JPH02173010A - Improved production of stereoregular polyolefin - Google Patents

Abstract

PURPOSE:To obtain the title polyolefin which has excellent properties, is free from coloration and odorization and need not be deashed in high yield by polymerizing an alpha-olefin in the presence of a specified catalyst system. CONSTITUTION:An alpha-olefin (e.g. propylene) is polymerized in the presence of a catalyst system comprising a solid catalyst component obtained by reacting a solid product obtained by reacting at least one aluminum halide (e.g. isobutylaluminum dichloride) with a homogenous solution containing at least either of a combination of Mg with an organic hydroxyl compound (e.g. 2- ethylhexanol) and an organic oxy compound of Mg (e.g. magnesium alkoxide), an organic oxy compound of Al (e.g. triisopropoxyaluminum) and an organic oxy compound of Si [e.g. tetrakis(2-ethylhexoxy)silane] with an electron-donating compound (e.g. diisobutyl phthalate) and a Ti halide compound (e.g. TiCl4); at least one component selected from organometallic compounds of the metals of Groups IA, IIA, IIB, IIIB and IVB of the periodic table (e.g. triethylaluminum) and an electron-donating compound (e.g. diisobutyldimethoxysilane).

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 aims to produce highly stereoregular polymers with good particle shape by using a specific catalyst in the polymerization of α-olefins having 3 or more carbon atoms (hereinafter, also includes copolymerization of other α-olefins). The present invention relates to a production method capable of obtaining coalescence in high yield.

[Conventional technology]

Conventionally, catalysts for olefin polymerization include α-type titanium trichloride obtained by reducing titanium tetrachloride with hydrogen, purple γ-type titanium trichloride obtained by reducing titanium tetrachloride with aluminum, or ball milling. δ-type titanium trichloride obtained by pulverization is known. Furthermore, as a method for modifying these catalysts, a method of mixing and pulverizing them together with various modifiers is also known. However, when polymerization is carried out using these catalysts, the polymerization activity is low, and the resulting polymer contains a large amount of catalyst residue, so that a so-called deashing step is indispensable. Furthermore, in recent years, many proposals have been made regarding the production of solid catalyst components containing magnesium, titanium, and halogen as main components. However, many of them require further improvement in terms of activity, stereoregularity of the polymer, powder properties, and the like.

The present inventors have already described a method for obtaining a stereoregular polyolefin in high yield using a specific solid catalyst component characterized by Mg, Ti, and halogen in JP-A No. 63-3007. Special application 1986. -151303゜Patent application 1986-154556
．． Patent application No. 62-322861 was proposed. In these methods, Mg.

A catalyst component with excellent stereoregularity and particle properties is obtained by reacting the reaction product of a homogeneous solution containing Ti and an electron-donating compound with an aluminum halide compound with titanium halide and an electron-donating compound. However, further improvement in catalytic activity has been desired.

[Problem to be solved by the invention]

Therefore, the present inventors overcame the inadequacies of the conventional technology, and
In the polymerization of α-olefins having 3 or more carbon atoms, we conducted intensive studies to find a production method that can produce highly stereoregular polymers with good powder properties at even higher yields.

[Means to solve the problem]

As a result, in the method shown in the above-mentioned Japanese Patent Application Laid-Open No. 63-3007, etc., the oxygen-containing organic compound of silicon and the oxygen-containing organic compound of aluminum are used instead of the oxygen-containing organic compound of tan. The present invention was completed by using a solid catalyst component produced using a homogeneous solution, an organometallic compound as a promoter, and an electron-donating compound. That is, in the present invention, in producing a stereoregular polyolefin in the presence of a catalyst consisting of a transition metal compound and an organometallic compound, (A)
As components: (1) 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; (1) an oxygen-containing organic compound of aluminum; and (1) an oxygen-containing organic compound of silicon. A solid catalyst component obtained by further reacting (y) an electron-donating compound and (1) a halogenated titanium compound with a solid product obtained by reacting at least one type of aluminum halide with a homogeneous solution containing and components (B) of periodic table 1A, IIA, nB, I [
[Process for producing stereoregular polyolefin using a catalyst system consisting of at least one selected from the group consisting of organometallic compounds of group B and IVB metals and an electron-donating compound as component (C).

[For production]

The solid catalyst components used in the present invention include (1) an organic compound of magnesium metal and hydroxide or an oxygen-containing organic compound of magnesium; (li) an oxygen-containing organic compound of aluminum; Obtained by reacting a solid product obtained by reacting a homogeneous solution obtained by reacting a containing organic compound with an aluminum halide compound (N) with an electron donating compound (v) and a halogen compound (vl). Can be done.

In the above (1), when metallic magnesium and a hydroxide organic compound are used, the metallic magnesium can be in various shapes, such as a single powder particle, foil or ribbon, and the hydroxide organic compound can be is alcohol.

Phenols and organic silanols are suitable.

As alcohols, straight-chain 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- propatool, n-butanol, i-butanol, n-hexanol, 2-ethylhexanol, n-octatool,
Examples include l-octatool, n-stearyl alcohol, cyclopentanol, cyclohexanol, and ethylene glycol. Furthermore, the organic silanol has at least one hydroxyl group, and has one organic group.
-0 selected from alkyl groups, cycloalkyl groups, arylalkyl groups, aryl groups and alkylaryl groups having ~12 carbon atoms, preferably 1 to 6 carbon atoms. 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, inpropylate, 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.

Sepagates, phthalates, acrylates and oleates, oximates such as butyloximate, dimethylglyoximate and cyclohexyloximate, hydroxamates, hydroxylamine salts such as N-nitrone-N-phenyl-hydroxylamine derivatives, erulates , for example acetylacetonate,
Examples include magnesium syralates, such as triphenylsilate. These oxygen-containing organomagnesium compounds may be used alone or as a mixture of two or more.

The oxygen-containing organic compound of aluminum which is the reactant of (Seal) is -format Affi (OR). Oxygen-containing compounds of the designation X3-n are used. However, in this form, R1 is a straight or branched alkyl group or cycloalkyl group having 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms.

It represents a hydrocarbon group such as an arylalkyl group, an aryl group or an alkylaryl group, n represents a number of 0 and n≦3, and X represents a halogen atom.

Specific examples of the oxygen-containing organic compound of aluminum include trimethoxyaluminum, triethoxyaluminum, tri-n-propoxyaluminum, tri-propoxyaluminum, tri-n-butoxyaluminum, tri-n-butoxyaluminum, tri-ter
t-Butoxyaluminum, tri(2-ethylhexoxy)aluminum, triphenoxyaluminum, tribenzoxyaluminum, dichloromethoxyaluminum, chlorodimethoxyaluminum, dichloro(2-ethylhexoxy)aluminum.

Chlorodi(2-ethylhexoxy)aluminum.

Examples include dichlorophenoxyaluminum and chlorodiphenoxyaluminum. The use of oxygen-containing organic compounds with several different hydrocarbons also falls within the scope of the invention. These oxygen-containing organic compounds of aluminum may be used alone or as a mixture of two or more.

Examples of the gaseous oxygen-containing organic compound serving as the reactant (Il) include tetramethoxysilane, tetraethoxysilane, and tetra-1-10boxysilane.

Tetra-n-70 boxysilane, tetra-n-butoxysilane, tetra-1-pentoxysilane.

Tetra-n-hexoxysilane, tetraphenoxysilane, tetrakis(2-ethylhexoxy)silane, tetrakis(2-ethylbutoxy)silane, tetrakis(2-ethylbutoxy)silane
-methoxyethoxy)silane.

Methyltrimethoxysilane, ethyltrimethoxysilane, n-butyltrimethoxysilane, phenyltrimethoxysilane, vinyltrimethoxysilane, tetraromethyltrimethoxysilane, 3-chloropropyltrimethoxysilane, 4-chlorophenyltrimethoxysilane, Trimethoxysilane.

Methyltriethoxysilane, ethyltriethoxysilane, n-propyltriethoxysilane, n-butyltriethoxysilane, phenyltriethoxysilane, vinyltriethoxysilane, 3-aminopropyltriethoxysilane, triethoxysilane, ethyltri-1-propoxy Silane, vinyltri-1-propoxysilane, l
-Pentyltri-n-butoxysilane, Methyltriamypentoxysilane, Ethyltri-l-pentoxysilane, Methyltri-n-hexoxysilane, Phenyltriamypentoxysilane, n-Propyltrimethoxysilane, i-Propyltrimethoxysilane, 1 -Butyltrimethoxysilane, dimethyldimethoxysilane, methylphenyldimethoxysilane, diphenyldimethoxysilane, methyldimethoxysilane, dimethyljethoxysilane, diethyljethoxysilane, diphenyljethoxysilane, methyldodecyljethoxysilane, methyloctadecyljethoxysilane , methylphenyldiethoxysilane, methyljethoxysilane, dibenzyljethoxysilane, jetoxysilane.

Dimethyldi-n-butoxysilane, dimethyldi-1-pentoxysilane, diethyldi-1-pentoxysilane,
Di-1-butyldimipentoxysilane, diphenyldimipentoxysilane.

Diphenyldi-n-octoxysilane, diisobutyldimethoxysilane, trimethylmethoxysilane, trimethylethoxysilane, dimethylethoxysilane, trimethyl-1-10boxysilane.

Trimethyl-n-propoxysilane, trimethyl-t-
Alkoxysilane or aryloxysilane such as butoxysilane, trimethyl-1-butoxysilane, trimethyl-n-butoxysilane, trimethyl-n-pentoxysilane, trimethylphenoxysilane, dichlorojethoxysilane, dichlorodiphenoxysilane, tribromo Examples include ethoxysilane, haloalkoxysilane, and heloaryloxysilane.

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

The reactant for (N), halogenated aluminum, is used. In the formula, R2 represents a hydrocarbon group having 1 to 20 carbon atoms, X represents a halogen atom, and n represents Own≦ Represents the number 2, R2 is a straight or branched alkyl group, an alkoxy group, a cycloalkyl group,
Preferably, it is selected from arylalkyl, aryl 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 mentioned above,
ether, ester, getone, phenol, amine, amide, imine, nitrile, phosphine, phosphite,
Mention may be made of stibine, arsine, phosphoramide and alcoholate. Among these, esters are preferred, and organic acid esters are most preferred. Examples of the organic acid esters include mono- or diesters of aromatic carboxylic acids, mono- or diesters of aliphatic carboxylic acids, and the like.

Specific examples thereof include butyl formate, ethyl acetate, butyl acetate, inbutyl 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,
Examples include diallyl phthalate, diphenyl phthalate, diethyl inphthalate, diynbutyl inphthalate, diethyl terephthalate, dibutyl terephthalate, diethyl naphthalate, dibutyl naphthalate, and the like. Electron-donating compounds (
v) is used alone or as a mixture of two or more.

A titanium compound represented by a halogenated titanium compound is used as the reactant (yl). In the formula, R3 represents a hydrocarbon group having 1 to 20 carbon atoms, X represents a halogen atom, f represents a number of 0≦f<4, R3 is a linear or branched alkyl group, an alkoxy group , cycloalkyl group, arylalkyl group, aryl group and alkylaryl group.

The above halogenated titanium compounds can be used alone or as a mixture of two or more. Specific examples of titanium halides include titanium tetrachloride, ethoxytitanium trichloride, propoxytitanium trichloride, butoxytitanium trichloride, phenoxytitanium trichloride, jetoxytitanium dichloride, triethoxytitanium chloride, and the like.

The solid catalyst component obtained in the present invention is the above-mentioned reactant (+).
, (i) and (厘) to react with a reactant <l, and the resulting solid product is then reacted with reactants (v) and (vl). can do.

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, dialicyclic 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-
Examples include dichloropropane, 1,4-dichlorobutane, trichloroethane, tetrachloroethane, tetrachloroethylene, carbon tetrachloride, chloro;1;lum, and the like. These organic solvents may be used alone or as a mixture, and when a halogen derivative or a mixture is used, good results may be obtained for the stereoregularity of the polymerization active monomer. .

Reactant (1), (N) used in the present invention.

There are no particular restrictions on the amounts of (1), (IN, (v), and (Yl)), but the molar ratio of magnesium atoms and aluminum (oxygen-containing organic compound N) is 1:0.01 to 1: 10
, preferably 1:0.05 to 1:4. Magnesium atom (+) and silicon atom <1. ) ratio is 1:0.01
It is preferable to adjust the amount used so that the ratio is 1:20 to 1:0.1 to 1:5, and the ratio of magnesium atoms to aluminum atoms in aluminum halide (N) is 1:0.1 to 1:5. :0.1 to 1:100, preferably 1:0.1 to 1:20, particularly 1:0.4 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.

The molar ratio of magnesium atoms and electron donating compound N) is 1
:0.05~1:2. O preferably 1:0.1 to 1:1
．． It is preferable to select the amount to be used so that the amount is 0. When it is outside these ranges, problems such as low polymerization activity and low stereoregularity occur. Furthermore, the ratio of magnesium atoms to titanium atoms (vl) is 1:1 to 1:10.
It is preferable to select the amount of the reactant to be used so that it is in the range of 0, preferably 1:3 to 1:50.If it is out of this range, problems such as low polymerization activity and coloring of the product may occur. arise.

The reaction conditions when obtaining a homogeneous solution using the reactant (1), (1), <1) are -50 to 300°C, preferably 0 to 200°C.
℃ for 0.5 to 50 hours, preferably 1
The reaction is carried out under normal or elevated pressure in an inert gas atmosphere for ~6 hours. Furthermore, in the reaction of reactant (IV), (N, (vl), -50 to 200°C1, preferably -30 to 1
The reaction conditions of the zero reactant (IV), which are carried out at a temperature in the range of 50° C. for 0.2 to 50 hours, preferably 0.5 to 5 hours, in an inert gas atmosphere or under pressure, are important. is extremely important because it plays a decisive role in the particle shape of the particles produced. Further, the reaction of the reactant 1) may be carried out in multiple stages. In this case, effects such as an increase in polymerization activity may be observed as a result.

The solid catalyst component (A) thus obtained may be used as it is, but if not, residual unreacted substances and by-products may be removed by filtration or decanting, and then the solid catalyst component (A) may be used several times with an inert organic solvent. After washing, it is suspended in an inert organic solvent and used.

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

The solid catalyst component of component (A) obtained as described above is used for olefin polymerization by being combined with the organometallic compound of component (B) and the electron-donating compound of component (C).

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.

As this alkyl group, a straight 11I or branched alkyl group having 1 to 20 carbon atoms is used. Specifically, for example, n-butyllithium, diethylmagnesium, diethylzinc, trimethylaluminum, triethylaluminum, trimybutylaluminum, tri-n-butylaluminum.

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

Particularly preferred is the use of trialkylaluminums having straight or branched C1-C10 alkyl groups, and also alkylmetal halides having C1-20 alkyl groups, such as ethylaluminum sesquichloride, diethylaluminum chloride. , diisobutylaluminum chloride or alkyl metal alkoxides such as diethylaluminum ethoxide can also be used.

These organometallic compounds may 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 reactant (v) used for preparing the solid catalyst of component (A). Among these, preferred are aliphatic carboxylic acid ester and aromatic carboxylic acid ester. Specifically, examples of the aliphatic carboxylic acid ester include ethyl acetate, globil acetate, butyl acetate, ethyl propionate, butyl propionate, and ethyl butyrate, each having 2 to 18 carbon atoms. Examples of aromatic carboxylic acid esters include methyl benzoate, ethyl benzoate, and methyl toluate having 8 to 24 carbon atoms.

Examples include ethyl 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 species.

Examples of the silicon oxygen-containing organic compound include the same compounds as the reactant in (m) above. The oxygen-containing organic compound of silicon may be used alone or as a mixture of two or more, and compounds of the same type or different type from the reactant (i) can be used.

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-dimethylamide, amide compounds such as tolyl 6NN-dimethylamide, 2゜2.6.6-titramethylpiveridine, 2.6-diisopropylaniline, 2,
6-diisobutylpyrrolidine, 2,6-dibutyl-4-methylpiperidine, 2,2,6-drimethylpiveridine, 2,2,6.6-titraethylpiveridine.

1.2.2,6.6-Pentamethylpiperidine.

2.2,6.6-tetramethyl-4-piperidylbenzoate, piperidine-based compound of bis(2,2,6,6-tetramethyl-4-piperidyl)sebacate, 2.6-
Pyridine compounds such as diisopropylpyridine, 26-butylpyridine, 2-isopropyl-6-methylpyridine, 2゜2.5.5-tetramethylpyrrolidine, 2.5-diisopropylpyrrolidine, 2,2.5 - Pyrrolidine compounds such as trimethylpyrrolidine, 1,2,2,5.5-pentamethylpyrrolidine, 2,5-diisobutylpyrrolidine, trimethylamine, triethylamine, tributylamine, tribenzylamine, tetramethylethylenediamine, diisopropylethylamine, t
-butyldimethylamine, diphenylamine, di0-
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 two or more kinds may be mixed or reacted together.

These electron-donating compounds may be used in combination.

The amount of the solid catalytic component (8) used in the reactor is 1! 0.001 to 2.5 mmol of titanium atoms (lno
It is preferred to use an amount corresponding to l).

The organometallic compound of component (B) is 0 per reactor 11.
．． 02-50niol, preferably 0.2-51no
Use at a concentration of 1.

The electron donating compound of component (C) is per reactor 11,
0.001~50n+l1ol, preferably 0.01~
Used at a concentration of 5111[+.

The mode of feeding the three components into the polymerization vessel in the present invention is not particularly limited, and for example, component (A), component (B
), a method in which each component (C) is separately fed into a polymerization machine, or a method in which component (A) and component (C) are brought into contact with each other, and then component (
A method of polymerizing by contacting with B), component (B) and component c
) may be brought into contact with each other and then brought into contact with component (A) for polymerization, or a method in which component (A), component (B), and component (C) are brought into contact with each other in advance for polymerization.

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 stereoregular polyolefin of the present invention has the form -R-CH=CH
α-olefin of 2 (in the formula, R is 1 to 10, especially 1 to
(representing a straight or branched substituted or unsubstituted alkyl group having 8 carbon atoms), specifically propylene, 1-butene, 1-pentene, 4-methyl-1-pentene. , 1-octene, etc.

These are not only homopolymerization but also random copolymerization.

Block copolymerization can be carried out. In copolymerization, two or more of the above α-olefins or an α-olefin and a diene such as butadiene or isoprene are used to copolymerize, particularly propylene.

It is preferable to carry out the polymerization using 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 the pressure is selected from 2 to 50 kg/d-G.

The reactor used in the polymerization step may be any one commonly used in the technical field6.
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. Furthermore, it is also possible to carry out the polymerization in two or more stages with different reaction conditions.

〔Effect of the invention〕

The first effect of the present invention is that it has excellent powder properties, such as the ability to obtain polymer particles with a small number of fine particles, an appropriate average particle size, and a high bulk density. It is effective when applied to phase polymerization method. It is also possible to obtain polymer particles with an extremely narrow particle size distribution. Therefore, in the polymerization process, the formation of deposits in the polymerization equipment is prevented, and in the polymer separation and drying process,
Separation and filtration of the polymer slurry are facilitated, and scattering of fine polymer particles to the outside of the system is prevented. In addition, improved fluidity improves drying efficiency. Furthermore, during the transfer process, no bridging occurs within the silo, eliminating transfer problems. Furthermore, it becomes possible to provide polymers with constant quality.

The second effect of the present invention is that a polymer can be obtained which has extremely high polymerization activity and does not require a deashing step for catalyst removal. Since it is highly active, there is no need to worry about coloring or odor of the product, and there is no need to purify the polymer, making it extremely economical.

The third effect of the present invention is that the polymer has extremely good tree regularity. Therefore, it is extremely advantageous for producing a polymer by a gas phase polymerization method that does not use a reaction medium.

〔Example〕

The present invention will be illustrated below by examples, but the present invention is not limited in any way by these examples.
In Examples and Comparative Examples, the melt flow rate (hereinafter abbreviated as MFR) was measured under ASTM D-1238 conditions.

The isotactic index (hereinafter abbreviated as II) indicates the proportion of the insoluble polymer after n-heptane extraction based on the total produced polymer in weight percentage.

The activity represents the amount of polymer produced (g) per 1 g of the solid catalyst component (A). The breadth and narrowness of the tL polymer particle size distribution can be approximated by plotting the results of classifying the polymer particles using a sieve on probability log paper. The geometric standard deviation was determined from the straight line using a known method and expressed as its common logarithm (hereinafter referred to as σ). Also,
The average particle diameter is the value obtained by reading the particle diameter corresponding to 50% of the weight integrated value of the approximate straight line. The r*m particle content indicates the proportion of fine particles with a particle size of 105 μm or less in weight percentage.

Example 1 (a) Preparation of solid catalyst component (A) 15 g (0.62 nol) of metallic magnesium powder was placed in a 3β flask equipped with a stirring device, and 0.75 g of iodine and 401 g of 2-ethylhexanol were added thereto. 7g
(3,1 mol) and tetrakis(2-ethylhexoxy)silane 336.4 g (0,62 nol)
, 126.5g of triiso-10boxaluminum<
After adding 0.62nol) and further adding decane 1β, the temperature was raised to 90°C and stirred for 1 hour under a nitrogen blanket. Subsequently, the temperature was raised to 140°C and reaction was carried out for 2 hours to obtain a homogeneous solution (Mg-3i-Ap warm solution) containing magnesium, silicon, and aluminum.

Mg Si A! in a flask with an internal volume of 500 m1. Hot solution 7) After adding 0.066 mol of Mg-exchanged jE and cooling to 0°C, a solution of 20.7 g (0,133 mol) of isobutylaluminum dichlorite diluted to 250% in decane was added over 2 hours.

After adding the entire amount, the temperature was raised to 40°C, and a slurry containing a white solid product was obtained, which was then washed with decane. After heating the slurry containing the four-colored solid product thus obtained to 100°C, 125 g of titanium tetrachloride (0
,66no! ) diluted with 125 g of chlorobenzene, and then add 7.3 g of diisobutyl phthalate.
(0,0264101) was added and reacted for 3 hours.

. Collect the solid part by filtering the product, and then
125 g of titanium tetrachloride was suspended in 125 g of chlorobenzene and stirred at 70°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 the solid catalyst component (8) suspended in hexane was obtained, the supernatant liquid was removed, the slurry was dried under a nitrogen atmosphere, and elemental analysis revealed that Ti was 3.3% by weight ( b) Polymerization internal volume of propylene 5! The interior of a stainless steel electromagnetic stirring autoclave was sufficiently purged with nitrogen, and triethylaluminum 1.41101° catalyst component (C) was added as catalyst component element 8).
as diisobutyldimethoxysilane Q, 35111
o1 and solid catalyst component (8) 10■ were added sequentially, the internal pressure of the autoclave was adjusted to 0.1 kg/aaG, 0.2 kg/- of hydrogen was added, and 2000 ml of liquid propylene was added.
In addition, after starting stirring, the temperature was raised to 70°C, and after the completion of the 0 polymerization reaction, which was polymerized for 90 minutes, stirring was stopped, and at the same time, unreacted propylene in the system was released, and the produced polymer was recovered. As a result, the amount of polymer produced was 611g, and the activity was 6110g.
Corresponds to 0g/g. In addition, when the properties of the polymer particles were measured, the MFR was 3.4 g/10 min, II 99.
4%2 Bulk density 0.448/Cl113. Average particle size 41
0μ, ty 0.10. R4 [[The result was that the combined amount of H1 molecules was 0% by weight.

Example 2 When preparing the solid catalyst component (8), Example 1 (I) was used except that 10.4 g (0,067101) of isobutylaluminum dichloride was used in (a) of Example 1 as the component (i). ) A solid catalyst component was obtained in the same manner as in (1).

Using the obtained solid catalyst component, propylene was polymerized under the same conditions as in Example 1 (b). The result is activity 49
000g/g. In addition, when the properties of the polymer particles were measured, MFR2.9g/10min, II 99
．． 5%, and the bulk density was 0.48 g/an3. Also, the average particle size is extremely large, 3810μ, cyo, 30. RA8
A result of 1 particle containing type weight % was obtained.

Example 3 When preparing the solid catalyst component (A), the following steps were carried out except that diisobutyldimethoxysilane was used as the component (11) in place of the tetrakis(2-ethylhexoxy)silane used in (a) of Example 1. A solid catalyst component (A) was obtained in the same manner as in Example 1 (a).

Using the obtained solid catalyst component (A), (b) of Example 1
Polymerization of propylene was carried out under the same conditions.

The result was an activity of 56,250 g/g. In addition, when the properties of the polymer particles were measured, MFR3.7g/
10 minutes, II 99.2%, bulk density 0.40g/an
3. Results were obtained with an average particle size of 342μ, aO, 014, FMIJ, and a fine particle content of 0.2% by weight.

Example 4 When preparing the solid catalyst component (A), Example 1 (I) was used except that ethylaluminum dichloride was used as the component (iv) in place of the isobutylaluminum dichloride used in Example 1 (a). ) A solid catalyst component (8) was obtained in the same manner as in (8).

Using the obtained solid catalyst component (A), (b) of Example 1
Polymerization of propylene was carried out under the same conditions.

The result was an activity of 51,200 g/g. In addition, when various properties of the polymer particles were measured, MFR3, 1g/10
min, II 98.7%, bulk density 0, 40 g/cm
3. Average particle size 400μ, σ0.13. Fine particle content Of
! Amount % results were obtained.

Comparative Example 1 The component (I was replaced with isobutylaluminum dichloride used in Example 1 (a), and titanium tetrachloride 62.7
Example 1 except that g<0.33 mol)
A solid catalyst component was obtained in the same manner as in (a).

Using the obtained solid catalyst component, propylene was polymerized under the same conditions as in Example 1 (b). The result is activity 46
It was 100g/g. In addition, when various properties of the polymer particles were measured, MFR 4° 4g/10 min, II 97
．． 7%, bulk density 0.30g/am3. Average particle size 210μ
, σ 0.36. A fine particle content of 3.9% by weight was obtained.

Comparative Example 2 When preparing the solid catalyst component (A), the reaction was carried out in the same manner as in Example 1 without adding tetrakis(2-ethylhexoxy)silane and triisopropoxyaluminum, resulting in an agar-like heterogeneous liquid. . Using this heterogeneous liquid,
Isobutylaluminum dichloride was added and the temperature was raised in the same manner as in Example 1, but no solid product was produced.

[Brief explanation of the drawing]

FIG. 1 shows another drawing (flow chart) of the catalyst used in the present invention. Procedural amendment dated 18th June 2008 6 Contents of amendment (1) The drawings will be corrected as shown in the attached sheet. (2) The description in the specification is corrected as follows. 1986 Patent Application No. 326199 2. Name of the invention Process for producing improved stereoregular polyolefin 3. Relationship with the case of the person making the amendment Patent applicant address: 4560 Tomita, Shinnanyo City, Yamaro Prefecture, 746 (contact information) ) Tosoh Corporation Patent Office 1-7-7 Akasaka, Minato-ku, Tokyo 107 Telephone number (505) 4471 4. Date of amendment order. 5. Subject of amendment.

Claims (1)

[Claims] (1) In producing stereoregular polyolefin in the presence of a catalyst consisting of a transition metal compound and an organometallic compound, component (A) is (i) a group consisting of metallic magnesium, an organic hydroxide compound, and an oxygen-containing organic compound of magnesium; (ii) an oxygen-containing organic compound of aluminum; and (iii) at least one member selected from
) an oxygen-containing organic compound of silicon and (iv) a solid product obtained by reacting at least one type of aluminum halide with a solid product further containing (v) an electron-donating compound and (vi) a titanium halide compound. The solid catalyst component obtained by reacting with component (B) is the periodic table IA, IIA, IIIB, III.
A method for producing a stereoregular polyolefin using a catalyst system comprising at least one selected from the group consisting of organometallic compounds of group B and IVB metals and an electron donating compound as component (C).