JPH0343405A - Production of stereoregular polyolefin - Google Patents

Abstract

PURPOSE:To obtain the subject polymer with a high molecular weight while maintaining a high stereolegurality by using a catalyst composed of a specified solid catalyst component, an organometallic compound, an electron donative compound and an oxygen-containing organic compound of Ti. CONSTITUTION:A homogeneous solution containing (A) one component selected from combinations of metallic Mg and a hydroxyorganic compound and oxygen- containing organic compounds of Mg, (B) an electron donative compound and (C) an oxygen-containing organic compound of Ti is initially reacted with (D) an aluminum halide compound to obtain a solid product. The resultant reaction product is then reacted with (E) an electron donative compound and (F) a titanium halide compound to prepare a solid catalyst component. The obtained solid catalyst component is subsequently combined with a compound selected from organometallic compounds of a metal belonging to periodic table Ia, IIa, IIb, IIIb or IVb, an electron donative compound and an oxygen-containing organometallic compound of Ti to obtain a catalyst and the objective polymer is produced by using the resultant catalyst.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a method for producing stereoregular polyolefins. More specifically, the present invention relates to a production method capable of obtaining a high molecular weight and highly stereoregular polymer by using a specific catalyst in the polymerization of an α-olefin having 3 or more carbon atoms.

[Conventional technology]

In recent years, many proposals have been made regarding the production of highly active and highly stereoregular solid catalyst components containing magnesium, titanium, and halogen as main components.

However, when trying to obtain a high molecular weight polymer by the methods of these inventions, methods such as lowering the polymerization temperature or not introducing hydrogen as a chain transfer agent can be used; The problem was that there was a limit to the molecular weight of the polymer.

[Problem to be solved by the invention]

Therefore, the present inventors overcame such drawbacks of the conventional technology, and
In the polymerization of α-olefins having 3 or more carbon atoms, intensive studies were conducted to find a production method that can produce polymers with higher molecular weight while maintaining high stereoregularity.

[Means to solve the problem]

As a result, the present inventors have found that in the polymerization of α-olefins having 3 or more carbon atoms, JP-A-63-3007 and JP-A-63
-314210, JP-A-63-317502, and Japanese Patent Application No. 62-154556.

As a specific solid catalyst component and co-catalyst shown in Japanese Patent Application No. 62-322861, an organometallic combination, an electron-donating compound,
The inventors have also discovered that by using a titanium alkoxy compound, it is possible to obtain a polymer with a higher molecular weight than before while maintaining stereoregularity, and have completed the present invention. That is, the present invention provides the following steps in producing stereoregular polyolefin in the presence of a catalyst comprising a transition metal compound and an organometallic compound: (A) 6. (i) at least one member selected from the group consisting of metallic magnesium and an organic hydroxide compound, and an oxygen-containing organic compound of magnesium; (ii) an electron-donating compound; and (i+i > an oxygen-containing organic compound of titanium). A homogeneous solution containing (iv) is reacted with at least one type of aluminum halide compound, and the obtained solid product is further reacted with (v) an electron-donating compound and (vi) a titanium halide compound. The solid catalyst component obtained by
.

at least one selected from the group of organometallic compounds of group MB and IVb metals; (C) at least one selected from electron-donating compounds as the component; and (D) at least one selected from the group of oxygen-containing organic compounds of titanium. A method for producing a stereoregular polyolefin, characterized by using a catalyst system consisting of one type.

[For production]

Examples of the metal magnesium, hydroxide organic compound, and magnesium oxygen-containing organic compound (i), which are the reactants used in the present invention, include the following.

First, when using magnesium metal and an organic hydroxide compound, the magnesium metal can be in various shapes, such as two powder particles, a foil or a ribbon, and the organic compound hydroxide can be Suitable examples include alcohols, organic silanols, and phenols.

As alcohols, linear or branched aliphatic alcohols, cycloaliphatic alcohols or aromatic alcohols having 1 to 18 carbon atoms can be used. Examples include methanol, ethanol, n-propanol, i-propanol, n-butanol, i-butanol, n-hexanol, 2-ethylhexanol, n-octatool,
Examples include i-octatool, n-stearyl alcohol, cyclopentanol, cyclohexanol, and ethylene glycol. Furthermore, the organic silanol has at least one hydroxyl group, and has one organic group.
selected from alkyl groups, cycloalkyl groups, arylalkyl groups, aryl groups and alkylaryl groups having ~12 carbon atoms, preferably 1 to 6 carbon atoms. For example, we can give the following example. Trimethylsilanol, triethylsilanol, triphenylsilanol, t-butyldimethylsilanol. Furthermore, phenols include phenol and cresol.

Examples include xylenol and hydroquinone.

These hydroxylated organic compounds may be used alone or as a mixture of two or more.

In addition, when metallic magnesium is used to obtain the solid catalyst component of component (A) described in the present invention, for the purpose of promoting the reaction, substances that react with metallic magnesium or produce addition compounds are used. , e.g. iodine, chloride
It is preferable to add one or more polar substances such as mercury, alkyl halides, and organic acids.

Next, examples of compounds belonging to oxygen-containing organic compounds of magnesium include magnesium alkoxides, such as methylate, ethylate, isopropylate, descartes,
methoxyethylate and cyclohexalte, magnesium alkyl alkoxides such as ethyl ethylate, magnesium hydroalkoxides such as hydroxymethylate, magnesium phenoxides such as phenate, naphthinate, phenanthrenate and cresolate, magnesium carboxylates, For example, acetate, stearate.

Benzoate, phenylacetate, adipate.

Sebacates, phthalates, acrylates and oleates, oximates such as butyloximate, dimethylglyoximate and cyclohexyloximate, hydroxamates, hydroxylamine salts such as N-nitroso-N-phenyl-hydroxylamine derivatives, elates , e.g. acetylacetonate, magnesium syralates, e.g. triphenylsilal-
and complex alkoxides of magnesium and other metals, such as MgCA1 (OC2H5)4]2.

These oxygen-containing organomagnesium compounds may be used alone or as a mixture of two or more.

Examples of the electron-donating compound as the reactant in (ii) above include ether, ester, ketone, phenol, amine, amide, imine, nitrile, phosphine, phosphite, stibine, arsine, phosphoramide, and alcoholate. Among them, esters are preferred;
Most preferred are organic acid esters. Examples of organic acid esters include aromatic carboxylic acid mono- or diesters, aliphatic carboxylic acid mono- or diesters, and the like.

Specific examples include butyl formate, ethyl acetate, butyl acetate, isobutyl isobutyrate, propyl pivalate, isobutyl pivalate, ethyl acrylate, methyl methacrylate, ethyl methacrylate, isobutyl methacrylate, diethyl malonate, and malonate. Diisobutyl acid, diethyl succinate.

Dibutyl succinate, diisobutyl succinate, diethyl glutarate, dibutyl glutarate, diisobutyl glutarate, diisobutyl adipate, dibutyl sebacate, diethyl maleate, dibutyl maleate, diisobutyl maleate, monomethyl fumarate, diethyl fumarate,
Diisobutyl fumarate, diethyl tartrate, dibutyl tartrate, diisobutyl tartrate, methyl benzoate, ethyl benzoate, methyl p-toluate, p-tertiary butyl ethyl benzoate, p-ethyl anisate, α-ethyl naphthoate, α - Isobutyl naphthoate, ethyl cinnamate, monomethyl phthalate, dibutyl phthalate, diisobutyl phthalate, dihexyl phthalate.

Dioctyl phthalate, di-2-ethylhexyl phthalate,
Diallyl phthalate, diphenyl phthalate.

Diethyl isophthalate, diisobutyl isophthalate, diethyl terephthalate, dibutyl terephthalate, diethyl naphthalate, f: dibutyl phthalate, and the like. The electron donating compound (ii) may be used alone or as a mixture of two or more.

The general formula is used as the oxygen-containing organic compound of titanium, which is the reactant of <i*i>. However, in the general formula, R1 has 1 to 20 carbon atoms. It preferably represents 1 to 10 hydrocarbon groups such as straight-chain or branched alkyl groups, cycloalkyl groups, arylalkyl groups, aryl groups and alkylaryl groups, and a and b are ako and b>o, and titanium It represents a number that is compatible with the valence, and m represents an integer. In particular, it is desirable to use an oxygen-containing compound in which a is a≦1 and m is 1≦m≦6.

A specific example is titanium tetraethoxide.

Titanium tetra-n-propoxide, titanium tetra-1-
Examples include propoxide, titanium tetra-n-butoxide, hexa-i-proboxydititanate, and the like. The use of oxygen-containing organic compounds having several different hydrocarbon groups also falls within the scope of the invention.

These oxygen-containing organic compounds of titanium may be used alone or as a mixture of two or more.

In addition, for the purpose of improving powder properties, reactant (i)
, (, ii), and (ili), it is also possible to use at least one silicon compound selected from polysiloxanes and silanes. Examples of these silicon compounds include the following. The polysiloxane has the general formula (wherein R2 and R3 are hydrocarbon groups such as alkyl groups and aryl groups having 1 to 12 carbon atoms, hydrogen, and 1 to 12 carbon atoms).
represents an atom or residue capable of bonding to silicon, such as an alkoxy group, an allyloxy group, or a fatty acid residue;
may be the same or different species, and p is usually 2 to 10,0
A siloxane polymer having a chain, cyclic or three-dimensional structure containing one or more types of repeating units (representing an integer of 00) in various ratios and distributions within the molecule (however, all except when R and R3 are hydrogen).

Specifically, examples of chain polysiloxane include hexamethyldisiloxane, octamethyltrisiloxane,
Dimethylpolysiloxane, diethylpolysiloxane, methylethylpolysiloxane.

Examples include dimethoxypolysiloxane, jetoxypolysiloxane, and diphenoxypolysiloxane.

Examples of the cyclic polysiloxane include hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane, hexaphenylcyclotrisiloxane, and octaphenylcyclotetrasiloxane.

Examples of the polysiloxane having a three-dimensional structure include those obtained by heating the above-mentioned chain or cyclic polysiloxane to have a crosslinked structure.

These polysiloxanes are desirably liquid in handling, and desirably have a viscosity at 25° C. of 1 to 10,000 centistokes, preferably 1 to 1,000 centistokes. However, it is not necessary to limit it to a liquid form, and a solid substance generally referred to as silicone grease may also be used.

It represents a group capable of bonding to silicon such as a hydrocarbon group such as a lyl group, an alkoxy group having 1 to 12 carbon atoms, an allyloxy group, a fatty acid residue, and each R4 may be different or the same, and q, s is an integer greater than or equal to 0, r is a natural number, and q
+5-2r+2).

Specifically, for example, trimethylphenylsilane.

Silica hydrocarbons such as allyltrimethylsilane, linear and cyclic organic silanes such as hexamethyldisilane and octaphenylcyclotetrasilane, organic silanes such as methylsilane, dimethylsilane and trimethylsilane, and trimethylmethoxysilane.

Examples include silane compounds containing fatty acid residues such as dimethyljethoxysilane and ethyltriacetoxysilane.

The above silicon compounds may be used alone, or two or more types may be mixed or reacted together.

As the reactant in (iv) above, the aluminum halide shown below is used. In the formula, R5 represents a hydrocarbon group having 1 to 20 carbon atoms, X represents a halogen atom, and n represents a number satisfying 0<n≦2. R5 is preferably selected from straight-chain or branched alkyl groups, alkoxy groups, cycloalkyl groups, arylalkyl groups, aryl groups and alkylaryl groups.

The above aluminum halide compounds can be used alone or in a mixture of two or more. A specific example of the aluminum halide compound is ethylaluminum dichloride.

n-propylaluminum dichloride, butylaluminum dichloride, i-butylaluminum dichloride, sesquiethylaluminum chloride, sesquiisobutylaluminum chloride, sesqui-1-propylaluminum chloride, sesqui-n-propylaluminum chloride, diethylaluminum chloride, Jimmy propyl aluminum chloride, di-n-
Examples include propylaluminum chloride, di-butylaluminum chloride, diethylaluminum bromide, and diethylaluminum iodide.

As the electron donating compound which is the reactant in (v) above,
Examples include the same compounds as the reactant in (ii) above.

The electron donating compound (v) may be used alone or as a mixture of two or more. Further, as the electron donating compound (v), a compound of the same type as the electron donating compound (ii) or a different type of compound can be used.

As the halogenated titanium compound which is the reactant in (vi) above, a titanium compound represented by the general formula Ti (OR) fX4i is used. In the formula, R6 represents a hydrocarbon group having 1 to 20 carbon atoms, X represents a halogen atom, and f represents a number satisfying Q<f≦4. R6 is preferably selected from straight-chain or branched alkyl groups, alkoxy groups, cycloalkyl groups, arylalkyl groups, aryl groups and alkylaryl groups.

The above halogenated titanium compounds can be used alone or as a mixture of two or more. c) Specific examples of titanium rogenide include titanium tetrachloride, ethoxytitanium trichloride, propoxytitanium trichloride, butoxytitanium trichloride, phenoxytitanium trichloride, jetoxytitanium dichloride, triethoxytitanium chloride, etc. It will be done.

Further, a surfactant can be used as appropriate along with the reactants (V) and (vi).

Surfactants that can be used include anionic surfactants, cationic surfactants, nonionic surfactants, and amphoteric surfactants. Among these, nonionic surfactants are most preferred.

Examples of nonionic surfactants include polyoxyethylene alkyl ethers, such as polyoxyethylene lauryl ether, polyoxyethylene cetyl ether, polyoxyethylene stearyl ether, and polyoxyethylene alkylaryl ethers, such as polyoxyethylene octylphenyl ether. , polyoxyethylene nonylphenyl ether, C12 of C-C polyhydric alcohol
Examples include 212 to C18 fatty acid esters, such as sorbitan fatty acid ester, ethylene glycol fatty acid ester, and polyoxyethylene alkylamine. Particularly preferred is sorbitan fatty acid ester. As the sorbitan fatty acid ester, sorbitan monourea
Examples include sorbitan monopalmitate, sorbitan distearate, and sorbitan distearate.

Furthermore, fluorine-based surfactants can also be used.

Examples of the fluorosurfactant include nonionic perfluoroalkylethylene oxide adducts.

Surfactants may be used alone or as a mixture of two or more.

The solid catalyst component obtained in the present invention includes the above-mentioned reactant (i)
, (ii) and (irt) are reacted with a reactant (iv), and the obtained solid product is then reacted with reactants (V) and (vi). It can be prepared by

These reactions are preferably carried out in a liquid medium. It should therefore be carried out in the presence of an inert organic solvent, especially if these reactants themselves are not liquid under the operating conditions or if the amount of liquid reactants is insufficient. As the inert organic solvent, any solvent commonly used in the art can be used, including aliphatic, alicyclic or aromatic hydrocarbons, their halogen derivatives, or mixtures thereof, such as isobutane, hexane, etc. .

Heptane, cyclohexane, benzene, toluene.

xylene, monochlorobenzene, benzyl chloride.

Methylene dichloride, 1,2-dichloroethane.

1,3-dichloropropane, 1,4-dichlorobutane, trichloroethane, tetrachloroethane.

Examples include tetrachloroethylene, carbon tetrachloride, and chloroform. These organic solvents may be used alone or as a mixture. Further, when a halogen derivative or a mixture is used, good results may be brought about in the stereoregularity of the polymerization active nine polymer.

Reactants (i) and (ii) used in the present invention.

There are no particular restrictions on the amounts of (m), (iv), (V) and (vi) used, but the ratio of magnesium atoms (i) to titanium atoms (iii) is 1:0.01 to 20, Preferably 1:0.1 to 1:5, the molar ratio of magnesium atom to electron donating compound (ii) and (V) is 1:0
．． 05-1:1.0. Preferably 1:0.1 to 1:O,
It is preferable to select the amount used so that S is obtained. When it is outside these ranges, problems such as low polymerization activity and low stereoregularity occur. Further, the amount of the reactant used is adjusted so that the ratio of magnesium atoms to aluminum atoms in aluminum halide (iv) is in the range of 1:0.1 to 1:100, preferably 1:1 to 1:20. It is preferable to choose. In particular, a range of 1:1 to 1:5 is suitable. If the ratio of aluminum atoms is too large outside this range, the catalytic activity will be low, and if it is too small, good powder properties will not be desired. Furthermore, the ratio of magnesium atoms to titanium atoms (vi) is 1:1 to
It is preferable to select the amount of the reactant to be used in a range of 1:100, preferably 1:3 to 1:50. If it is out of this range, problems such as low polymerization activity and coloring of the product will occur. The amount of surfactant used is 50 to 50,000 ppm, preferably 10 to 50,000 ppm based on the total content.
A range of 0 to 110,000 pp is suitable. If the amount of surfactant used is too small outside this range, agglomeration phenomenon of the solid product will occur, resulting in poor powder properties of the polymer particles, and if it is too large, the polymerization activity will be low or the product will be damaged. This causes problems such as coloring. If the amount of surfactant used is appropriate, polymerization activity or stereoregularity may be improved.

Further, when a silicon compound is used in preparing a homogeneous Mg-Ti solution, the ratio of magnesium atoms to silicon compounds is preferably selected to be 1:20 or less, preferably 1:5 or less. If it is out of this range, problems such as low polymerization activity and failure to improve powder properties will occur.

Reactant (i), (ii), (i+i
) to obtain a homogeneous solution, the reaction conditions are -50 to 300
0.5 °C, preferably at a temperature in the range of 0 to 200 °C
The reaction is carried out for ~50 hours, preferably 1 to 6 hours, in an inert gas atmosphere under normal pressure or increased pressure. Furthermore, the reactant (iv
), (V) and (vi) in the reaction of -50-2
00°C, preferably -30 to 150°C, for 0.2 to 50 hours, preferably 0.5 to 5 hours, in an inert gas atmosphere or under pressure. The reaction of the reactant (vi) may be divided into multiple stages.

In this case, an effect such as an increase in polymerization activity may be observed due to an increase in the Ti content in the catalyst component.

The thus obtained solid catalyst component (A) may be used as it is, but generally, remaining unreacted substances and by-products are removed by filtration or decanting, and then washed several times with an inert organic solvent. , suspended in an inert organic solvent.

It can also be used which is isolated after washing and heated under normal pressure or reduced pressure to remove the inert organic solvent.

Component (A) prepared as described above consists of component (B), an organometallic compound of group 1a, na, mb, and IVb metals of the periodic table, component (C), an electron-donating compound, and component (D )
of titanium in combination with an oxygen-containing organic compound and used for polymerization.

The organometallic compound of component (B) is lithium.

Examples include organometallic compounds consisting of a metal such as magnesium, zinc, tin, or aluminum and an organic group.

As the above-mentioned organic group, an alkyl group can be exemplified.

This alkyl group is linear or branched and has 1 to 1 carbon atoms.
Twenty alkyl groups are used. Specifically, for example,
n-butyllithium, diethylmagnesium, diethylzinc, trimethylaluminum, triethylaluminum, trimybutylaluminum, tri-butylaluminum.

Examples include tri-n-decylaluminum, tetraethyltin, and tetrabutyltin.

Above all, it is preferable to use trialkylaluminum having a linear or branched alkyl group having 1 to 10 carbon atoms. Also usable are alkyl metal halides having an alkyl group having 1 to 20 carbon atoms, such as ethyl aluminum sesquichloride, diethylaluminum chloride, diisobutyl aluminum chloride, or alkyl metal alkoxides, such as diethylaluminum ethoxide.

These organometallic compounds can be used alone or as a mixture of two or more.

Suitable examples of the electron-donating compound as component (C) include organic acid esters, oxygen-containing organic compounds of silicon, and nitrogen-containing organic compounds.

Examples of the organic acid ester include the same compounds as the reactants used in the preparation of the solid catalyst of component (A).

Among them, aliphatic carboxylic acid esters are preferred.

Examples include aromatic carboxylic acid esters. in particular,
The aliphatic carboxylic acid ester has 2 to 1 carbon atoms.
8, ethyl acetate, propyl acetate, butyl acetate,
Examples include ethyl propionate, butyl propionate, and ethyl butyrate. As the aromatic carboxylic acid ester, methyl benzoate has 8 to 24 carbon atoms.

Examples include ethyl benzoate, methyl toluate, methyl anisate, and ethyl anisate.

The above organic acid esters may be used alone, or two
It is also possible to use a mixture or reaction of more than one type.

The oxygen-containing organic compound of silicon has 1 to 12 carbon atoms.
Examples include compounds in which the hydrocarbon group is bonded to silicon via oxygen.

Specifically, for example, trimethylmethoxysilane, trimethylethoxysilane, dimethylethoxysilane, and trimethyl-i-propoxysilane.

Trimethyl-n-propoxysilane, trimethyl-1-
Butoxysilane, trimethyl-i-butoxysilane, trimethyl-〇-butoxysilane, trimethyl-n-pentoxysilane, trimethylphenoxysilane, dimethyldimethoxysilane, methylphenyldimethoxysilane,
Diphenyldimethoxysilane 2 Methyldimethoxysilane, Dimethyljethoxysilane, Diethyljethoxysilane.

Diphenyljethoxysilane Methyldodecyljethoxysilane, methyloctadecyljethoxysilane, methylphenyldiethoxysilane, methyljethoxysilane, dibenzyljethoxysilane, jetoxysilane, dimethyldi-n-butoxysilane, dimethyldi-miepentoxy Silane.

Diethyldi-mi-pentoxysilane, di-mi-butyldi-mi-pentoxysilane, diphenyldi-n-octoxysilane, methyltrimethoxysilane, ethyltrimethoxysilane, n-butyltrimethoxysilane, phenyltrimethoxysilane.

Vinyltrimethoxysilane, chloromethyltrimethoxysilane, 3-chloropropyltrimethoxysilane, 4-
Chlorophenyltrimethoxysilane.

Trimethoxysilane, methyltriethoxysilane.

Ethyltriethoxysilane, n-propyltriethoxysilane, n-butyltriethoxysilane.

Phenyltriethoxysilane, vinyltriethoxysilane, 3-aminopropyltriethoxysilane, triethoxysilane, ethyltriamypropoxysilane, vinyltriamypropoxysilane, i-pentyltriethoxysilane
-butoxysilane, methyltrimypentoxysilane, ethyl-i-pentoxysilane, methyltri-n-
Hexoxysilane, phenyltri-l-pentoxysilane.

Tetramethoxysilane, tetraethoxysilane.

Tetra-1-propoxysilane, tetra-n-propoxysilane, tetra-n-butoxysilane.

Alkoxysilanes or aryloxysilanes such as tetra-i-pentoxysilane, tetra-n-hexoxysilane, tetraphenoxysilane, tetramethyljethoxydisilane, dimethyltetraethoxydisilane, dichlorojethoxysilane.

Examples include haloalkoxysilane or haloaryloxysilane such as dichlorodiphenoxysilane and tribromoethoxysilane.

The above oxygen-containing organic compounds of silicon may be used alone, or two or more types may be mixed or reacted together.

Examples of nitrogen-containing organic compounds include compounds that have a nitrogen atom in the molecule and function as a Lewis base.

Specifically, acetic acid N, N-dimethylamide, benzoic acid N
, N-diethylamide, toluic acid N.

Amide compounds such as N-dimethylamide, 2°2.6
．． 6-tetramethylbiperidine, 2,6-diisopropylpyrrolidine, 2,6-diisobutylpyrrolidine, 2.
6-dibutyl-4-methylpiperidine, 2,2.6
-) Limethylpiperidine, 2,2.6.6-titraethylpiperidine.

1.2,2.6.6-pentamethylpiperidine.

2.2.6.6-tetramethyl-4-piperidylbenzoate, piperidine-based compounds of bis(2,2,6,6-tetramethyl-4-piperidyl)sebacate, 2,6-
Pyridine compounds such as diitubrobylpyridine, 2゜6-shiitubutylpyridine, 2-isopropyl-6-methylpyridine, 2゜2.5.5-tetramethylpyrrolidine, 2.5-diisopropylpyrrolidine, 2. 2.5-
Trimethylpyrrolidine, 1,2,2.5.5-pentamethylpyrrolidine, 2,5-diisobutylpyrrolidine pyrrolidine compounds, trimethylamine, triethylamine, tributylamine, tribenzylamine, tetramethylethylenediamine, diisopropylethylamine,
t-butyldimethylamine, diphenylamine, di-0
Examples include amine compounds such as -tolylamine, and aniline compounds such as N,N-diethylaniline and N,N-diisopropylaniline.

The above nitrogen-containing organic compounds may be used alone, or 2F! The above can also be used by mixing or reacting them.

Preferred examples of the titanium oxygen-containing organic compound of component (D) include titanium tetraalkoxide. Specific examples include tetraethyl titanate, tetra-n-propyl titanate, having 1 to 20 carbon atoms, particularly 2 to 18 carbon atoms;
Tetra-i-propyl titanate Tetra-n-butyl titanate, Tetra-1-butyl titanate, Tetra-
Examples include 2-ethylhexyl titanate and tetrastearyl titanate.

The amount of the solid catalyst component (A) used is 0.001 to 265 mmol (-mol) of titanium atoms per reactor 11.
) is preferably used in an amount corresponding to .

The organoaluminum compound of component (B) is added in an amount of 0.0% per reactor 11. 02-5 (1+mol, preferably 0.
Use at a concentration of 2-5 gaol.

The electron-donating compound of component (C) is added in an amount of 0. 001~50+mol, preferably 0.01~
Use at a concentration of 5.01.

Component (D), the titanium oxygen-containing organic compound, is in reactor IA.
per 0-005~50 m@ols preferably 0.005 to 50 m@ols.
Use at a concentration of 05-5 gaol.

The mode of feeding the four components into the polymerization vessel in the present invention is not particularly limited, and for example, component (A), component (B),
〉, a method in which component (C) and component (D) are each separately fed into a polymerization vessel, or a method in which component (A) and component (C) are brought into contact and then component (B) and component (D) are separately fed into a polymerization vessel. A method in which component (A), component (B), and component (C) are brought into contact with each other and then brought into contact with component (D) for polymerization. A method in which component (C) and component (D) are brought into contact and polymerized can be employed.

Polymerization of olefins is carried out in the gas phase or in the liquid phase at a reaction temperature below the melting point of the polymer.

If the polymerization is carried out in the liquid phase, the olefin itself may be used as the reaction medium, but it is also possible to use an inert solvent as the reaction medium. The inert solvent can be any commonly used in the art, but especially alkanes, cycloalkanes having 4 to 20 carbon atoms, such as isobutane, pentane, hexane, cyclohexane, etc. is appropriate.

The olefin to be polymerized in the method for producing a polyolefin of the present invention is an α-olefin of the general formula R-CH-CH2 (wherein R is a linear or branched chain having 1 to 10 carbon atoms, particularly 1 to 8 carbon atoms). (representing substituted or unsubstituted alkyl groups in the chain). Specifically, propylene, 1-butene, 1-pentene, 4-methyl-1-
Penten.

Examples include 1-octene. These can be subjected to not only homopolymerization but also random copolymerization and block copolymerization. During copolymerization, two of the above α-olefins
Polymerization is carried out using more than one species or α-olefin and dienes such as butadiene and isoprene. In particular, it is preferable to carry out the polymerization using propylene, propylene and ethylene, propylene and the above α-olefins other than propylene, propylene and dienes.

The polymerization reaction conditions are not particularly limited as long as the reaction temperature is lower than the melting point of the polymer, but usually the reaction temperature is 20 to 110 ℃.
℃ and pressure 2 to 50 kg/c-.G.

As the reactor used in the polymerization step, any reactor commonly used in the technical field can be used as appropriate.

For example, using a stirred tank reactor, a fluidized bed reactor, or a circulation reactor, the polymerization operation can be carried out in a continuous mode, a semi-batch mode, or a batch mode.

[Effect of the invention] Using the catalyst of the present invention, the conventional method, that is, JP-A-83
-3007, JP-A-63-314210, JP-A-6
It is possible to produce high molecular weight polyolefins while maintaining the high stereoregularity of the catalysts disclosed in No. 3-317502, Japanese Patent Application No. 154556/1982, and Japanese Patent Application No. 322861/1982.

〔Example〕

The present invention will be illustrated below by examples, but the present invention is not limited in any way by these examples.

The properties of the polymers in Examples, Reference Examples, and Comparative Examples were measured by the following methods.

Intrinsic viscosity [η]: M1 is constant in orthodichlorobenzene at 140°C, but the intrinsic viscosity [η] and viscosity average molecule f
There is the following formula between l M v.

4 [77] -1,88X 10 , the filtrate is collected. After most of the xylene in the filtrate has been evaporated, it is further vacuum dried to collect the xylene-soluble content, which is calculated as a percentage of the weight of the original sample.

Example 1 (a) [Preparation of solid catalyst component (A)] 15 g (0.62 wol) of metallic magnesium powder was placed in a 31 flask equipped with a stirrer, and 0.75 g of iodine and 401 g of 2-ethylhexanol were added thereto. 7g (
3.1 mol) and titanium tetrabutoxide 211.
After adding 0 g (0.62 mol), the temperature was raised to 90° C., and the mixture was stirred for 2 hours under a nitrogen blanket while excluding generated hydrogen gas. Subsequently, the temperature was raised to 140°C and reaction was carried out for 2 hours. Next, keep the temperature at 100℃ and add 100ml of hexane.
After diluting with 1, 47.7 g of diisobutyl phthalate (0,
17 mol) was added and reacted at 70°C for 1 hour to form a homogeneous solution containing magnesium and titanium (Mg-Ti solution).
I got it.

Mg in Mg-Ti solution in a flask with an internal volume of 500 ml.
After adding 0.066 mol of 1,2-dichloroethane to 20.5 g of isobutylaluminum dichloride (a solution diluted to 50% with hexane) and raising the temperature to 45°C,
A solution containing 2.3 ml was added dropwise over 1 hour. Next, the temperature was raised to 70°C over 1 hour, and the mixture was further stirred at 70°C for 1 hour to obtain a slurry containing a white solid product, which was then washed with hexane. Titanium tetrachloride 130,
6ml (1,19sol) of chlorobenzene
After adding the entire amount of the solution diluted to 0.6 ml, it was heated at 60°C for 1
After reacting at 90°C for 1.5 hours, the temperature was lowered to 60°C and 7.3g of diisobutyl phthalate (0,0264s+ol
) was added and reacted at 110°C for 2 hours.

The solid part was collected by filtering the product and again
130.6 ml of titanium tetrachloride and 130 ml of chlorobenzene.
The mixture was suspended in 6 ml and stirred at 60°C for 1 hour and at 110°C for 1 hour. Hexane was added to the product and the product was thoroughly washed until no titanium compound released was detected.

In this way, a slurry of solid catalyst component (A) suspended in hexane was obtained. The supernatant liquid was removed, dried under a nitrogen atmosphere, and elemental analysis revealed that T1 was 3.3% by weight.

(b) Propylene polymerization The interior of a stainless steel electromagnetic stirring autoclave having an internal volume of 51 liters was sufficiently purged with nitrogen, and 3.5 mmol of triethylaluminum was added as the catalyst component (B).

Diphenyldimethoxysilane as catalyst component (C) 0.
87■■of, solid catalyst component (A) 25■ and tetranonyl titanate as catalyst component (D) 0.87gaol
were added sequentially to increase the autoclave internal pressure to 0.1 kg/
After adjusting the temperature to cd G and adding 2500 ml of liquid propylene and starting stirring, the temperature was raised to 70°C and polymerization was carried out for 90 minutes. After the polymerization reaction was completed, stirring was stopped, unreacted propylene in the system was discharged, and the produced polymer was recovered. As a result, the amount of polymer produced was 213g, and the activity was 11,200g/
Corresponds to g. In addition, when the strength characteristics of the polymer particles were measured, [η]4.79g/dj2. A result of 1 wt% of Xyl was obtained.

Comparative Example 1 Polymerization of propylene was carried out under the same conditions as in (b) of Example 1 except that the tetranonyl titanate used in (b) of Example 1 was not added as component (D). The result is activity 2
6000g/g, [η]4.12g/djl,
A result of 3 wt% was obtained.

Comparative Example 2 Propylene was added under the same conditions as in (b) of Example 1, except that 0.87°C mol of titanium tetrachloride was added as component (D) in place of the tetranonyl titanate used in (b) of Example 1. Polymerization was carried out. The result is activity 10600g/g
, [η13.65g/dJ, Xy1.4wt%.

Example 2 Polymerization of propylene was carried out under the same conditions as in (b) of Example 1, except that 1.7 maol of tetranonyl titanate was used as the catalyst component (B) in Example 1. The results are: activity 5000g/g, [η] 5.00g/dj! ,
Xy1.6wt% was obtained.

Example 3 Polymerization of propylene was carried out under the same conditions as in (b) of Example 1, except that 0.35a+l1ol of tetranonyl titanate was used as the catalyst component (B) in Example 1. The result was an activity of 18,500g/g.

[7714, 66g/djl, Xyl, 7wt% to 11
Ta.

Example 4 Polymerization of propylene was carried out under the same conditions as in (b) of Example 1 except that the polymerization temperature was changed to 80° C. in (b) of Example 1. The results were: activity 15200g/g, [η14.4
3 g/dJ, Xyl, 5 wt% was obtained.

Example 5 In place of the tetranonyl titanate used in (b) of Example 1, 0.8% of tetra(2-ethylhexyl) titanate was used.
Polymerization of propylene was carried out under the same conditions as in Example 1 (b) except that 7 mmol was added. The result is activity 21
400g/g, [η]4.71g/dj2. Xyl, 2
wt% was obtained.

Example 6 Tetra(n-butyl) titanate 0.87a+m was used in place of the tetranonyl titanate used in (b) of Example 1.
Polymerization of propylene was carried out under the same conditions as in Example 1 (b) except that ol was added. The result is 7400g of activity.
/g, [η] 4.83 g/di, Xyl, 6 wt% was obtained.

[Brief explanation of drawings]

FIG. 1 is a flowchart depicting the steps for preparing a catalyst in the present invention.

Claims (1)

[Claims] (1) Component (A) includes (i) at least one member selected from the group consisting of magnesium metal, an organic hydroxide compound, and an oxygen-containing organic compound of magnesium, (ii) an electron-donating compound, and (iii) a titanium compound. A homogeneous solution containing an oxygen-containing organic compound is reacted with (iv) at least one type of aluminum halide compound, and the resulting solid product is further reacted with (v) an electron-donating compound and (vi) a halogenated A solid catalyst component obtained by reacting a titanium compound, and (B) component Ia, IIa, IIb of the periodic table,
At least one selected from the group of organometallic compounds of Group IIIb and IVb metals; (C) At least one selected from electron-donating compounds as a component; (D) At least one selected from the group of oxygen-containing organic compounds of titanium. A method for producing a stereoregular polyolefin, characterized by using a catalyst system consisting of one type.