JPS62143905A - Production of olefin polymer - Google Patents

Abstract

PURPOSE:To obtain a polymer of narrow particle size distribution with little fine powder, high stereoregularity and little catalyst residue, by polymerization of an olefin in the presence of a catalyst made up of specific solid catalyst component, organoaluminum compound and electron donor. CONSTITUTION:The objective polymer can be obtained by polymerization of an olefin in the presence of a catalyst made up of (A) a catalyst carrier prepared by (i) bringing at least one kind of oxide of element selected from the group II-IV elements in the periodic table (e.g. MgO, B2O3) and/or composite inorganic oxide containing at least one kind of the above oxide (e.g. SiO2-Al2O3) into contact with (ii) a silicon halide and if needed, an alcohol followed by bringing a solid product formed by separation into contact with a magnesium alkoxide-contg. liquid followed by adding a separating agent (e.g. methanol), (B) an electron-donating compound (e.g. n-butyl benzoate) and (C) an organoaluminum compound (e.g. trimethylaluminum).

Description

[Detailed Description of the Invention] [Industrial Application Field] The present invention relates to a method for producing an olefin polymer, and more specifically, the present invention relates to a method for producing an olefin polymer, which has a narrow particle size distribution, almost no fine powder, high stereoregularity, and The present invention relates to a method for producing an olefin polymer with less residue.

[Conventional techniques and their problems j Conventionally, as a method for polymerizing olefins, an electron-donating compound and a halogenated titanium compound are reacted on a carrier in which magnesium alkoxide is deposited on an oxide such as silica! A method using a large amount of solid catalyst components is known (JP-A-58-162607). However, this method has the disadvantage that the resulting polymer has insufficient particle size characteristics due to insufficient deposition of the magnesium dialkoxide.

In addition, after reacting silica etc. with an organosilicon compound, a halogenated alkylmagnesium compound (RMgX)'J
A solid catalyst component has also been proposed in which a magnesium compound and an alcohol are sequentially reacted to form a carrier, and this is combined with a titanium halide (Japanese Patent Publication No. 60-8982).
However, in this method, the hydroxyl groups on the silica surface react with the titanium halide, and the effective amount of titanium decreases, so the catalytic activity per titanium is low and it cannot be put to practical use.

This invention uses a highly active catalyst, has high stereoregularity,
It is an object of the present invention to provide a method for producing an olefin polymer having a narrow particle size distribution and an extremely small amount of fine powder.

[Purpose of the invention] This invention was made based on the above-mentioned 23 circumstances.

That is, an object of the present invention is to provide a method for producing an olefin polymer with high stereoregularity, narrow particle size distribution, and extremely little fine powder using a highly active catalyst.

[Means for Achieving the Object] As a result of intensive research by this inventor to achieve the above object, a composite inorganic material containing an oxide of an element belonging to Groups II to IV of the periodic table and/or a liquefied product thereof. It was discovered that when the oxide is treated with a silicon halide and, if necessary, an alcohol in this order, the hydroxyl groups in the oxide become inactive, and the catalytic activity of the supported titanium increases. The inventors have arrived at this invention by discovering that the above object can be achieved by using a polymerization catalyst.

The outline of the present invention for solving the above problems includes an oxide of at least one element selected from the elements belonging to Groups II to IV of the periodic table and/or at least one of these oxides. Obtained by contacting a composite inorganic oxide with a silicon halide and optionally an alcohol, and then separating for one step, contacting a magnesium alkoxide-containing liquid with a solid, and then adding a precipitating agent. A catalyst consisting of a solid catalyst component (A) obtained by contacting a catalyst carrier (a), an electron donating compound (b), and a halogenated titanium compound (C), an organoaluminum compound (B), and an electron donor (C) This is a method for producing an olefin polymer, characterized by polymerizing an olefin in the presence of.

The catalyst used in the process of this invention is supported by a specific catalyst support (a
) is a highly active hair tentacle made of a specific component including a specific solid catalyst component (A), and can be obtained as follows.

The catalyst carrier (a) can be obtained as follows.

First, an oxide of at least one element selected from the elements belonging to Groups II to IV of the periodic table and/or a composite inorganic oxide containing at least one of these oxides (hereinafter referred to as inorganic oxide) ) and the silicon halide are brought into contact.

The reason why the inorganic oxide component and the silicon halide are brought into contact is to remove hydroxyl groups in the oxide or composite inorganic oxide.

Here, examples of oxides of elements belonging to groups II to IV of the periodic table include Mg O, C'a 01B203
．． Examples of the composite inorganic oxide include Si 02 , Sn 02 , A1203, etc., and examples include Si 02 , Sn 02 , A1203, and the like.
02-A AC 203, S + 02-Mg 01Si
O2-Ti02, Si02-V2O3, Si
02-Cr207, Si02-Ti02-
Examples include MgO. These various oxides and composite inorganic oxides may be used individually, two or more of the above oxides may be used together, or two or more of the above complex inorganic oxides may be used simultaneously. They may be used in combination, or the oxide and the composite inorganic oxide may be used in combination at the same time.

Among the various oxides and composite inorganic oxides, 5i02 is particularly preferred.

In addition, these various oxidizing agents and composite Ja-free oxides serve as carriers for the catalyst, so if we define a preferable form from the viewpoint of properties as a carrier, the specific surface area (
BET method) is 10 to 800 rn'/g.

Average pore size is 10λ or more, average particle size is 0.1-1000
Those within the gm range are preferred.

The silicon halide represented by the following general formulas (1) and (2) can be used.

S inH* X l (1) S 1oR
p
and P+q=2o+2, R represents alkylno, (or represents an alkenyl group, and X represents any one of a fluorine atom, a chlorine atom, a sulfur atom, and an iodine atom) as a specific example of the silicon halide For example, Si
C view a, 5i2C standing 6, Si3C view 8.5ia
Cu+o, Si HCl3, CH3Si C13, (C
H3) 2 Si C look? , (CH3)3
Si C1, (CH3h Si C1,C;+
H5Si 0 sentence 3, CC2H5)2 Si
C 2, (C7H5)3 Si C, etc., 10 elements, fluorides in which the 11 elements in the chloride are replaced with fluorine atoms, oxalium atoms, iodine atoms,
Various oxalides and iodides can be mentioned. Among these, the above-mentioned chlorinated compounds are preferable, especially SiC,
CH3Si C intersection 3, (CH3)Z Si C sentence? ,(
CH:+)3sic is preferred.

The amount of silicon halide that comes into contact with the inorganic oxide component may be in excess of the inorganic oxide component, and is usually t-too times the mole of the Group II to IV elements of the periodic table. Preferably, it is 1 to 50 times the mole amount.

The temperature at which the inorganic oxide component and the silicon halide are brought into contact is preferably in the range of 0 to 200°C.

If the temperature during contact is as high as 300° C., thermal decomposition of the silicon halide may occur, which is not preferable.

1) The inorganic oxide component No. 0 and the /\silicon halogenide may be brought into contact as they are, or, for example, hexane,
The contact may be carried out in a hydrocarbon solvent such as heptane, benzene, toluene, xylene, etc.

The contact time between the inorganic oxide component and the I\silicon halogenide is usually 5 minutes to 24 hours. Further, the contact is preferably carried out under an atmosphere of an inert gas such as nitrogen.

After the contact, the inorganic oxide component is preferably washed by decantation. Wash? ? This is because the + treatment allows the subsequent contact with alcohol to proceed conveniently if necessary. The above-mentioned hydrocarbon solvent can be used as the cleaning solvent.

Next, the inorganic oxide component and alcohol after contact with the silicon halide are brought into contact with each other, if necessary.

By bringing the inorganic oxide component into contact with the alcohol after contact with the silicon halide, deactivation of the supported titanium compound can be prevented, and reduction of titanium effective for polymerization can be prevented.

As the alcohols, -hydric alcohols and polyhydric alcohols can be used.

+iif-hydric alcohols include, for example, aliphatic saturated alcohols such as methanol, ethanol, propatool, isopronormale, butanol, and pentanol; aliphatic unsaturated alcohols such as allyl alcohol and crotyl alcohol; cyclopentamel; Alicyclic alcohols such as cyclohexanol; M aromatic alcohols such as benzyl alcohol and cinnamyl alcohol; heterocyclic alcohols such as furfuryl alcohol; examples of the polyhydric alcohols include ethylene glycol, diethylene glycol, Examples include triethylene glycol, propylene glycol, glycerin, and the like. Among these, the aliphatic alcohols mentioned above are preferred, and methanol, ethanol, and propatool are particularly preferred.

Further, -1 of the alcohol brought into contact with the inorganic oxide component after contacting with the silicon halide is usually 1 to 100 times as much as 1 to the silicon halide reacted by contacting with the inorganic oxide component. A mole is fine.

The contact between the inorganic oxide component and the alcohol is preferably carried out under an inert atmosphere such as nitrogen. Further, the temperature at which the inorganic oxide component and the alcohol are brought into contact may range from room temperature to reflux temperature, but is usually reflux temperature. The contact time is not particularly limited, but it is preferably 0.5 to 24 hours under reflux.

After completion of the contact reaction, it is preferable to thoroughly wash the inorganic oxide component with the alcohol or the washing solvent.

In the method of this invention, it is important to separate the solid matter after the contact between the alcohol and the inorganic oxide component is completed.

If alcohol remains in the solid, the magnesium alkoxide added in the next step will react with the remaining alcohol, which will adversely affect catalyst performance. Therefore, it is preferable to dry the separated solid matter sufficiently.

Next, in the method of the present invention, the solid material is brought into contact with a magnesium alkoxide-containing liquid.

As the magnesium alkoxide-containing liquid, a mixture of magnesium alkoxide and at least one selected from the group consisting of hydrocarbons, electron donating substances, and alkoxy titanium can be suitably used. Among the hydrocarbons, electron donating substances and alkoxy titanium,
Alkoxytitanium is preferred.

Examples of the hydrocarbon include pentane, hexane,
Aliphatic hydrocarbons such as heptane, octane, decane, dodecane, tetradecane, kerosene, ligroin, petroleum ether; alicyclic hydrocarbons such as cyclopentane, methylcyclopenkune, cyclohexane, methylcyclohexane, cyclooctane, cyclohexene; benzene, Examples include aromatic hydrocarbons such as toluene, xylene, ethylbenzene, cumene, and cymene; halogenated hydrocarbons such as dichloropropane, trichloroethylene, carbon tetrachloride, and chlorobenzene; and the like.

Among these, hexane, heptane, and octane are preferred.

Further, as the electron donating substance, aliphatic alcohol,
Examples include aromatic alcohols, ethers, aldehydes, ketones, carboxyl alcohols, carboxyl anhydrides, acid halides, amines, amides, nitriles, incyanates, etc. Among these, alcohols are preferred, and methanol, ethanol, etc. are particularly preferred.

Examples of the alkoxy titanium include tetramethoxy titanium, tetraethoxy titanium, tetra n-butoxy titanium,
Examples include tetraisopropoxytitanium, and tetra-n-butoxytitanium is particularly preferred.

The magnesium alkoxide has, for example, the general formula: Mg (OR' ) r (OR' ) 2-r [wherein R1 and R2 are an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group, an aryl group, or It is an aralkyl group, R1 and R2 may be different or the same, and r is a positive number of O to 2. ] It can be expressed as As such magnesium alkoxide, for example, Mg・(−〇CH:+)2
．． Mg(-0C2H5)2. Mg(-OC3H+)2
, Mg (-0CA R9)2 , Mg(-0C6H
I3)2, Mg(-0CaHu)2.

Mg(-0CH3)(-0C2Hs)alkoxymagnesium.

The above-mentioned magnesium alkoxide-containing liquid made by WB cannot be classified as one type because it differs depending on the type of magnesium alkoxide, hydrocarbon, electron donating substance, and alkoxytitanium.
Examples include a method of mixing the magnesium alkoxide with any one or a mixture of two or more of the hydrocarbon, electron donor, and alkoxytitanium, or a method of mixing while heating.

As a preparation method, for example, (1) when alcohol and hydrocarbon are used as electron donating substances, about 1 mol or more of alcohol is used per 911 mol of magnesium alkoxide, and the alcohol, hydrocarbon, and magnesium alkoxide are mixed. (2) When using tetraalkoxy titanium, magnesium alfuki 91
0.5 mole or more of tetraalkoxytitanium per mole.

Preferably 0.5 to 10 mol, particularly preferably 0.5 to 10 mol
There is a method of mixing tetraalkoxytitanium magnesium alkoxide in an amount of 5 moles.

The magnesium alkoxide-containing liquid thus obtained is brought into contact with the solid material at a temperature of 0 to 100°C, preferably 10 to 100°C.
This can be carried out by mixing the magnesium alkoxide-containing liquid and the solid substance at a temperature of 30°C. At the time of this mixing, it is preferable to mix the magnesium alkoxide-containing liquid with respect to the solid material described in iiiI in a proportion of 0.01 to 11 parts based on magnesium atoms.

Further, the contact time between the magnesium alkoxide-containing liquid and the solid substance is usually 1 to 5 minutes to 24 hours.

The catalyst carrier (a) for olefin polymerization can be obtained by filtering the mixture of the magnesium alkoxide-containing liquid and the solid substance, but when a precipitation agent is added to the mixture, the magnesium compound is sufficiently removed. Since the supported catalyst carrier (a) for olefin polymerization is deposited, it is preferable to separate this by decantation.

As the precipitating agent, lower alcohols such as methanol, ethanol, propatool, butanol, and pentanol, halogenating agents described below, and the like can be used.

When a magnesium alkoxide-containing liquid is prepared using tetraalkoxytitanium, the lower alcohol used is preferably an alcohol having an alkyl group having a smaller number of carbon atoms than the alkyl group of tetraalkoxytitanium.

Examples of the halogenating agent described in No. 1111 include silicon tetrachloride, trichlorosilane, monomethyldichlorosilane, dimethylchlorosilane, ethyldichlorosilane, n-propyldichlorosilane, vinyldichlorosilane, n-butyldichlorosilane, phenyl Halosilanes such as dichlorosilane, benzyldichlorosilane, allyldichlorosilane, monomethylmonochlorosilane, monoethylmonochlorosilane, trimethylmonochlorosilane, monomethyltrichlorosilane; diprolaluminum chloride, ethylaluminum dichloride, ethylaluminum sesquichloride, dimethylaluminum Organoaluminum halides such as chloride, methylaluminum dichloride, methylaluminum sesquichloride, propylaluminum dichloride, dipropylaluminum chloride; 1
Thionyl 0ide; halogenated hydrocarbons or halogenated carbons such as chloroform, hexachloroethane, carbon tetrachloride, carbon tetrabromide, carbon tetraiodide, t-butyl chloride:
A text C13, AuBr3, Sn C1a.

BCJI:1, Sb CfL3, Zn C1z
metal halides such as; hydrogen halides such as hydrogen chloride;
Examples include halogens such as chlorine. Among these, halosilane is preferred, and tetrachlorosilane is particularly preferred.

The amount of the precipitating agent added is sufficient to precipitate magnesium onto the catalyst carrier for olefin polymerization.

Note that it is not preferable to bring the solid substance into contact with the magnesium alkoxide-containing liquid and the precipitating agent at the same time, because the polymerization activity of the supported catalyst metal will decrease.

The solid material obtained as described above is different from the above-mentioned brewer used as a carrier when it contains only the complex inorganic oxide or when it is a mixture of the above-mentioned oxide and the complex inorganic oxide. 0.1 to 20 weight ψ%, especially 0.5 to 10% as magnesium atoms based on the total amount of oxides! Tr
Those containing Iit% are preferred.

The catalyst for olefin polymerization in this method is a solid catalyst component (A) in which a titanium compound is supported on the catalyst carrier (a).
), organoaluminum compound (B), and electron donor (C)
It becomes a catalyst for olefin polymerization.

Next, the preparation of the solid catalyst component (A), the preparation of the catalyst for olefin Togane, and the polymerization of olefin using this catalyst will be explained.

The solid catalyst component (A) is preferably prepared by contacting the catalyst carrier (a) obtained by the method of the present invention, the electron donating compound (b), and the halogenated titanium compound (G). carrier (a) and the electron donating compound (
b) and the halogenated titanium compound (C
) can be obtained by contacting with.

Examples of the electron-donating compound (1+) include organic acid esters, aliphatic carboxylic acid esters, aliphatic dicarboxylic acid diesters, aromatic monocarboxylic acid esters, and aromatic dicarboxylic acid diesters.

Examples include aromatic dicarboxylic acid monoesters.

Among these, aromatic monocarboxylic acid esters and aromatic dicarboxylic acid diesters are preferred.

Examples of the aromatic monocarboxylic acid esters include lower alkyl esters of benzoic acid such as methyl, ethyl, propyl, and n-butyl.
Butyl is preferred.

Examples of aromatic dicarboxylic acid diesters include lower alkyl diesters of phthalic acid, terephthalic acid, and isophthalic acid, and more specifically,
Dimethyl phthalate, diethyl phthalate, dipropyl phthalate, diisobutyl phthalate, methyl ethyl phthalate, methyl propyl phthalate, methyl isobutyl phthalate, ethyl propyl phthalate, ethyl isobutyl phthalate, propyl isobutyl phthalate, dimethyl terephthalate, diethyl terephthalate, dipropyl terephthalate, diisobutyl terephthalate,
Methyl ethyl terephthalate, methylpropyl terephthalate, methyl isobutyl terephthalate, ethylpropyl terephthalate, ethyl isobutyl terephthalate, propyl isobutyl terephthalate, dimethyl isophthalate, diethyl isophthalate, dipropylisophthalate, diisobutyl isophthalate, methylethyl isophthalate, methylpropylisophthalate , methyl isobutyl isophthalate, ethyl propyl isophthalate, ethyl imbutyl isophthalate, propyl isobutyl isophthalate, and the like. Among these, preferred are dipropylphthalate, diisobutyl phthalate, and the like.

As the halogenated titanium compound CC), those represented by the following general formula can be used.

T i (OR' )4-5XS (3) [
However, Hl is an alkyl group, a cycloalkyl group, an aryl group, or an aralkyl group having carbon a1 to a10, (wherein S is a real number of 0 or more and less than 4, and X represents a halogen atom.) The halogenated titanium compound ( If C) is specifically shown,
Ti C1a, Ti Br4. Tetrahalogenated titanium such as Ti Is; Ti (OCH3)CJL3
, Ti(OC2R5) C13, (n-CsHg
0) TiCfB, Ti(OC2Hs)Br
Trihalogenated alkoxytitanium such as 3; Ti(QC
H:l)2 C12, Ti (OC2R5)2
C standing 2.

(n-C4R50)2Ti C12,Ti (OC3
Hr ) 2 Dihalogenated alkoxy titanium such as C structure 7; Ti (OCR3) 3 C stand, Ti (O
C2R5)3C1, (n-Ca Hq 0)3Ti C
1, monohalogenated trialkoquititanium such as Ti(QCH3)3Br, etc. can be exemplified. These may be used alone or as a mixture. Among these, it is preferable to use a high halogen-containing substance, and it is particularly preferable to use titanium tetrachloride.

The reaction product of the catalyst carrier (a) and the electron donating compound (b) and the halogenated titanium compound (C) are usually 0
~200℃, preferably 10~150℃, 2 minutes~2
The contact may be carried out for 4 hours, preferably for 1 to 5 hours.

The solid catalyst component (A) thus prepared preferably contains 0.1 to 20% titanium atoms, particularly 0.5 to 1% by amount of titanium. is desirable.

Further, when an olefin is brought into contact with the catalyst obtained from the solid catalyst component (A), the organoaluminum compound (B), and the 11 electron bodies (C) obtained as described above, a polyolefin can be obtained.

The organoaluminum compound (B) is not particularly limited and has the following general formula.

A Cross R2LX3-t AM2R2X3 [wherein R7 is an alkyl group having 1 to 10 carbon atoms,
cycloalkyl group or aryl group, t is 1 to 3
is a real number between 1 and 2, and X represents a halogen atom such as chlorine or bromine. Specifically, trialkylaluminum such as trimethylaluminum, trialkylaluminum, triisopropylaluminum, triisobutylaluminum, trioctylaluminum, etc., and diethylaluminum monochloride, diisopropylaluminum monochloride, diimbutylaluminum monochloride, dioctylaluminum monochloride, etc. Dialkyl aluminum monohalide and ethyl aluminum sesquichloride are preferred, and mixtures thereof are also preferred.

The electron donor (G) is an organic compound containing oxygen, nitrogen, phosphorus, or sulfur. Specifically, amines, amides, ketones, nitriles, phosphines, phosphoramides, esters, ethers, thioethers, thionisnil, acid anhydrides, halides, acid amides, and aldehydes. , organic acids 5i-0-C
Examples include organic silane compounds having bonds.

More specifically, organic acids such as aromatic carboxylic acids such as benzoic acid and p-oxybenzoic acid; anhydrous substances such as succinic anhydride, benzoic anhydride, and p-toluic anhydride; acetone, methyl ethyl ketone; , methyl isobutyl ketone,
Ketones with r-wing element a 3 to 5 such as acetophenone, benzophenone, and henzoquinone; aldehydes with 2 to 15 carbon atoms such as acetaldehyde, propionaldehyde, octylaldehyde, benzaldehyde, tolualdehyde, nathaldehyde; methyl formate, methyl acetate ,
Ethyl acetate, vinyl acetate, propyl acetate, octyl acetate, cyclohexyl acetate, ethyl propionate, ethyl butyrate, ethyl valerate, methyl chloroacetate, ethyl dichloroacetate, methyl methacrylate, ethyl crotonate, ethyl piperate, dimethyl maleate, Ethyl cyclohexanecarboxylate, methyl benzoate, ethyl benzoate, propyl benzoate, butyl benzoate, octyl benzoate,
Cyclohexyl benzoate, phenyl benzoate, ammonium, hensyl qzoate, methyl toluate, ethyl toluate, amyl toluate, ethyl ethyl benzoate, methyl anise, ethyl anis, ethyl ethoxybenzoate, P-butoxybenzoic acid Ethyl, ethyl 0-chlorobenzoate, ethyl naphthoate, γ-butyrolactone, δ-valerolactone, coumarin, phthalide, esters with 2 to 18 carbon atoms such as ethylene chloride; acetyl chloride, benzyl chloride, toluic acid chloride , C2-C15 halides such as anisyl chloride: C2-C20 ethers such as methyl ether, ethyl ether, isopropyl ether, n-butyl ether, amyl ether, tetrahydrofuran, anisole, diphenyl ether, ethylene glycol butyl ether, etc. Acid amides such as acetic acid amide, benzoic acid amide, toluic acid amide; Tributylamine, N,N'-dimethylpiperazine,
tribenzylamine, aniline, pyridine, picoline,
Examples include amines such as tetramethylethylenediamine, nitriles such as acetonitrile, benzonitrile, and tolnitrile: tetramethylurea, nitrobenzene, lithium butyrate, and the like. In addition, the above 5i
Examples of organosilicon compounds having a -0-C bond include alkoxysilanes and aryloxysilanes. Examples of this include the general formula %) [wherein R4 represents an alkyl group, a cycloalkyl group, an aryl group, an alkenyl group, a haloalkyl group, an aminoalkyl group, or a halogen, and R5 represents an alkyl group, a cycloalkyl group, group, aryl group, alkenyl group, (or alkoxyalkyl group. Also, V is O≦V≦3. However, even if 7 R' and (4-v) OR5 are the same, Examples include silicic acid esters represented by ], which may be different from each other.Other examples include siloxanes having an OR5 group or silyl esters of carboxylic acids.Furthermore, other examples include , a silicon compound that does not have a 5t-0-C bond and an O-
Examples include those in which a compound having a C bond is reacted in advance or during the polymerization of an α-olefin to convert it into an organosilicon compound having a 5i-0-C bond.
A combination of iC1a and alcohol is considered.

Specific examples of the organosilicon compounds having the 5i-0-C bond include trimethylmethoxysilane, trimethylethoxysilane, dimethyldimethoxysilane, dimethyljethoxysilane, diphenyldimethoxysilane,
Methylphenyldimethoxysilane, diphenyljethoxysilane, ethyltrimethoxysilane, vinyltrimethoxysilane, methyltrimethoxysilane, phenyltrimethoxysilane, r-chloropropyltrimethoxysilane, methyltriethoxysilane, ethyltriethoxysilane, vinyltrimethoxysilane Ethoxysilane, butyltriethoxysilane, phenyltriethoxysilane, r-aminopropyltriethoxysilane, chlortriethoxysilane,
Ethyltriisopropoxysilane, vinyltributoxysilane.

Ethyl silicate, butyl silicate, trimethylphenoxysilane, methyltriaryloxysilane, vinyl tris (β
-methoxyethoxy)silane, vinyltriacetoxysilane, dimethyltetraethoxydisiloxane, etc.

Among the various electron donors (C), preferred are esters, ethers, ketones, non-woody materials, 5
These include organic silane compounds having an i-0-C bond.

In particular, alkyl esters of aromatic carboxylic acids, such as benzoic acid, P-methoxybenzoic acid, P-ethoxybenzoic acid, toluic acid, etc., have a carbon number of l to
Preferred are alkyl esters and trialkoxysilanes of No. 4, and also preferred are aromatic ketones such as benzoquinone, aromatic carboxylic acid anhydrides such as benzoic anhydride, and ethers such as ethylene glycol butyl ether.

Moreover, this electron donor (G) may be the same as or different from the electron donating compound (b) used for preparing the solid catalyst component (A).

As for the composition of each component of the catalyst for olefin polymerization, the solid catalyst component (A) is usually in an amount such that the titanium concentration is 0.001''1 mm;
Regarding the organic aluminum compound (El), the aluminum/titanium atomic ratio is 1 to 1000, preferably 5 to 50.
41: which is 0, and for the electron donor CC),
? [The child donor (C) (mol)/titanium (atomic) ratio is 0
．． It is 01-100.

The method of this invention produces olefin beads by polymerizing α-olefin in the presence of the catalyst.

The α-olefin can be represented by the general formula %c, where R6 represents hydrogen, an alkyl group having 1 to 20 carbon atoms, or a cycloalkyl group, such as ethylene, propylene, butene-1 Examples include linear monoolefins such as , pentene-1, and octene-1, branched monoolefins such as 4-methyl-pentene-1, and vinylcyclohexene.

The α-olefin to be subjected to polymerization is not limited to one type alone, and multiple types of α-olefins may be copolymerized to produce a random copolymer or a block copolymer.

During copolymerization, unsaturated compounds such as conjugated dienes and non-conjugated dienes can also be copolymerized.

For the polymerization reaction in the method of the present invention, methods and conditions conventionally used in the field of olefin polymerization technology can be employed.

As the polymerization method, a slurry polymerization method, a bulk polymerization method, a gas phase polymerization method, etc. can be adopted.

The polymerization temperature at that time is 20 to 100°C, preferably 40 to 100°C.
The temperature range is 90℃, and the polymerization pressure is usually 1 to 100Kg.
/cm'G, preferably 5-50Kg/c
m'G range.

The polymerization reaction can generally be carried out by a solution polymerization method using aliphatic, alicyclic, aromatic hydrocarbons or a mixture thereof as a solvent, such as propane, butane, and pentane.

Hexane, heptane, cyclohexane, benzene, etc.
and mixtures thereof can be used. Also applicable are gas phase polymerization and bulk polymerization using the liquid monomer itself as a solvent.

The molecular weight of the olefin polymer produced in the method of this invention varies depending on the reaction mode, catalyst system, and polymerization conditions, but can be controlled by adding hydrogen, alkyl halides, dialkylzinc, etc., if necessary.

[Effects of the Invention] According to this invention, (+) Since a catalyst with high catalytic activity and long activity duration is used, the polymerization reaction can be carried out stably even when performing multi-stage polymerization. (2) Almost no catalyst residue remains in the produced olefin polymer, and the olefin polymer can be molded and processed well.

(3) It is possible to produce an odorless olefin polymer with high stereoregularity, and (4) the produced olefin polymer contains 100g of
Since there is almost no polymer fine powder of less than m, the olefin polymer can be transported in powder form without clogging pipes.

It is possible to provide a useful method for producing an olefin polymer having a number of advantages such as.

[Examples] Next, Examples and Comparative Examples of the present invention will be shown to further specifically illustrate the present invention.

(Example 1) ■ Preparation of catalyst carrier Calcined silicon oxide (manufactured by Fuji Davison, grade 952) 3 was placed in a 0-5 glass container purged with argon.
Add 5g and 175mJL of trimethylchlorosilay.
The reaction was allowed to proceed for 12 hours while stirring under a flowing stream. Then n
- Using 100 mjL of heptane, washing with 1 liter of Denkatake was repeated three times and then dried.

Jetoxymagnesium (15
0 mm), tetra-n-butoxytitanium (90 mm
150 mL of a n-hebutane solution containing (or) was added, and the mixture was brought into contact at room temperature for 1 hour. After that, Improper Tools 50+n
After adding JJ dropwise and stirring at 80°C for 1 hour, decantation was repeated 5 times with 100ml of n-hebutane.
A white catalyst carrier was obtained by drying under reduced pressure at 0°C for 1 hour. This catalyst carrier contained 3.1iiJ% of magnesium atoms.

Catalyst carrier thus obtained 8. Pour Og into a 0.5× glass container, and add 50 mfL of n-heptane and 3.0 mf of n-butyl benzoate. Eim mol and titanium tetrachloride 4
0g was added. The mixture was stirred under reflux for 1 hour. After that, the supernatant liquid was removed by decantation,
A solid catalyst component was obtained by sufficiently washing the obtained solid portion with hot n-hebutane. This catalyst contained 2.2% by weight of Ti.

■Polymerization of propylene 0.008 m of the solid catalyst component was suspended in 50 m of hexane in an argon-substituted autoclave.
g M (in terms of titanium atoms), 1.5 mmon of triethylaluminum, and 0.45 mmon of methyl P-toluate were added. After reducing the pressure in the autoclave to remove argon, 310 g of propylene and 0.7 Nl of hydrogen were charged.

After 5 minutes, the temperature was raised to 70°C, and polymerization was carried out at 70°C for 2 hours. After cooling the autoclave, the propylene was purged, and the contents were taken out and dried under reduced pressure to obtain 101 g of polypropylene powder. The bulk density of this powder is 0.38 g/crn',
The fine powder of 100 gm or less was 0.4% by weight and had excellent fluidity. Further, the ratio (1,1,) of the residual polymer after boiling n-hebutane extraction in this powder was 86.2%. Further, the amount of chlorine in this polymer analyzed by fluorescent X-ray analysis was 18 ppm.

(Comparative Example 1) In Example 1 (2), the reaction with trimethylglolsilane was not performed, and the solid catalyst component (2) was used at 0.012 mg.
The same procedure was performed except that atoms were used. The obtained polypropylene powder weighed 17.3 g-t' and contained 1.1. The a was 5.8%. Further, the amount of chlorine in this polymer analyzed by fluorescent X-ray analysis was 195 ppm.

(Comparative Example 2) The same procedure as in Example 1 (2) was repeated except that methyltrichlorosilane was used instead of trimethylglolsilane and butylethylmagnesium was used instead of jetoxymagnesium. The obtained polypropylene powder was 45 g, and 1.1. was 8B, 3%. Further, the amount of chlorine in this polymer analyzed by fluorescent X-ray analysis was 33 ppm.

(Example 2) The same procedure as in Example 1 (2) was carried out except that ethanol was used instead of the impropatol (precipitating agent). The obtained polypropylene powder weighs 105 g, its bulk density is 0.38 g/ctn', the fine powder below 1100 IL is 0.3 ffr1%, 1.1. was 87.0%.

Further, the amount of chlorine in this polymer analyzed by fluorescent X-ray analysis was 18 ppm.

(Example 3) The same procedure as in Example 1■ was carried out using tetrachlorosilane instead of Improper Tool (precipitated).The obtained polypropylene powder was j!Og, and its high density was 0.41g. /crn', IQ (IILm or less fine powder was 0.2% by weight, 1.1. was 97.3%.

In addition, 1' in this polymer analyzed by fluorescence x6 analysis
! ! The raw material r^ was 14 ppm.

(Comparative Example 3) In Example 1■, Impropatool (precipitating agent) n-
The same procedure was carried out except that hebutane was distilled off under reduced pressure. The obtained polypropylene powder weighs 75 g, its high density is 0.29 g/crn', the fine powder of 1100 JL or less is 25% by weight, ■, 1. was 86.9%. Further, the amount of chlorine in this polymer analyzed by fluorescent X-ray analysis was 25 ppm.

(Example 4) 2.0 mmoKL of diisobutyl phthalate instead of benzoic FMfn-butyl in Example 1 (2), and 0.15 m of triethoxysilane in place of methyl P-)ruylate in Example 1 (2).
The same procedure as in Example 1 was carried out using mon. The obtained PP powder is 212g, and its high density is 0.42g.
/cm', fine powder of 1004 m or less has 0.3 double strands%, 1.
L was 87.5%. Further, the amount of chlorine in this polymer analyzed by fluorescent X-ray analysis was 8 ppm.

Procedural amendment document December 1988, Japanese Patent Application No. 60-284099 2 Name of the invention Process for producing olefin polymer 3 Relationship to the case of the person making the amendment Patent applicant address 131 Shiratama-chome, Maruno, Chiyoda-ku, Tokyo Name: Idemitsu Petrochemical Co., Ltd. Representative: Takeshi Yamato 4 Agent address: 6, 3rd floor, Central Nishi-Shinjuku, 8-9-5 Nishi-Shinjuku, Shinjuku-ku, Tokyo Number of inventions to be increased by the amendment Contents of the O8 amendment (1) Page 3 Line 1O states “(Tokuko Showa 6G
-6962) L/Kazi," was changed to
2). However, it is corrected to ``.

(2) In page 17, line 7, "because is precipitated," is corrected to "because is obtained."

(3) “Less than 4” written in the 5th line from the bottom of page 22 is corrected to “4 or less.”

(4) Delete "the amount of the solid catalyst component (A) that satisfies the following" from lines 14 to 16 on page 30.

(5) As stated on page 33, lines 10 to 12, “It has high stereoregularity and can be produced.
(4)" is deleted.

(6) "(Instead of precipitation)" written in page 37, lines 13 to 14, "instead of (precipitating agent)"
Correct to.

(7) Correct "high density" written in page 37, line 16 to "bulk density".

(8) "
(Precipitating agent) n Habutan” is corrected to “N Habutan without using (depositing agent).”

(9) Change “high density” in line 4 of page 38 to “
Bulk density”.

(10) "High density" written in lines 13 to 14 of page 38 is corrected to "bulk density."

(11) 3rd trial - ``(
(precipitating agent) n-hebutane" is corrected to "(precipitating agent) is not used, n-hebutane".

−1 or more

Claims (3)

[Claims] (1) an oxide of at least one element selected from the elements belonging to Groups II to IV of the periodic table and/or a composite inorganic oxide containing at least one of these oxides;
Catalyst carrier (a) obtained by contacting a silicon halide and, if necessary, an alcohol, and then contacting a solid obtained by separation with a magnesium alkoxide-containing liquid, and then adding a precipitating agent; Electron-donating compounds (
b) and the solid catalyst component (A) obtained by contacting the halogenated titanium compound (c), the organoaluminum compound (
B) and in the presence of a catalyst consisting of an electron donor (C),
A method for producing an olefin polymer, which comprises polymerizing an olefin. (2) The olefin polymer according to claim 1, wherein the magnesium alkoxide-containing liquid is a mixture of magnesium alkoxide and at least one selected from the group consisting of hydrocarbons, electron donating substances, and alkoxy titanium. manufacturing method. (3) The method for producing an olefin polymer according to claim 1, wherein the magnesium alkoxide-containing liquid is a mixture of alkoxytitanium and magnesium alkoxide.