JP2721997B2 - Catalyst component for olefin polymerization - Google Patents

Description

Description: TECHNICAL FIELD The present invention relates to a catalyst component for olefin polymerization.

Prior Art In order to use an olefin polymerization catalyst industrially,
In the olefin polymerization step, it is essential that the polymer particles obtained there have catalytic performance so as not to be destroyed.

In particular, when the catalyst activity is high in the early stage of polymerization, the polymer particles tend to be easily broken. In order to suppress the initial activity of the catalyst, a method of treating the catalyst with a small amount of an activity inhibitor such as water is also recognized (for example, JP-A-62-119205), but these treatments lower the catalyst performance itself. There is fear.

In order to prevent the destruction of the polymer particles, the catalyst component is treated in the presence of an olefin, that is, by so-called pre-polymerization,
A method has also been adopted in which a polyolefin is incorporated into a catalyst component to increase its strength. This pre-polymerization is usually performed under mild conditions in order not to cause the destruction of the catalyst component particles that grow in the pre-polymerization. Therefore, in order to obtain a specific amount of the prepolymerized polymer, it is necessary to lengthen the prepolymerization time.

The so-called magnesium-carrying type catalyst, in which a magnesium component carries a titanium component, shows high activity, but the activity tends to decrease with the lapse of polymerization time, and therefore, the catalyst preliminarily polymerized for a long time has a reduced catalytic activity. .

Problems to be Solved by the Invention The present invention provides a catalyst component which is a magnesium-supported catalyst component, which has a low initial polymerization activity, does not cause destruction of catalyst particles by prepolymerization, and can suppress a decrease in catalyst activity. The purpose is to provide.

Means for Solving the Problems As a result of intensive studies, the present inventors have found that the titanium / magnesium ratio (A) of the catalyst component and the titanium / magnesium ratio
The inventors have found that the relationship with the magnesium ratio (B) affects the initial polymerization activity and the catalytic activity of the catalyst component, and that the relationship A> B can achieve the object of the present invention, thereby completing the present invention. .

SUMMARY OF THE INVENTION The present invention relates to (1) a compound represented by the general formula MgR ¹ R ^{2 wherein} R ¹ is an OR group (R
Represents a hydrocarbon group), and R ² represents a halogen atom. A solid obtained by treating the magnesium compound represented by the formula (1) with a halogen-containing alcohol, and then treating the solid with a tetravalent chlorinated titanium compound, wherein the titanium content is 1 to 8% by weight. A catalyst component for olefin polymerization, which satisfies the following relationship:

A> B [where A is the titanium / magnesium ratio (atomic ratio) of the solid and is 0.02 to 0.2, and B is the titanium / magnesium ratio (atomic ratio) of the solid surface measured by X-ray photoelectron spectroscopy. It is 0.05 or less. (2) The catalyst component according to (1), wherein the solid further contains an electron donating compound.

(3) The catalyst component according to (1) or (2), wherein the solid further contains 0.01 to 500 g of a polyolefin per 1 g of the solid.

Method for Preparing Catalyst Component The catalyst component of the present invention is a solid containing magnesium, titanium and chlorine or an electron-donating compound as an essential component, and the solid has a titanium / magnesium ratio (atomic ratio) on the surface.
(B) is the titanium / magnesium ratio (atomic ratio) of all solids
It has a smaller relationship than (A). The value of B was measured by X-ray photoelectron spectroscopy (hereinafter referred to as XPS).

Such a catalyst component can be prepared by using a magnesium compound as a starting material and bringing it into contact with a tetravalent chlorinated titanium compound or further an electron-donating compound.

The magnesium compound used as a starting material is represented by the general formula MgR ¹ R ² . In the formula, R ¹ represents an OR group (R is a hydrocarbon group), and R ² represents a halogen atom. More specifically, as the OR group, R is an alkyl group having 1 to 12 carbon atoms,
The cycloalkyl group, the aryl group, and the aralkyl group include, as halogen atoms, chlorine, bromine, iodine, and fluorine.

Specific examples of these compounds are shown below. In the chemical formula, Et: ethyl, Bu: butyl, He: hexyl, and Ph: phenyl are shown, respectively.

 EtOMgCl, BuOMgCl, HeOMgCl, PhOMgCl, EtOMgBr.

The magnesium compound can be prepared from metallic magnesium or another magnesium compound by a known method.

The catalyst component of the present invention is obtained by contacting the magnesium compound with a tetravalent chlorinated titanium compound or further an electron-donating compound.Before contacting the compound, the magnesium compound is converted into magnesium dihalide. Contact with a halogen-containing alcohol which is not converted until.

As the halogen-containing alcohol, a mono- or polyhydric alcohol having one or two or more hydroxyl groups in one molecule means a compound in which any one or two or more hydrogen atoms other than a hydroxyl group are substituted with a halogen atom. I do. Examples of the halogen atom include chlorine, bromine, iodine and fluorine atoms, and a chlorine atom is preferable.

Illustrating those compounds are 2-chloroethanol,
1-chloro-2-propanol, 3-chloro-1-propanol, 1-chloro-2-methyl-2-propanol, 4-chloro-1-butanol, 5-chloro-1-pentanol, 6-chloro-1 -Hexanol, 3-chloro-1,2-propanediol, 2-chlorocyclohexanol, 4-chlorobenzhydrol, (m, o, p) -chlorobenzyl alcohol, 4-chlorocatechol, 4-
Chlor- (m, o) -cresol, 6-chloro- (m, o)-
Cresol, 4-chloro-3,5-dimethylphenol,
Chlorohydroquinone, 2-benzyl-4-chlorophenol, 4-chloro-1-naphthol, (m, o, p) -chlorophenol, p-chloro-α-methylbenzyl alcohol, 2-chloro-4-phenylphenol, 6-chlorothymol, 4-chlororesorcin, 2-bromoethanol, 3-bromo-1-propanol, 1-bromo-
2-propanol, 1-bromo-2-butanol, 2-
Brom-p-cresol, 1-bromo-2-naphthol, 6-bromo-2-naphthol, (m, o, p) -bromophenol, 4-bromoresorcinol, (m, o, p) -fluorophenol, p -Iodophenol: 2,2-dichloroethanol, 2,3-dichloro-1-propanol, 1,3-dichloro-2-propanol, 3-chloro-1- (α-chloromethyl) -1-propanol, 2 , 3-Dibromo-1
-Propanol, 1,3-dibromo-2-propanol,
2,4-dibromophenol, 2,4-dibromo-1-naphthol: 2,2,2-trichloroethanol, 1,1,1-trichloro-2-propanol, β, β, β-trichloro-tert
-Butanol, 2,3,4-trichlorophenol, 2,4,5-
Trichlorophenol, 2,4,6-trichlorophenol, 2,4,6-tribromophenol, 2,3,5-tribromo-2-topyroxytoluene, 2,3,5-tribromo-4-
Topiroxytoluene, 2,2,2-trifluoroethanol, α, α, α-trifluoro-m-cresol, 2,4,
6-triiodophenol: 2,3,4,6-tetrachlorophenol, tetrachlorohydroquinone, tetrachlorobisphenol A, tetrabromobisphenol A, 2,2,
Examples include 3,3-tetrafluoro-1-propanol, 2,3,5,6-tetrafluorophenol, tetrafluororesorcin and the like.

The contact between the magnesium compound and the halogen-containing alcohol is performed in the presence of an inert medium. The contact may be performed under heating.

As the inert medium, saturated aliphatic hydrocarbons such as hexane, heptane and octane, saturated alicyclic hydrocarbons such as cyclopentane and cyclohexane, and aromatic hydrocarbons such as benzene, toluene and xylene can be used.

The magnesium compound contacted with the halogen-containing alcohol and the tetravalent chlorinated titanium compound or further contact with the electron-donating compound may be performed in the same manner as in the case of the contact between the magnesium compound and the halogen-containing alcohol, When contacting with the titanium compound, especially 50 ~ 150 ℃
It is desirable to carry out under heating.

The contact with the titanium compound and the electron-donating compound may be carried out by using both at the same time, or may be brought into contact with one of them and then with the other.

Furthermore, after contacting with a tetravalent chlorinated titanium compound,
Halogenated hydrocarbons (hereinafter referred to as E component)
Can be contacted.

Examples of the tetravalent chlorinated titanium compound include titanium tetrachloride, trichloroethoxytitanium, trichlorobutoxytitanium, dichlorodiethoxytitanium, dichlorodibutoxytitanium, dichlordiphenoxytitanium, chlorotriethoxytitanium, and chlorotributoxytitanium which are liquid at room temperature. Titanium and the like can be mentioned.

Examples of the electron donating compound include carboxylic acids, carboxylic anhydrides, carboxylic esters, carboxylic halides, alcohols, ethers, ketones, amines, amides, nitriles, aldehydes, alcoholates, Phosphorus bonded to an organic group via carbon or oxygen,
Examples include arsenic and antimony compounds, phosphoamides, thioethers, thioesters, carbonate esters and the like. Of these, carboxylic acids, carboxylic anhydrides, carboxylic esters, carboxylic halides, alcohols and ethers are preferably used.

Specific examples of carboxylic acids include aliphatic monocarboxylic acids such as formic acid, acetic acid, propionic acid, butyric acid, isobutyric acid, valeric acid, caproic acid, pivalic acid, acrylic acid, methacrylic acid, crotonic acid, malonic acid, and succinic acid. , Glutaric acid, adipic acid, sebacic acid, maleic acid, aliphatic dicarboxylic acids such as fumaric acid, aliphatic oxycarboxylic acids such as tartaric acid,
Cyclohexane monocarboxylic acid, cyclohexene monocarboxylic acid, cis-1,2-cyclohexane dicarboxylic acid,
Aromatic carboxylic acids such as cis-4-methylcyclohexene-1,2-dicarboxylic acid, aromatic monocarboxylic acids such as benzoic acid, toluic acid, anisic acid, p-tert-butyl benzoic acid, naphthoic acid, and cinnamic acid Carboxylic acid, phthalic acid, isophthalic acid,
Aromatic polycarboxylic acids such as terephthalic acid, naphthalic acid, trimellitic acid, hemimellitic acid, trimesic acid, pyromellitic acid, and melitic acid are exemplified.

As the carboxylic acid anhydride, the acid anhydrides of the above carboxylic acids can be used.

As the carboxylate, mono- or polyvalent esters of the above carboxylic acids can be used. Specific examples thereof include butyl formate, ethyl acetate, butyl acetate, isobutyl isobutyrate, propyl pivalate, isobutyl pivalate, and acrylic. Ethyl acrylate, methyl methacrylate, ethyl methacrylate, isobutyl methacrylate, diethyl malonate, diisobutyl malonate, diethyl succinate, dibutyl succinate, diisobutyl succinate, diethyl glutarate, dibutyl glutarate, diisobutyl glutarate,
Diisobutyl adipate, dibutyl sebacate, diisobutyl sebacate, diethyl maleate, dibutyl maleate, diisobutyl maleate, monomethyl fumarate, diethyl fumarate, diisobutyl fumarate, diethyl tartrate, dibutyl tartrate, diisobutyl tartrate, diisobutyl tartrate, ethyl cyclohexanecarboxylate, Methyl benzoate, ethyl benzoate, methyl p-toluate, ethyl p-tert-butyl benzoate, ethyl p-anisate, ethyl α-naphthoate, isobutyl α-naphthoate, ethyl cinnamate, monomethyl phthalate , Monobutyl phthalate, dibutyl phthalate, diisobutyl phthalate, dihexyl phthalate, dioctyl phthalate, di-2-ethylhexyl phthalate, diallyl phthalate, diphenyl phthalate, diethyl isophthalate, isophthalic acid Examples include diisobutyl, diethyl terephthalate, dibutyl terephthalate, diethyl naphthalate, dibutyl naphthalate, triethyl trimellitate, tributyl trimellitate, tetramethyl pyromellitate, tetraethyl pyromellitate, tetrabutyl pyromellitate, and the like.

As the carboxylic acid halide, acid halides of the above carboxylic acids can be used, and specific examples thereof include acetic acid chloride, acetic acid bromide, acetic acid iodide, propionic acid chloride, butyric acid chloride, butyric acid bromide, butyric acid iodide, and pivalin. Acid chloride, pivalic acid bromide, acrylic acid chloride, acrylic acid bromide, acrylic acid iodide, methacrylic acid chloride,
Methacrylic acid bromide, methacrylic acid iodide, crotonic acid chloride, malonic acid chloride, malonic acid bromide, succinic acid chloride, succinic acid bromide, glutaric acid chloride, glutaric acid bromide, adipic acid chloride,
Adipic acid bromide, sebacic acid chloride, sebacic acid bromide, maleic acid chloride, maleic acid bromide,
Fumaric acid chloride, fumaric acid bromide, tartaric acid chloride, tartaric acid bromide, cyclohexanecarboxylic acid chloride, cyclohexanecarboxylic acid bromide, 1-cyclohexenecarboxylic acid chloride, cis-4-methylcyclohexenecarboxylic acid chloride, cis-4-methylcyclohexenecarboxylic acid bromide Benzoyl chloride, benzoyl bromide, p-toluic acid chloride, p-toluic acid bromide, p-anisic acid chloride, p-anisic acid bromide,
α-naphthoic acid chloride, cinnamate chloride, cinnamate bromide, phthalic dichloride, phthalic dibromide,
Isophthalic acid dichloride, isophthalic acid dibromide, terephthalic acid dichloride, naphthalic acid dichloride. Also, adipic acid monomethyl chloride, maleic acid monoethyl chloride, maleic acid monomethyl chloride,
Monoalkyl halides of dicarboxylic acids such as butyl phthalate chloride may also be used.

Alcohols are represented by the general formula ROH. In the formula, R is an alkyl, alkenyl, cycloalkyl, aryl, aralkyl having 1 to 12 carbon atoms. Specific examples thereof include methanol, ethanol, propanol, isopropanol, butanol, isobutanol,
Pentanol, hexanol, octanol, 2-ethylhexanol, cyclohexanol, benzyl alcohol, allyl alcohol, phenol, cresol, xylenol, ethylphenol, isopropylphenol, p-tert-butylphenol, n-octylphenol and the like. Ethers represented by the general formula ROR ^1. In the formula, R and R ¹ are alkyl, alkenyl, cycloalkyl, aryl and aralkyl having 1 to 12 carbon atoms, and R and R ¹ may be the same or different. Specific examples thereof include diethyl ether, diisopropyl ether, dibutyl ether, diisobutyl ether, diisoamyl ether, di-2-ethylhexyl ether,
Diallyl ether, ethyl allyl ether, butyl allyl ether, diphenyl ether, anisole, ethyl phenyl ether and the like.

Examples of the halogenated hydrocarbon include mono- and polyhalogen-substituted saturated or unsaturated aliphatic, alicyclic and aromatic hydrocarbons having 1 to 12 carbon atoms. Specific examples of those compounds include, for aliphatic compounds, methyl chloride, methyl bromide, methyl iodide, methylene chloride, methylene bromide, methylene iodide, chloroform, bromoform, iodoform, carbon tetrachloride,
Carbon tetrabromide, carbon tetraiodide, ethyl chloride, ethyl bromide, ethyl iodide, 1,2-dichloroethane, 1,2-dibromoethane, 1,2-diiodoethane, methyl chloroform, methyl bromoform, methyl iodoform, 1,1 1,2-trichloroethylene, 1,1,2-tribromoethylene, 1,1,2,2-tetrachloroethylene, pentachloroethane, hexachloroethane, hexabromoethane, n-propyl chloride, 1,2-di Chlorpropane, hexachloropropylene, octachloropropane,
Decabromobutane, chlorinated paraffins, alicyclic compounds chlorocyclopropane, tetrachlorocyclopentane, hexachlorocyclopentadiene, hexachlorocyclohexane, aromatic compounds chlorobenzene, bromobenzene, o-dichlorobenzene, p- Examples thereof include dichlorobenzene, hexachlorobenzene, hexabromobenzene, benzotrichloride, and p-chlorobenzotrichloride. These compounds may be used alone or in combination of two or more.

The titanium compound is used in such a manner that the solid content of the catalyst component, which is the final target, is 1 to 8% by weight, and the titanium / magnesium (atomic ratio) (A) is in the range of 0.02 to 0.2. If the titanium content is less than 1% by weight, the performance as a catalyst is significantly reduced, and if it exceeds 8% by weight, the relationship of the inequality A> B is not satisfied. The electron donating compound is used in an amount of 0.005 to 10 gram mole per gram atom of magnesium in the catalyst solid.

Although the catalyst component according to the present invention is obtained as described above, the following method can be mentioned as a more detailed preparation method.

The magnesium compound (component A), the halogen-containing alcohol (component D), the electron donating compound (component B), and the tetravalent chlorinated titanium compound (component C) are brought into contact with each other in this order.

The A component, the D component, the C component and the B component are respectively brought into contact in that order.

The A component, the D component, the C component, and the E component (halogenated hydrocarbon) are respectively brought into contact in that order.

The A component, the D component, the C component, the B component and the E component are respectively brought into contact in that order.

The catalyst component thus obtained satisfies the relationship of A> B, but if the relationship is not satisfied, the intended object of the present invention is not achieved. The value of B is 0.05 or less.

In a preferred embodiment, the present invention is a catalyst component further containing 0.01 to 500 g, preferably 0.1 to 50 g, of a polyolefin per 1 g of the catalyst component solid. The polyolefin is contained by pre-polymerizing the olefin. Pre-polymerization, in the presence of an organoaluminum compound, if necessary, in combination with the electron-donating compound,
This is achieved by contacting the catalyst component with an olefin. The prepolymerization is performed at -20 ° C in the presence of the above-mentioned inert medium.
It is desirable to carry out at a low temperature of ~ 40 ° C.

The olefins include ethylene, propylene,
-Butene, 4-methyl-1-pentene, 1-hexene,
Alpha-olefins such as 1-octene can be used. Two or more olefins may be used in combination.

As the organic aluminum compound, the general formula R _n AlX _3-n
(Where R represents an alkyl group or an aryl group, X represents a halogen atom, an alkoxy group or a hydrogen atom, and n represents 1 ≦ n ≦
Any number in the range of 3. ),
For example, alkyl aluminum having 1 to 18 carbon atoms, preferably 2 to 6 carbon atoms, such as trialkylaluminum, dialkylaluminum monohalide, monoalkylaluminum dihalide, alkylaluminum sesquihalide, dialkylaluminum monoalkoxide and dialkylaluminum monohydride. Compounds or mixtures or complex compounds thereof are particularly preferred. Specifically, trimethylaluminum, triethylaluminum, tripropylaluminum, triisobutylaluminum, trialkylaluminum such as trihexylaluminum, dimethylaluminum chloride, diethylaluminum chloride, diethylaluminum bromide, diethylaluminum iodide, diisobutylaluminum chloride and the like Monoalkylaluminum dihalides such as dialkylaluminum monohalide, methylaluminum dichloride, ethylaluminum dichloride, methylaluminum dibromide, ethylaluminum dibromide, ethylaluminum diiodide, isobutylaluminum dichloride, and alkylaluminum sesquichloride such as ethylaluminum sesquichloride , Dimethyl aluminum methoxide,
Diethylaluminum ethoxide, diethylaluminum phenoxide, dipropylaluminum ethoxide,
Examples thereof include dialkylaluminum monoalkoxides such as diisobutylaluminum ethoxide and diisobutylaluminum phenoxide, dimethylaluminum hydride, dialkylaluminum hydride, dialkylaluminum hydride, and dialkylaluminum hydride such as diisobutylaluminum hydride.

Olefin polymerization catalyst The catalyst component of the present invention is used as a catalyst for homopolymerization of olefins or copolymerization with other olefins in combination with an organic compound of a Group I to Group III metal of the periodic table.

Organic Compounds of Group I to Group III Metals As the organometallic compounds, organic compounds of lithium, magnesium, calcium, zinc and aluminum can be used. Among these, an organoaluminum compound is particularly preferable. The organoaluminum compound that can be used is selected from the above-mentioned compounds used when pre-polymerizing the catalyst component of the present invention.

As organic compounds of metals other than aluminum metal,
Diethyl magnesium, ethyl magnesium chloride,
In addition to diethylzinc, etc., LiAl (C ₂ H ₅ ) ₄ , LiAl (C ₇ H ₁₅ ) ₄
And the like.

Further, the organometallic compound may be used alone or in combination with an electron donating compound. As the electron donating compound, any compound may be used as long as it is a compound used at the time of preparing the catalyst component.Other electron donating compounds composed of an organic silicon compound, and electron donating compounds containing hetero atoms such as nitrogen, sulfur, oxygen, and phosphorus. Sexual compounds can also be used.

Specific examples of the organosilicon compound include tetramethoxysilane, tetraethoxysilane, tetrabutoxysilane,
Tetraisobutoxysilane, tetraphenoxysilane,
Tetra (p-methylphenoxy) silane, tetrabenzyloxysilane, methyltrimethoxysilane, methyltriethoxysilane, methyltributoxysilane, methyltriphenoxysilane, ethyltriethoxysilane, ethyltriisobutoxysilane, ethyltriphenoxysilane, Butyltrimethoxysilane, butyltriethoxysilane, butyltributoxysilane, butyltriphenoxysilane, isobutyltriisobutoxysilane, vinyltriethoxysilane, allyltrimethoxysilane, dimethyldiisopropoxysilane, dimethyldibutoxysilane, dimethyldihexyloxy Silane, dimethyldiphenoxysilane, diethyldiethoxysilane, diethyldiisobutoxysilane, diethyldiphenoxysilane,
Dibutyldiisopropoxysilane, dibutyldibutoxysilane, dibutyldiphenoxysilane, diisobutyldiethoxysilane, diisobutyldiisobutoxysilane,
Diphenyldimethoxysilane, diphenyldiethoxysilane, diphenyldibutoxysilane, dibenzyldiethoxysilane, divinyldiphenoxysilane, diallyldipropoxysilane, diphenyldiallyloxysilane,
Methylphenyldimethoxysilane, chlorophenyldiethoxysilane and the like can be mentioned.

Specific examples of the electron-donating compound containing a hetero atom, as a compound containing a nitrogen atom, 2,2,6,6-tetramethylpiperidine, 2,6-dimethylpiperidine, 2,6-diethylpiperidine, 2,6 -Diisopropylpiperidine, 2,6
-Diisobutyl-4-methylpiperidine, 1,2,2,6,6-
Pentamethylpiperidine, 2,2,5,5-tetramethylpyrrolidine, 2,5-dimethylpyrrolidine, 2,5-diethylpyrrolidine, 2,5-diisopropylpyrrolidine, 1,2,2,5,5-
Pentamethylpyrrolidine, 2,2,5-trimethylpyrrolidine, 2-methylpyridine, 3-methylpyridine, 4-methylpyridine, 2,6-diisopropylpyridine, 2,6-diisobutylpyridine, 1,2,4-trimethylpiperidine ,
2,5-dimethylpiperidine, methyl nicotinate, ethyl nicotinate, nicotinamide, benzoamide, 2-
Methylpyrrole, 2,5-dimethylpyrrole, imidazole, toluic acid amide, benzonitrile, acetonitrile, aniline, paratoluidine, orthotoluidine, metatoluidine, triethylamine, diethylamine, dibutylamine, tetramethylenediamine, tributylamine, etc. Thiophenol, thiophene, ethyl 2-thiophenecarboxylate,
Ethyl 3-thiophenecarboxylate, 2-methylthiophene, methylmercaptan, ethylmercaptan, isopropylmercaptan, butylmercaptan, diethylthioether, diphenylthioether, methylbenzenesulfonate, methylsulfite, ethylsulfite, etc., are compounds containing an oxygen atom As, tetrahydrofuran, 2-methyltetrahydrofuran, 3-methyltetrahydrofuran, 2-methyltetrahydrofuran, 2,2,
5,5-tetraethyltetrahydrofuran, 2,2,5,5-tetramethyltetrahydrofuran, 2,2,6,6-tetraethyltetrahydropyran, 2,2,6,6-tetrahydropyran,
Dioxane, dimethyl ether, diethyl ether, dibutyl ether, diisoamyl ether, diphenyl ether, anisole, acetophenone, acetone, methyl ethyl ketone, acetylacetone, o-tolyl-t-
Butyl ketone, methyl-2,6-di-t-butylphenyl ketone, ethyl 2-furate, isoamyl 2-furate,
Examples of the compound containing a phosphorus atom such as 2-methyl furarate and propyl 2-furarate include triphenyl phosphine, tributyl phosphine, triphenyl phosphite, tribenzyl phosphite, diethyl phosphate, diphenyl phosphate and the like.

Two or more of these electron donating compounds may be used.
These electron donating compounds may be used when the organometallic compound is used in combination with the catalyst component, or may be used after being brought into contact with the organometallic compound in advance.

The amount of the organometallic compound to be used for the catalyst component of the present invention is generally 1 to 1 gram atom of titanium in the catalyst component.
2,000 gmol, especially 20-500 gmol, is desirable.

The ratio of the organometallic compound to the electron-donating compound is selected in the range of 0.1 to 40, preferably 1 to 25 g atoms, of the organometallic compound as aluminum per mole of the electron-donating compound.

Polymerization of olefin The catalyst comprising the catalyst component and the organometallic compound (and the electron donating compound) obtained as described above has 2 to 2 carbon atoms.
It is useful as a catalyst for homopolymerization of 10 monoolefins or copolymerization with other monoolefins or diolefins having 3 to 10 carbon atoms. Several to six α-olefins such as propylene, 1-butene,
-Methyl-1-pentene, random and block copolymerization with 1-hexene and the like, and the above-mentioned α-olefin homopolymerization or the above-mentioned α-olefin mutual and / or random and block copolymerization catalyst with ethylene are extremely useful. Shows excellent performance.

The polymerization reaction may be any of a gas phase and a liquid phase.When the polymerization is performed in a liquid phase, an inert carbon such as normal butane, isobutane, normal pentane, isopentane, hexane, heptane, octane, cyclohexane, benzene, toluene, or xylene is used. It can be carried out in hydrogen and in liquid monomers. The polymerization temperature is usually in the range of -80C to + 150C, preferably 40 to 120C. The polymerization pressure is, for example, 1 to 60
Atmospheric pressure is fine. Adjustment of the molecular weight of the resulting polymer is carried out in the presence of hydrogen or other known molecular weight regulators. The amount of the other olefin to be copolymerized with the olefin in the copolymerization is usually selected up to 30% by weight, especially in the range of 0.3 to 15% by weight based on the olefin. The polymerization reaction using the catalyst system of the present invention is carried out by a continuous or batch reaction, and the conditions may be those commonly used. Further, the copolymerization reaction may be performed in one stage, or may be performed in two or more stages.

Effect of the Invention The catalyst component of the present invention has a low initial polymerization activity, so that catalyst particles are less likely to be destroyed in prepolymerization with an olefin, and the prepolymerized catalyst component has a small decrease in catalyst activity.

EXAMPLES Next, the present invention will be specifically described with reference to examples and application examples. However, the present invention is not limited only by the examples. The percentages (%) shown in Examples and Application Examples are based on polymerization unless otherwise specified.

The heptane-insoluble matter (hereinafter abbreviated as HI), which indicates the proportion of the crystalline polymer in the polymer, is the remaining amount when extracted with boiling n-heptane for 6 hours using an improved Soxhlet extractor. Melt flow rate (MFR) and melt index (MT) were measured according to ASTM-D1238. The bulk density was measured according to ASTM-D 1895-69 Method A.

XPS measurement was performed using the Kratos Exam 800, and the Mg K
α ray was used as the X-ray source. After applying a double-sided tape to the sample table, placing the sample on it and reducing the pressure to 10 ^-8 torr or less, start irradiating X-rays. For magnesium atoms, the bond energy is 85 to 95 (eV). For titanium atoms, Binding energy
The measurement was performed in the range of 450 to 460 (eV). In addition, the binding energy used the spectrum (peak position) based on carbon 1S electron of a double-sided tape as a reference. As the X-ray irradiation time became longer, a change in the spectrum (peak intensity) of each element was observed. The change in the peak intensity with respect to the X-ray irradiation time was tracked, and the peak intensity extrapolated to the X-ray irradiation time 0 was used. The amount of the element was determined. Next, the peak intensity at X-ray irradiation time 0 indicating each element was corrected by a quantitative factor, and the atomic ratio of titanium / magnesium was determined.

Example 1 In a 500 ml reaction vessel equipped with a reflux condenser, 8.3 g of chip-shaped metallic magnesium and n-
After adding 250 ml of hexane and stirring at 68 ° C. for 1 hour, the metallic magnesium was taken out and dried by heating under reduced pressure to obtain preactivated metallic magnesium. Next, 140 ml of n-butyl ether and 0.5 ml of a 10% n-butyl ether solution of iodine were added to the metallic magnesium, heated to 65 ° C., and a solution consisting of 50 ml of n-butyl ether and 38.5 ml of n-butyl chloride was added dropwise over 50 minutes. did. After reacting at 70 ° C. for 4 hours with stirring, the reaction solution was cooled to 0 ° C.

To this reaction solution, 55.7 ml of HC (OC ₂ H ₅ ) _{3 was} added dropwise over 1 hour, the temperature was raised to 35 ° C. over 1 hour, and maintained at the same temperature for 1 hour. At this time, formation of a solid was observed. The temperature was raised to 50 ° C. over 1 hour and maintained at the same temperature for 1 hour. Further, the temperature was raised to 80 ° C. in one hour and maintained at the same temperature for two hours. Generate solid at 60 ℃
After washing 6 times with 300 ml each of n-hexane and drying under reduced pressure at room temperature for 1 hour, 33.8 g of a magnesium-containing solid (A) containing 19.0% of magnesium and 28.9% of chlorine was recovered.

300m equipped with reflux condenser, stirrer and dropping funnel
1 g of the solid (A) in a nitrogen atmosphere.
And 50 ml of n-heptane, and stirred at room temperature
A mixed solution of 2.0 ml of 2-trichloroethanol and 11 ml of n-heptane was added dropwise over 30 minutes, and the mixture was further stirred at 80 ° C. for 1 hour.
The obtained solid was separated by filtration and washed four times with 100 ml each of n-hexane at room temperature and twice with 100 ml each of toluene to obtain a toluene slurry of the solid (B).

Toluene was added to the slurry of the solid (B) so that the amount of toluene became 40 ml, and titanium tetrachloride was further added so that the volume ratio of titanium tetrachloride / toluene became 3/2, and the temperature was raised to 90 ° C. Under stirring, di-n-butyl phthalate 3 ml and toluene 5 ml
Was added dropwise over 5 minutes, followed by stirring at 120 ° C. for 2 hours. The obtained solid was separated by filtration at 90 ° C., and each 100 ml of toluene was removed.
2 times at 90 ° C. Then, after washing 5 times each time with 100 ml of n-hexane at room temperature, 100 ml of n-hexane was newly added.
Add a solution of 5 g of hexachloroethane in ml, and add
Stirred at C for 1 hour. The solid was separated by filtration, washed seven times with 100 ml each of n-hexane at room temperature, and dried under reduced pressure at room temperature for 1 hour to obtain 5.6 g of a catalyst component [catalyst (1)]. The catalyst (1)
It contained 1.7% Ti and 20.3% Mg. Therefore, A = 0.043
Met. B = 0.03 ± 0.003 by XPS measurement.

Example 2 In a nitrogen gas atmosphere, 2.0 g of the catalyst (1) and 42.5 ml of n-heptane were put in a 300 ml reaction vessel equipped with a stirrer and a dropping funnel, and stirred at 0 ° C. Next, the pressure in the yarn was reduced, and then propylene was introduced to saturate the solvent with propylene. 7.5 ml of n-heptane solution (TEAL concentration: 0.1 mol / l) of triethylaluminum (TEAL) was added to polymerize propylene. Propylene was continuously supplied, and polymerization was continued until 6.0 g of polypropylene was produced. After purging propylene gas in the gas phase with nitrogen gas, the solid phase was washed with 50 ml of n-hexane five times at room temperature. Further, a pre-polymerized catalyst component [Catalyst (2)] was prepared by drying under reduced pressure at room temperature for 1 hour.

Example 3 A toluene slurry of the solid (B) was prepared in the same manner as in Example 1. Next, toluene was added so that the toluene became 45 ml, and the volume ratio of titanium tetrachloride / toluene was further increased.
Titanium tetrachloride was added so as to be 1/2. After reacting at 95 ° C. for 2 hours, the solid substance was separated by filtration at 90 ° C., and washed five times with 100 ml of n-hexane at room temperature. Next, a solution obtained by dissolving 5 g of hexachloroethane in 100 ml of n-heptane was newly added, and heat-treated at 80 ° C. for 1 hour. Thereafter, it was washed 7 times with 100 ml of n-hexane at room temperature,
Further, the catalyst component was dried under reduced pressure at room temperature for 1 hour [catalyst (3)].
6.2 g were obtained.

Catalyst (3) contained 2.3% Ti and 21.2% Mg.
Therefore, A was 0.055. B = 0.041 by XPS measurement
± 0.004.

Example 4 A catalyst component [catalyst (4)] was prepared by prepolymerizing the catalyst (3) except that the catalyst (1) was changed to the catalyst (3) and propylene was changed to ethylene. The content of polyethylene per 1 g of the catalyst (3) was 0.5 g.

Comparative Example 1 A stainless steel mill pot having an internal volume of 300 ml was filled with 650 g of stainless steel balls having a diameter of 8 mm. To this, 10.5 g of anhydrous magnesium chloride and 5.3 ml of di-n-butyl phthalate were introduced under a nitrogen gas atmosphere, and the mixture was vibrated for 13 hours and pulverized.
6m of crushed solid, 300m
Then, a mixed solution of 20 ml of titanium tetrachloride and 50 ml of toluene was added thereto, and the mixture was stirred at 70 ° C. for 2 hours. The solid phase was separated by filtration, and 8 times with 70 ml each of toluene at room temperature.
Washed three times with 70 ml each of hexane. Furthermore, it dried under reduced pressure at room temperature for 1 hour, and prepared 5.0 g of catalyst components [catalyst (5)].

Catalyst (5) contained 3.7% Ti and 21.0% Mg. Therefore, A was 0.089. B = 0 by XPS measurement.
It was 12 ± 0.02.

Comparative Example 2 Preliminary polymerization of the catalyst (5) was carried out in the same manner as in Example 2 except that the catalyst (1) was changed to the catalyst (5) to obtain a catalyst component [catalyst (6)]. The content of polypropylene per 1 g of the catalyst (6) was 3 g.

Comparative Example 3 49 ml of 2-ethylhexanol was added to a slurry of 10 g of anhydrous magnesium chloride and 51 ml of n-dodecane, and reacted at 130 ° C. for 2 hours to obtain a homogeneous solution. Where phthalic anhydride
2.4 g was added and dissolved. 250 ml of titanium tetrachloride was cooled to -20 ° C, and 60 ml of the above solution was added dropwise thereto with stirring over 20 minutes. Then, the temperature was raised to 120 ° C. over 4 hours, and 4.2 ml of di-n-butyl phthalate was added and reacted for 2 hours. 1 solid phase
After filtering off at 20 ° C., 250 ml of titanium tetrachloride was newly added and reacted at 120 ° C. for 2 hours. The solid phase was washed six times with 100 ml of n-hexane at room temperature and dried under reduced pressure at room temperature for 1 hour to obtain 6.3 g of a catalyst component [catalyst (7)].

Catalyst (7) contained 2.9% Ti and 21.4% Mg. Therefore, A was 0.069. B = 0 by XPS measurement.
It was 12 ± 0.02.

Comparative Example 4 Preliminary polymerization of the catalyst (7) was carried out in the same manner as in Example 2 except that the catalyst (1) was changed to the catalyst (7) to obtain a catalyst component [catalyst (8)]. The content of polypropylene per 1 g of the catalyst (7) was 10 g.

Comparative Example 5 A stainless steel mill pot having an internal volume of 300 ml was filled with 650 g of stainless steel balls having a diameter of 8 mm. To this, 17.1 g of diethoxymagnesium was introduced in a nitrogen gas atmosphere, and 13
Pulverized by shaking for hours. 6 g of the pulverized solid was placed in a 300-ml flask equipped with a stirrer previously purged with nitrogen gas, and a mixed solution of 20 ml of titanium tetrachloride and 50 ml of toluene was added thereto.
Stirred at C for 2 hours. The solid phase was separated by filtration and washed eight times with 70 ml each of toluene at room temperature and three times each with 70 ml each of n-hexane at room temperature. Furthermore, it dried under reduced pressure at room temperature for 1 hour, and prepared 5.0 g of catalyst components [catalyst (9)]. The catalyst (9) converts Ti to 3.
It contained 2% and 20.7% of Mg. Therefore, A = 0.078. B = 0.21 ± 0.02 by XPS measurement.

Comparative Example 6 Preliminary polymerization of the catalyst (9) was carried out except that the catalyst (1) was changed to the catalyst (9) and propylene was changed to ethylene, to obtain a catalyst component [catalyst (10)]. The content of polyethylene per 1 g of the catalyst (9) was 0.5 g.

Application Example 1 In a 1.5-liter stainless steel (SUS 315) autoclave equipped with a stirrer, under a nitrogen gas atmosphere, 2.0 ml of TEAL n-heptane solution (0.2 mol / l) and n-heptane solution of phenyltrixylsilane are added. (0.04 mol / l) 2.0 ml were mixed, and a mixed solution kept for 5 minutes was added. Next, 300 ml of hydrogen gas and 1 l of liquid propylene as a molecular weight controlling agent were injected under pressure.
After the temperature of the reaction system was raised to 70 ° C., 10 mg of the catalyst (1) obtained in Example 1 was introduced. After polymerization of propylene at 70 ° C. for 1 hour, unreacted propylene was purged to obtain 230 g of transparent polypropylene powder. [Catalyst efficiency (K _C )
(G of polymer produced per gram of catalyst component) = 23,000]
The resulting polymer has a HI of 97.2%, an MFR of 6.0 g / 10 min, and a bulk density of
It was 0.44 g / cm ³ .

Application Example 2 Propylene was polymerized in the same manner as in Application Example 1, except that the catalyst (1) was changed to 40 mg of the catalyst (2). K _P (the amount of the produced polymer per 1 g excluding the amount of the pre-polymerized polymer in the catalyst component) = 22,500, and the HI of the produced polymer is 97.0.
%, MFR was 6.1 g / 10 min, and bulk density was 0.47 g / cm ³ .

Application Example 3 Stainless steel (SUS 32) with an internal volume of 1.5 l equipped with a stirrer
In a nitrogen autoclave, 10 mg of the catalyst (3) obtained in Example 3 was added in a nitrogen gas atmosphere.
7 mmol and 390 g of isobutane were charged, and the polymerization system was heated to 85 ° C.
The temperature rose. Next, hydrogen was introduced until the hydrogen partial pressure became 2.0 kg / cm ^2, and then ethylene was introduced until the ethylene partial pressure became 0.5 kg / cm ² . The polymerization was carried out for 60 minutes while continuously supplying ethylene so that the total pressure of the polymerization system became constant. After completion of the polymerization, the polymerization solvent, unreacted ethylene is purged, the polymer in the form of a white powder is taken out, and dried at 70 ° C. under reduced pressure for 10 hours.MI 3.0 g / 10 min, bulk density is 0.37 g. / cm ³ of polyethylene powder was obtained. K _CE (g of polymer produced per 1 g of catalyst component and 1 kg / cm ^{2 of} ethylene partial pressure) was 4,720.

Application Example 4 The polymerization of ethylene was carried out in the same manner as in Application Example 3, except that the catalyst (3) was changed to 15 mg of the catalyst (4).

K _PE (Part 1 excluding the amount of prepolymerized polymer in the catalyst component
g and the amount of polymer produced per 1 kg / cm ^{2 of} ethylene partial pressure)
The resulting polymer has an MI of 2.8 g / 10 min and a bulk density of 4,590.
0.39 g / cm ³ Application Examples 5 to 8 Instead of the catalyst (1), the catalysts (5) to (8) were replaced with the first.
Propylene was polymerized in the same manner as in Application Example 1 except that the amounts shown in the table were used, and the results are shown in Table 1.

Application Example 9 The polymerization of ethylene was carried out in the same manner as in Application Example 3, except that the catalyst (9) was used instead of the catalyst (3). as a result,
K _CE is 2,170 and MI of the obtained polymer is 2.5 g / 10
The bulk density was 0.28 g / cm ³ .

Application Example 10 The polymerization of ethylene was carried out in the same manner as in Application Example 3, except that the catalyst (3) was changed to 15 mg of the catalyst (10). As a result, K
_PE is 1,090, and MI of the obtained polymer is 1.4 g / 10
The bulk density was 0.28 g / cm ³ .

[Brief description of the drawings]

FIG. 1 is a flowchart showing a method for preparing a catalyst component of the present invention.

 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Teruo Yatsushiro 1-3-1, Nishitsurugaoka, Oi-machi, Iruma-gun, Saitama Prefecture Within Toa Fuel Industry Co., Ltd. (72) Inventor Kaoru Yamamoto Oimachi, Iruma-gun, Saitama 1-3-1 Nishitsurugaoka Research Institute, Toa Fuel Industry Co., Ltd. (72) Inventor Masafumi Imai 1-3-1, Nishitsurugaoka, Oimachi, Iruma-gun, Saitama Prefecture Research Institute, Toa Fuel Industry Co., Ltd.

Claims (3)

(57) [Claims] 1. A compound of the general formula MgR ¹ R ^{2 wherein} R ¹ is an OR group (R is a hydrocarbon group) and R ² is a halogen atom. A solid obtained by treating a solid obtained by treating the magnesium compound represented by the above with a halogen-containing alcohol with a tetravalent chlorinated titanium compound which is liquid at room temperature, wherein the titanium content is 1 to 8% by weight; The solid component satisfies the following relational expression. A> B [where A is the titanium / magnesium ratio (atomic ratio) of the solid and is 0.02 to 0.2, and B is the titanium / magnesium ratio (atomic ratio) of the solid surface measured by X-ray photoelectron spectroscopy. It is 0.05 or less. ] 2. The catalyst component according to claim 1, wherein said solid further contains an electron donating compound. 3. The catalyst component according to claim 1, wherein said solid further contains 0.01 to 500 g of polyolefin per 1 g of said solid.