, ethoxytitanium trichloride, propoxytitanium trichloride, n-butoxytitanium trichloride, ethoxytitanium tribromide; dimethoxytitanium dichloride, diethoxytitanium dichloride, diisopropoxytitanium dichloride, di Dihalogenated dialkoxytitanium such as -n-propoxytitanium dichloride and diethoxytitanium dibromide; trimethoxytitanium chloride, triethoxytitanium chloride, triisopropoxytitanium chloride, tri-n-propoxytitanium chloride, tri-
Examples include monohalogenated trialkoxytitanium such as n-butoxytitanium chloride. Of these, titanium compounds having a high halogen content, particularly titanium tetrachloride, are preferred from the viewpoint of polymerization activity. These halogen-containing titanium compounds may be used alone or in combination of two or more.

[B] Organoaluminum Compound As the organoaluminum compound [B] used in the present invention, those having an alkyl group, a halogen atom, a hydrogen atom or an alkoxy group, aluminoxane and a mixture thereof can be preferably used. Specifically, trialkylaluminums such as trimethylaluminum, triethylaluminum, triisopropylaluminum, triisobutylaluminum and trioctylaluminum; dialkyls such as diethylaluminum monochloride, diisopropylaluminum monochloride, diisobutylaluminum monochloride and dioctylaluminum monochloride. Examples include aluminum monochloride; alkylaluminum sesquihalides such as ethylaluminum sesquichloride; and chain aluminoxanes such as methylaluminoxane. Among these organoaluminum compounds, trialkylaluminum having a lower alkyl group having 1 to 5 carbon atoms, particularly trimethylaluminum,
Triethyl aluminum, tripropyl aluminum and triisobutyl aluminum are preferred. These organoaluminum compounds may be used alone or in combination of two or more.

[C] Electron-donating Compound The electron-donating compound [C] is optionally used in the olefin polymerization catalyst of the present invention. As such an electron-donating compound [C], an organosilicon compound having an alkoxy group, a nitrogen-containing compound, a phosphorus-containing compound and an oxygen-containing compound can be used. Among these, it is particularly preferable to use an organosilicon compound having an alkoxy group.

Specific examples of the organosilicon compound having an alkoxy group include trimethylmethoxysilane, trimethylethoxysilane, triethylmethoxysilane, triethylethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, ethylisopropyldimethoxysilane and propylisopropyldimethoxysilane. , Diisopropyldimethoxysilane, diisobutyldimethoxysilane, isopropylisobutyldimethoxysilane, di-t-butyldimethoxysilane, t-butylmethyldimethoxysilane, t-butylethyldimethoxysilane, t
-Butylpropyldimethoxysilane, t-butylisopropyldimethoxysilane, t-butylbutyldimethoxysilane, t-butylisobutyldimethoxysilane, t-
Butyl (s-butyl) dimethoxysilane, t-butylamyldimethoxysilane, t-butylhexyldimethoxysilane, t-butylheptyldimethoxysilane, t-butyloctyldimethoxysilane, t-butylnonyldimethoxysilane, t-butyldecyldimethoxysilane , T
-Butyl (3,3,3-trifluoromethylpropyl)
Dimethoxysilane, cyclohexylmethyldimethoxysilane, cyclohexylethyldimethoxysilane, cyclohexylpropyldimethoxysilane, dicyclohexyldimethoxysilane, cyclohexyl-t-butyldimethoxysilane, cyclopentylmethyldimethoxysilane,
Cyclopentylethyldimethoxysilane, cyclopentylpropyldimethoxysilane, cyclopentyl-t-butyldimethoxysilane, dicyclopentyldimethoxysilane, cyclopentylcyclohexyldimethoxysilane, bis (2-methylcyclopentyl) dimethoxysilane, bis (2,3-dimethylcyclopentyl) dimethoxysilane, α-naphthyl-1,1,2-trimethylpropyldimethoxysilane, n-tetradecanyl-1,1,
2-trimethylpropyldimethoxysilane, 1,1,2
-Trimethylpropylmethyldimethoxysilane, 1,
1,2-trimethylpropylethyldimethoxysilane,
1,1,2-trimethylpropylisopropyldimethoxysilane, 1,1,2-trimethylpropylcyclopentyldimethoxysilane, 1,1,2-trimethylpropylcyclohexyldimethoxysilane, 1,1,2-trimethylpropylmyristyldimethoxysilane, diphenyldimethoxy Silane, diphenyldiethoxysilane, phenyltriethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, propyltrimethoxysilane, isopropyltrimethoxysilane, butyltrimethoxysilane, butyltriethoxy Silane, isobutyltrimethoxysilane, t-butyltrimethoxysilane, s-butyltrimethoxysilane, amyltrimethoxysilane, isoamido Trimethoxysilane, cyclopentene trimethoxysilane, cyclohexyl trimethoxysilane, norbornane Nantes trimethoxysilane, indenyl trimethoxysilane, 2-methyl cyclopentene trimethoxysilane, ethyl triisopropoxysilane, methylcyclopentyl (t-butoxy) dimethoxysilane,
Isopropyl (t-butoxy) dimethoxysilane, t-
Butyl (t-butoxy) dimethoxysilane, (isobutoxy) dimethoxysilane, vinyltriethoxysilane,
Vinyltributoxysilane, chlorotriethoxysilane, γ-chloropropyltrimethoxysilane, γ-aminopropyltriethoxysilane, 1,1,2-trimethylpropyltrimethoxysilane, 1,1,2-trimethylpropylisopropoxydimethoxysilane , 1, 1,
2-trimethylpropyl (t-butoxy) dimethoxysilane, tetramethoxysilane, tetraethoxysilane,
Tetrabutoxysilane, tetraisobutoxysilane, ethyl silicate, butyl silicate, trimethylphenoxysilane, methyltriaryloxysilane, vinyltris (β-
Examples include methoxyethoxy) silane, vinyltrisacetoxysilane, and dimethyltetraethoxydisiloxane. These organosilicon compounds may be used alone or in combination of two or more.

As such an organosilicon compound, a silicon compound not having a Si--O--C bond and an O--C compound can be used.
A compound obtained by previously reacting an organic compound having a bond or by reacting it at the time of polymerization of α-olefin can also be mentioned. Specific examples include compounds obtained by reacting silicon tetrachloride with alcohol.

Specific examples of the nitrogen-containing compound include 2,6
-Diisopropylpiperidine, 2,6-diisopropyl-4-methylpiperidine, N-methyl-2,2,6,6
-2,6-Substituted piperidines such as tetramethylpiperidine; 2,5-diisopropylazolidine, N-methyl-
2,2,5,5-Tetramethylazolidine and other 2,5-
Substituted azolidines; Substituted methylenediamines such as N, N, N ', N'-tetramethylmethylenediamine, N, N, N', N'-tetraethylmethylenediamine; 1,3
-Dibenzyl imidazolidine, 1,3-dibenzyl-2
-Substituted imidazolidines such as phenylimidazolidine and the like can be mentioned.

Specific examples of the phosphorus-containing compound include triethyl phosphite, tri n-propyl phosphite, triisopropyl phosphite, tri n-butyl phosphite, triisobutyl phosphite, diethyl n-butyl phosphite, diethyl phenyl phosphite. Examples include phosphite esters such as fight.

Specific examples of the oxygen-containing compound include 2,
2,5,5-tetramethyltetrahydrofuran, 2,
2,5,5-tetraethyltetrahydrofuran, etc.
5-Substituted tetrahydrofurans; 1,1-dimethoxy-
2,3,4,5-tetrachlorocyclopentadiene,
Examples include dimethoxymethane derivatives such as 9,9-dimethoxyfluorene and diphenyldimethoxymethane.

2. [A] Preparation method of solid catalyst component As a preparation method of the solid catalyst component [A], oxides of the II-IV group elements carrying the above-mentioned alkoxy group-containing magnesium compound or alcohol complex of halogen-containing magnesium compound ( a) and a specific amount of the halogen-containing silicon compound (b) are brought into contact with each other to react with each other, and the electron-donating compound (c) and the halogen-containing titanium compound (d) 120
After contacting and reacting at a temperature of ℃ or more and 150 ℃ or less, and washing with an inert solvent, contact the halogen-containing titanium compound (d) at a temperature of 120 ℃ or more and 150 ℃ or less again The contact order is not particularly limited.

However, when the component (a) and the halogen-containing silicon compound (b) are brought into contact with each other, the halogen-containing titanium compound (d) is brought into contact with the electron-donating compound (c), the polymerization activity is increased. Is sometimes high, which is preferable.

Each of these components may be contacted in the presence of an inert solvent such as a hydrocarbon, or may be diluted in advance with an inert solvent such as a hydrocarbon and contacted.
Examples of the inert solvent include octane, decane,
Aliphatic hydrocarbons or alicyclic hydrocarbons such as ethylcyclohexane, aromatic hydrocarbons such as toluene, ethylbenzene and xylene, and halogenated hydrocarbons such as chlorobenzene, tetrachloroethane and chlorofluorocarbons, or a mixture thereof. To be Of these, aliphatic hydrocarbons and aromatic hydrocarbons are preferable, and aliphatic hydrocarbons are particularly preferable.

Here, the halogen-containing titanium compound (d)
Is usually 0.5 to 100 mol, relative to 1 mol of magnesium of the alcohol complex of the above alkoxy group-containing magnesium compound or halogen-containing magnesium compound,
Preferably, 1 to 50 mol is used. If this molar ratio deviates from the above range, the catalytic activity may become insufficient.

The electron-donating compound (c) is the magnesium 1 of the alcohol complex of the above-mentioned alkoxy group-containing magnesium compound or halogen-containing magnesium compound.
The amount is usually 0.01 to 10 mol, preferably 0.05 to 1.0 mol, based on mol. If this molar ratio deviates from the above range, the catalytic activity and stereoregularity may be insufficient.

Further, a halogen-containing silicon compound (b)
Is usually 0.20 in terms of halogen / magnesium molar ratio with respect to the above-mentioned alcohol complex of an alkoxy group-containing magnesium compound or a halogen-containing magnesium compound.
The amount is preferably 0.4 to 4.0, more preferably 1.0 to 2.5. If this amount is less than the above range, the catalytic activity, the effect of improving stereoregularity will not be sufficiently exhibited, and the amount of fine powder of the produced polymer will increase, and the bulk density will decrease. It never grows.

In the catalytic reaction of the above compounds (a) to (d), after all of them are added, preferably 120 to 150
C., particularly preferably in the temperature range of 125 to 140.degree. If the contact temperature is out of the above range, the catalytic activity and the stereoregularity may not be sufficiently improved. The contact is usually for 1 minute to 24 hours, preferably 10 minutes.
Minutes to 6 hours. When a solvent is used, the pressure at this time varies depending on the type, contact temperature, etc., but is usually atmospheric pressure to 5 MPa, preferably atmospheric pressure to 1 MPa. Further, during the contact operation, it is preferable to perform stirring from the viewpoint of contact uniformity and contact efficiency. These contact conditions are the same for the second and subsequent contact reactions of the halogen-containing titanium compound (d).

When a solvent is used in the contact operation of the halogen-containing titanium compound (d), it is usually 5,000 ml or less, preferably 10-1, or less, per 1 mol of the halogen-containing titanium compound (d). Use 000 milliliters of solvent. If this ratio deviates from the above range, the uniformity of contact and the contact efficiency may deteriorate.

After the first contact and reaction of the halogen-containing titanium compound (d), it may be desirable to wash with an inert solvent at a temperature of 100 to 150 ° C, particularly preferably 120 to 140 ° C. If the washing temperature is out of the above range, the catalytic activity and the stereoregularity may not be sufficiently improved. Examples of the inert solvent include, for example,
Octane, decane, aliphatic hydrocarbons or alicyclic hydrocarbons such as ethylcyclohexane, aromatic hydrocarbons such as toluene, xylene, ethylbenzene, halogenated hydrocarbons such as chlorobenzene, tetrachloroethane, chlorofluorocarbons or the like A mixture may be mentioned. Of these, aliphatic hydrocarbons and aromatic hydrocarbons are preferably used.

The washing temperature after the contact and reaction of the halogen-containing titanium compound (d) for the second and subsequent times is 100 to 150 ° C., particularly preferably 120, from the viewpoint of stereoregularity.
In some cases it may be better to wash with an inert solvent at a temperature of ~ 140 ° C.

The washing method is not particularly limited, but decantation, filtration and the like are preferable. There are no particular restrictions on the amount of the inert solvent used, the washing time, or the number of washings, but it is usually 10 per 1 mol of the magnesium compound.
0-100,000 ml, preferably 500
~ 50,000 ml of solvent used, usually 1
Minutes to 24 hours, preferably 10 minutes to 6 hours.
If this ratio deviates from the above range, cleaning may be incomplete.

The pressure at this time varies depending on the type of solvent, the washing temperature, etc., but is usually atmospheric pressure to 5 MPa, preferably atmospheric pressure to 1 MPa. Further, during the washing operation, it is preferable to perform stirring from the viewpoint of washing uniformity and washing efficiency. The obtained solid catalyst component can be stored in a dry state or in an inert solvent such as hydrocarbon.

In the solid catalyst component [A] thus obtained, the molar ratio (RO / Ti) of the amount of remaining alkoxy groups (RO) to the amount of titanium supported (Ti) is preferably 0.70 or less. . This is because if the molar ratio exceeds 0.70, the desired catalyst may not be obtained. It is more preferable that the molar ratio is 0.50 or less,
It is more preferable to set it to 0.45 or less.

Further, the residual amount (RO) of the alkoxy group is 0.
It is preferably 50 mmol / g or less. The reason for this is that when the residual amount of alkoxy groups exceeds 0.50 mmol / g, the polymerization activity is low, and the cost of the catalyst increases and the amount of residual catalyst such as Cl in the powder increases, which may deteriorate the quality. is there. Further, the residual amount of alkoxy groups is more preferably 0.35 mmol / g or less, further preferably 0.20 mmol / g or less. The residual amount of alkoxy groups can be controlled by preparing a catalyst under specific reaction conditions. At this time, especially compound (a)-
The order of contact of (d), the amount of compound (b) used, and the reaction temperature of compound (d) are important.

The amount of titanium supported is preferably 1.0% by weight or more. The reason for this is that the amount of titanium supported is 1.
If it is less than 0% by weight, the activity per catalyst may be low even if the activity per titanium is high (RO / Ti is low). Also, the amount of titanium supported is 1.2
It is more preferably at least wt%, and even more preferably at least 1.5 wt%. The amount of titanium supported can be controlled by selecting the component (a) having a specific composition or preparing a catalyst under specific reaction conditions. At this time,
Regarding the component (a), the composition of the oxide, the content of the magnesium compound, etc. are considered to be important. Further, in the reaction conditions, the reaction temperature of the compound (d) and the washing temperature after the reaction of the compound (d) are particularly important.

3. Method for producing olefin polymer Regarding the amount of each component of the olefin polymerization catalyst of the present invention, the solid catalyst component [A] is converted into titanium atom,
The amount used is usually in the range of 0.00005 to 1 mmol per liter of reaction volume.

The organoaluminum compound [B] is used in such an amount that the aluminum / titanium (atomic ratio) is usually in the range of 1 to 1,000, preferably 10 to 500. If this atomic ratio deviates from the above range, the catalytic activity may become insufficient.

When the electron-donating compound [C] is used, [C] / [B] (molar ratio) is usually 0.001 to
The amount used is in the range of 5.0, preferably 0.01 to 2.0, more preferably 0.05 to 1.0.
If this molar ratio deviates from the above range, sufficient catalytic activity and stereoregularity may not be obtained. However, when performing prepolymerization, the amount of the electron-donating compound [C] used can be further reduced.

As the olefin used in the present invention,
Α-Olefin represented by the following general formula (III) is preferable. _{^{R 3 -CH = CH 2 ··· (}} III)

In the above general formula (III), R ³ is a hydrogen atom or a hydrocarbon group, and the hydrocarbon group may be a saturated group or an unsaturated group, or may be a straight chain or branched chain. It may have or have an annular shape. Specifically, ethylene, propylene, 1-butene, 1-pentene, 1
-Hexene, 1-heptene, 1-octene, 1-decene, 3-methyl-1-pentene, 4-methyl-1-pentene, vinylcyclohexane, butadiene, isoprene, piperylene and the like. These olefins may be used alone or in combination of two or more. Among the above olefins, ethylene and propylene are particularly preferable.

In the polymerization of the olefin in the present invention, the olefin is preliminarily polymerized and then the main polymerization is carried out, if desired, in view of the catalytic activity during the polymerization, the stereoregularity of the olefin polymer and the powder form. May be. In this case, 1 to 1 of the olefin is usually added in the presence of a catalyst prepared by mixing the solid catalyst component [A], the organoaluminum compound [B], and optionally the electron donating compound [C] at a predetermined ratio. At a temperature in the range of 100 ° C., prepolymerization is carried out at atmospheric pressure to a pressure of about 5 MPa, and then olefin is main polymerized in the presence of a catalyst and a prepolymerized product.

The polymerization method in this main polymerization is applicable to any of solution polymerization, slurry polymerization, gas phase polymerization, bulk polymerization and the like, and further applicable to both batch polymerization and continuous polymerization. It is also applicable to two-step polymerization and multi-step polymerization under different conditions.

Regarding the reaction conditions, the polymerization pressure is usually atmospheric pressure to 8 MPa, preferably 0.2 to 5 MPa, and the polymerization temperature is usually 0 to 20 from the viewpoint of polymerization activity.
It is appropriately selected in the range of 0 ° C, preferably 30 to 100 ° C. The polymerization time depends on the type of olefin as a raw material and the polymerization temperature, but is usually 5 minutes to 20 hours, preferably 10 minutes to 1
It is about 0 hours.

The molecular weight of the olefin polymer can be adjusted by adding a chain transfer agent, preferably hydrogen. Further, an inert gas such as nitrogen may be present. Regarding the catalyst component in the present invention, the solid catalyst component [A], the organoaluminum compound [B] and the electron donating compound [C] are mixed at a predetermined ratio and contacted, and then the olefin is immediately introduced. Polymerization may be performed, or after contacting, aging may be performed for about 0.2 to 3 hours, and then olefin may be introduced to perform polymerization. Further, this catalyst component can be supplied by suspending it in an inert solvent, olefin or the like. In the present invention, post-treatment after polymerization can be carried out by a conventional method. That is, in the gas phase polymerization method, after the polymerization, the polymer powder discharged from the polymerization vessel may be passed through a nitrogen stream or the like in order to remove olefins and the like contained therein. Depending on the case, it may be pelletized by an extruder, and in that case, a small amount of water, alcohol or the like may be added in order to completely deactivate the catalyst. Further, in the bulk polymerization method, after the polymerization, the monomer can be completely separated from the polymer discharged from the polymerization vessel, and then pelletized.

The residual Cl in the olefin polymer obtained using the olefin polymerization catalyst of the present invention is preferably 35 ppm or less. The reason for this is that if it exceeds 35 ppm, not only the cost of the neutralizing agent increases, but also corrosion of the mold and foaming and the generation of foreign matter may be induced during molding. Further, it is more preferable that the amount of residual Cl is 30 ppm or less.

[0070]

EXAMPLES Next, the present invention will be illustrated concretely by examples, but the present invention is not limited to the following examples.
The average particle size (D ₅₀ ) of the oxide (a), the remaining amount of alkoxy groups in the solid catalyst component, the amount of Ti supported, the bulk density of the polymer powder, the average particle size (D ₅₀ ), the amount of fine powder, the amount of coarse powder, The intrinsic viscosity [η], stereoregularity [mmmm], and Cl content of the polymer were determined as follows.

(1) Average particle size (D ₅₀ ) of oxide (a):
The oxide (a) is suspended in a hydrocarbon solvent and measured by a light transmission method. The particle size distribution obtained by this method was plotted on a log-normal probability paper, and the 50% particle size was obtained as the average particle size.

(2) Remaining amount of alkoxy groups in the solid catalyst component:
After the solid catalyst component was sufficiently dried, it was precisely weighed, tightly sealed in a vial bottle, and thoroughly decalcified with 1.2N hydrochloric acid.
Then, the insoluble matter was filtered, the amount of alcohol in the filtrate was quantified by gas chromatography, and the corresponding residual amount of alkoxy was calculated.

(3) Ti supported amount of solid catalyst component: After the solid catalyst component was sufficiently dried, it was precisely weighed and thoroughly decalcified with 3N sulfuric acid. Then, the insoluble matter was filtered, phosphoric acid was added to the filtrate as a masking agent, and 3% hydrogen peroxide solution was further added to develop the color of the solution. The absorbance at 420 nm was measured using FT-IR to measure the Ti concentration. Then, the amount of supported Ti in the solid catalyst component was calculated.

(4) Bulk density of polymerized powder: JIS K
It measured based on 6721.

(5) Average particle size (D ₅₀ ) of the polymer powder,
Amount of fine powder, amount of coarse powder: The particle size distribution measured using a sieve was plotted on a log-normal probability paper, and the 50% particle size was determined as the average particle size. Further, the weight fraction with an opening size of 250 μm or less was defined as a fine powder amount, and the weight fraction with an opening size of 2830 μm or more was defined as a coarse powder amount, and these were obtained.

(6) Intrinsic viscosity of polymer [η]: The polymer was dissolved in decalin and measured at 135 ° C.

(7) Stereoregularity of polymer [mmmm]:
The polymer was dissolved in a 90:10 (volume ratio) mixed solution of 1,2,4-trichlorobenzene and heavy benzene, and ¹³ C-NM was added.
R (manufactured by JEOL Ltd., trade name: LA-500) was used to quantify using the signal of the methyl group measured by the proton complete decoupling method at 130 ° C.

The isotactic pentad fraction [m
mmm] means A. Zambell
i) etc. are Macromolecules (Macromolec)
ules) Vol. 6, page 925 (1973), and means the isotactic fraction in the pentad unit in the polypropylene molecular chain, which is determined from the ¹³ C-NMR spectrum. Further, the method for determining the attribution of the peak in the ¹³ C-NMR spectrum is described in A. Zambe (A. Zambe).
Macromolecules (Macromol)
ecules) Vol. 8, page 687 (1975).

(8) Cl content of polymer: A sample was hot-pressed to prepare a plate, which was quantified by fluorescent X-ray analysis.

Example 1 (1) Preparation of Solid Oxide Bearing Alkoxy Group-Containing Magnesium Compound A three-necked flask with an internal volume of 0.5 liter equipped with a stirrer was replaced with nitrogen gas, and then dehydrated heptane. 200 ml, average particle size D ₅₀ is 5
0 μm, specific surface area 300 m ² / g, pore volume 1.6
40 g (667 mmol) of silica gel (cm ³ / g) and butylethylmagnesium (222 mmol) were mixed and heated at 90 ° C. for 1.5 hours. Then, it cooled to 5 degreeC, ethanol 28.6 milliliter (489 mmol) was dripped, and it heated at 80 degreeC for 1 hour. Then, wash with room temperature three times with 200 ml of dehydrated heptane,
When the composition of the obtained solid component was investigated, the magnesium content was 6.9 wt% and the ethoxy group content was 23.7 wt% (OEt / Mg molar ratio: 1.85).

(2) Preparation of solid catalyst component A three-necked flask with an internal volume of 0.5 liter equipped with a stirrer was replaced with nitrogen gas, and then 80 ml of dehydrated octane was added to the magnesium ethoxylate prepared in (1) above. 16 g of silica support carrying Mg (Mg: 45.4 mmol) was added. After adding 2.60 ml (22.7 mmol) of silicon tetrachloride dropwise at 40 ° C. and stirring for 4 hours, 77 ml (702 mmol) of titanium tetrachloride was added dropwise, the temperature of this solution was raised to 65 ° C., and then continued. Di-n-butyl phthalate 1.21 ml (4.54
Mmol) was added. Then, stirring was carried out at an internal temperature of 125 ° C. for 1 hour to perform a contact operation, the stirring was stopped, the solid was allowed to settle, and the supernatant was extracted. Add 100 ml of dehydrated octane and raise the temperature to 125 ° C with stirring and
After holding for a minute, stirring was stopped, the solid was allowed to settle, and the supernatant was extracted. This washing operation was repeated 7 times. Then, 122 ml (1.11 mol) of titanium tetrachloride was added, and the mixture was stirred at an internal temperature of 125 ° C. for 2 hours to perform a contact operation, and then washed with dehydrated octane at 125 ° C. as described above.
The solid catalyst component thus obtained was evaluated once. The results are shown in Table 1.
Shown in.

(3) Propylene Polymerization A stainless steel autoclave with an internal volume of 1 liter equipped with a stirrer was sufficiently dried, and after nitrogen substitution, 400 ml of heptane dehydrated at room temperature was added. 2.0 mmol of triethylaluminum, 0.25 mmol of dicyclopentyldimethoxylane, 0.0025 mmol of the solid catalyst component prepared in the above (2) in terms of Ti atom was added, 0.1 MPa of hydrogen was added, and then propylene was introduced. While raising the temperature to 80 ° C. and the total pressure up to 0.8 MPa,
Polymerization was carried out for a time. Then, the temperature was lowered and the pressure was released, and the contents were taken out and put into 2 liters of methanol to deactivate the catalyst. It was filtered off and dried in vacuum to obtain a propylene polymer. The evaluation results are shown in Table 1.

Example 2 (1) Preparation of solid catalyst component In Example 1 (2), except that the washing temperature with octane after the second supporting reaction of titanium tetrachloride was room temperature,
The same operation as in Example 1 was performed to evaluate the obtained solid catalyst component. The results are shown in Table 1.

(2) Propylene Polymerization In Example 1 (3), 0.5 mmol of cyclohexylmethyldimethoxysilane was used in place of dicyclopentyldimethoxysilane, and the solid catalyst component prepared in (1) above was converted into Ti atoms. Propylene was polymerized in the same manner as in Example 1 except that 0.005 mmol was added and hydrogen was added at 0.05 MPa, and the obtained propylene polymer was evaluated. The results are shown in Table 1.

Example 3 (1) Preparation of solid catalyst component A three-necked flask having an internal volume of 0.5 liter and equipped with a stirrer was replaced with nitrogen gas, and then 80 ml of dehydrated octane was used. 16 g of silica carrier supporting magnesium ethoxide prepared in (Mg: 45.4
Mmol) was added. After adding 2.60 ml (22.7 mmol) of silicon tetrachloride dropwise at 40 ° C. and stirring for 4 hours, 77 ml (702 mmol) of titanium tetrachloride was added dropwise, the temperature of this solution was raised to 65 ° C., and then continued. 1.21 ml of di-n-butyl phthalate (4.5
4 mmol) was added. Then, at an internal temperature of 125 ° C,
After stirring for a period of time to carry out a contact operation, the stirring was stopped, the solid was allowed to settle, and the supernatant was extracted. Add 100 ml of dehydrated octane and raise the temperature to 125 ° C with stirring,
After holding for 1 minute, stirring was stopped, the solid was allowed to settle, and the supernatant was extracted. This washing operation was repeated 7 times. Then, 122 milliliters (1.11 mol) of titanium tetrachloride was added, the mixture was stirred at an inner temperature of 125 ° C. for 2 hours to perform a contact operation, and then the washing with dehydrated octane at 125 ° C. was repeated 7 times. Further, 122 ml (1.11 mol) of titanium tetrachloride was added, the mixture was stirred at an internal temperature of 125 ° C. for 2 hours to perform a contact operation, and then the washing with dehydrated octane at 125 ° C. was repeated 7 times to obtain The solid catalyst components were evaluated. The results are shown in Table 1.

(2) Propylene Polymerization Propylene was polymerized in the same manner as in Example 1 except that the solid catalyst component prepared in the above (1) was used in Example 1 (3) to obtain a propylene polymer. The coalescence was evaluated. The results are shown in Table 1.

Example 4 (1) Preparation of solid catalyst component Example 1 (2) was carried out except that decane was used in place of octane as the preparation solvent and the washing solvent, and the reaction temperature and the washing temperature were 135 ° C. The same operation as in Example 1 was performed and the obtained solid catalyst component was evaluated. The results are shown in Table 1. (2) Propylene Polymerization In Example 1 (3), propylene was polymerized in the same manner as in Example 1 except that the solid catalyst component prepared in (1) above was used, and the obtained propylene polymer was evaluated. . The results are shown in Table 1.

Example 5 (1) Preparation of Solid Oxide Supporting Alcohol Complex of Halogen-Containing Magnesium Compound A three-necked flask with an internal volume of 0.5 liter equipped with a stirrer was replaced with nitrogen gas, and then magnesium chloride was added. 12.7g
(133 mmol) was suspended in 127 ml of heptane, and 73.4 ml of butanol (8 ml) at 40 ° C.
(00 mmol) was added dropwise and heated at 98 ° C. for 1 hour. Thereafter, the mixture was cooled to 70 ° C., 40 g (667 mmol) of silica gel having an average particle diameter D ₅₀ of 50 μm, a specific surface area of 300 m ² / g and a pore volume of 1.6 cm ³ / g was added for 0.5 hours. It was stirred. Further, 200 ml of dehydrated heptane was used to perform room temperature washing three times, and the composition of the obtained solid component was examined. As a result, the magnesium content was 4.0 wt%, the chlorine content was 11.3 wt%, and the butoxy group content was 39.1 wt.
% (Cl / Mg molar ratio: 1.93, OBu / M
g molar ratio: 3.25).

(2) Preparation of solid catalyst component A three-necked flask with an internal volume of 0.5 liter equipped with a stirrer was replaced with nitrogen gas, and then 80 ml of dehydrated octane was added to the magnesium chloride prepared in (1) above. 16 g of a silica carrier carrying the butanol complex (Mg:
26.3 mmol) was added. After 1.51 ml (13.2 mmol) of silicon tetrachloride was added dropwise at 40 ° C. and stirred for 4 hours, 77 ml (702 mmol) of titanium tetrachloride was added dropwise and the temperature of this solution was raised to 65 ° C. 0.70 ml (2.63 mmol) of di-n-butyl phthalate was added. Then, the internal temperature 1
The mixture was stirred at 25 ° C. for 1 hour to perform a contact operation, the stirring was stopped to settle the solid, and the supernatant was extracted. Add 100 ml of dehydrated octane and stir at 125 ℃
After the temperature was raised to 1 minute and held for 1 minute, stirring was stopped, the solid was allowed to settle, and the supernatant was extracted. This washing operation was repeated 7 times. Then, 122 ml (1.11 mol) of titanium tetrachloride was added, the mixture was stirred at an internal temperature of 125 ° C. for 2 hours to carry out a contact operation, and then washed with dehydrated octane at 125 ° C. seven times to obtain a product. The solid catalyst component was evaluated. The results are shown in Table 1.

(3) Propylene Polymerization Propylene was polymerized in the same manner as in Example 1 except that the solid catalyst component prepared in (2) above was used in Example 1 (3) to obtain propylene polymer. The coalescence was evaluated. The results are shown in Table 1.

Comparative Example 1 (1) Preparation of solid catalyst component A three-necked flask having an internal volume of 0.5 liter and equipped with a stirrer was replaced with nitrogen gas, and then 80 ml of dehydrated octane was used. 16 g of silica carrier supporting magnesium ethoxide prepared in (Mg: 45.4
Mmol) was added. After adding 2.60 ml (22.7 mmol) of silicon tetrachloride dropwise at 40 ° C. and stirring for 4 hours, 77 ml (702 mmol) of titanium tetrachloride was added dropwise, the temperature of this solution was raised to 65 ° C., and then continued. Di-n-butyl phthalate 1.21 ml (4.54
Mmol) was added. After that, the mixture was stirred at an internal temperature of 125 ° C. for 1 hour to perform a contact operation, the stirring was stopped, the solid was allowed to settle, and the supernatant was extracted. Further, 100 ml of dehydrated octane was added and the mixture was stirred at room temperature. The stirring was stopped, the solid was allowed to settle, and the supernatant was extracted. This washing operation was repeated 7 times, and the obtained solid catalyst component was evaluated. The results are shown in Table 1.

(2) Propylene Polymerization Propylene was polymerized in the same manner as in Example 1 except that the solid catalyst component prepared in the above (1) was used in Example 1 (3) to obtain the obtained propylene polymer. The coalescence was evaluated. The results are shown in Table 1.

Comparative Example 2 (1) Preparation of solid catalyst component A three-necked flask having an internal volume of 0.5 liter and equipped with a stirrer was replaced with nitrogen gas, and then 80 ml of dehydrated heptane was added to Example 1 (1). 16 g of silica carrier supporting magnesium ethoxide prepared in (Mg: 45.4
Mmol) was added. Heat to 70 ° C and di-n phthalate
-Butyl 1.21 ml (4.54 mmol) was added. The temperature of this solution was raised to 80 ° C., 77 ml (702 mmol) of titanium tetrachloride was then added dropwise, and the internal temperature was 110 ° C., and the mixture was stirred for 2 hours for contact operation. Then, stirring was stopped, the solid was allowed to settle, and the supernatant was extracted. 100 ml of dehydrated heptane was added, the temperature was raised to 90 ° C. with stirring, the temperature was maintained for 1 minute, the stirring was stopped, the solid was allowed to settle, and the supernatant was extracted. This washing operation was repeated 7 times. After that, 122 ml (1.11 mol) of titanium tetrachloride was added, and a contact operation was performed by stirring at an internal temperature of 110 ° C. for 2 hours, stirring was stopped to precipitate a solid, and a supernatant was extracted. afterwards,
The above washing operation at 90 ° C. with heptane was repeated 7 times, and the obtained solid catalyst component was evaluated. The results are shown in Table 1.

(2) Propylene Polymerization Propylene was polymerized in the same manner as in Example 1 except that the solid catalyst component prepared in (1) above was used in Example 1 (3) to obtain a propylene polymer. The coalescence was evaluated. The results are shown in Table 1.

[0095]

[Table 1]

[0096]

EFFECT OF THE INVENTION According to the present invention, a solid catalyst component for olefin polymerization, a catalyst for olefin polymerization and an olefin polymer having high polymerization activity, little residual Cl, excellent stereoregularity and powder form are obtained. It is possible to provide a method for producing a united body.

[Brief description of drawings]

FIG. 1 is a schematic diagram showing a method for producing an olefin polymerization catalyst and an olefin polymer of the present invention.

Continued front page    F-term (reference) 4J028 AA01A AB01A AC03A AC04A                       AC05A AC06A BA00A BA01A                       BB00A BC07A BC15B BC16B                       BC19B BC25B CA15A CA16A                       CA24A CA25A CA26A CA27A                       CA28A CB93A EA01 EB01

Claims (10)

[Claims] 1. The following compounds (a) and (b-1) are reacted with each other and the following compounds (c) and (d) at 120 ° C.
After reacting at a temperature of 150 ° C or lower and washed with an inert solvent, the following compound (d) is again heated at 120 ° C or higher and 150 ° C or higher.
A solid catalyst component for olefin polymerization obtained by reacting at a temperature of ℃ or below and washing with an inert solvent. (A) an oxide of an alkoxy group-containing magnesium compound or one or more elements selected from Group II to IV elements carrying an alcohol complex of a halogen-containing magnesium compound (b-1) in the oxide (a) On the other hand, halogen-containing magnesium compound having a halogen / magnesium molar ratio of 0.20 or more (c) electron-donating compound (d) halogen-containing titanium compound 2. The washing temperature with an inert solvent after the first reaction of the compounds (a) to (d) is 100 ° C. or higher and 150.
The solid catalyst component for olefin polymerization according to claim 1, which has a temperature of not higher than 0 ° C. 3. The solid catalyst component for olefin polymerization according to claim 1, wherein the molar ratio (RO / Ti) of the residual amount of alkoxy groups (RO) to the amount of titanium supported (Ti) is 0.70 or less. 4. (a) an alkoxy group-containing magnesium compound, or an oxide of one or more elements selected from Group II to IV elements carrying an alcohol complex of a halogen-containing magnesium compound, and (b) a halogen-containing silicon. Compound,
Titanium supported amount (Ti) obtained by reacting (c) an electron-donating compound and (d) a halogen-containing titanium compound.
Molar ratio of residual alkoxy group (RO) to (RO / T
A solid catalyst component for olefin polymerization having i) of 0.70 or less. 5. The halogen-containing silicon compound (b),
The solid catalyst component for olefin polymerization according to any one of claims 1 to 4, wherein (b-1) is silicon tetrachloride. 6. The solid catalyst component for olefin polymerization according to claim 3, wherein the molar ratio (RO / Ti) is 0.50 or less. 7. The solid catalyst component for olefin polymerization according to claim 1, wherein the residual amount (RO) of the alkoxy group is 0.50 mmol / g or less. 8. The solid catalyst component for olefin polymerization according to claim 1, wherein the amount of supported titanium is 1.0% by weight or more. 9. An olefin polymerization catalyst containing the following components [A] and [B] or the following components [A], [B] and [C]. [A] Solid catalyst component for olefin polymerization [B] Organoaluminum compound [C] Electron donating compound according to any one of claims 1 to 8. 10. A method for producing an olefin polymer, which comprises polymerizing an olefin using the olefin polymerization catalyst according to claim 9.