JPH0725808B2 - Method for producing olefin polymer - Google Patents

Description

Description: TECHNICAL FIELD The present invention relates to a method for producing an olefin polymer, and more specifically, it has a narrow particle size distribution, almost no fine powder, and high stereoregularity. The present invention relates to a method capable of producing an olefin polymer having less residue.

[Prior Art and its Problems] Conventionally, as a method for polymerizing olefins, a solid catalyst obtained by reacting an electron donating compound and a titanium halide compound on a carrier prepared by depositing magnesium alkoxide on an oxide such as silica. A method using components is known (Japanese Patent Laid-Open No. 162607/1983). However, this method has a drawback in that the particle size characteristic of the obtained polymer is insufficient because the deposition state of magnesium dialkoxide is insufficient.

Also, after reacting silica or the like with an organosilicon compound, a magnesium catalyst such as an alkylmagnesium halide compound (RMgX) and an alcohol are sequentially reacted to form a carrier, and a solid catalyst component in which this is combined with titanium halide is also proposed. (Japanese Patent Publication No. 60-6962). However, this method has a drawback in that the hydroxyl group on the silica surface reacts with titanium halide to reduce the amount of effective titanium, so that the catalytic activity per titanium is low and it cannot be put to practical use.

This invention uses a highly active catalyst and 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 a small amount of fine powder.

[Object of the Invention] The present invention has been made based on the above circumstances.

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

[Means for Achieving the Object] As a result of earnest research by the inventor in order to achieve the object, a solid oxide of an element belonging to Groups II to IV of the periodic table and / or this solid oxide When the solid complex inorganic oxide containing is treated with silicon halide and optionally alcohols in this order, the hydroxyl group in the oxide becomes inactive, and the catalytic activity of titanium to be supported is increased. The present invention has been accomplished by finding that the above object can be achieved by using this highly active polymerization catalyst.

An outline of the present invention for solving the above problems is to provide a solid oxide of at least one element selected from elements belonging to Groups II to IV of the periodic table and / or at least one of these solid oxides. After contacting a solid state composite inorganic oxide containing a silicon halide and optionally alcohols, a solid product obtained by separation is contacted with a magnesium alkoxide-containing liquid, and then a lower alcohol or halogen. Solid catalyst component (A) obtained by contacting the catalyst carrier (a) obtained by adding the agent, the electron-donating compound (b) and the titanium halide compound (c), the organoaluminum compound (B), and An olefin polymer is characterized by polymerizing an olefin in the presence of an electron donor (a catalyst from C).

The catalyst used in the method of the present invention is a highly active polymerization catalyst comprising a specific component including a specific solid catalyst component (A) using a specific catalyst carrier (a), and is obtained as follows. be able to.

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

First, solid oxides of at least one element selected from elements belonging to Groups II to IV of the periodic table and / or solid composite inorganic oxides containing at least one of these solid oxides (hereinafter, these Is sometimes abbreviated as a solid inorganic oxide component) and a silicon halide are brought into contact with each other.

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

Here, the solid oxide of an element belonging to periodic table II~IV group, for _{example, MgO, CaO, B 2 O} 3, SiO 2, SnO 2,
Al ₂ O ₃ and the like, and as a solid composite inorganic oxide containing at least one solid oxide of elements belonging to Groups II to IV of the periodic table, SiO ₂ -Al ₂ O ₃ , SiO ₂ −MgO, SiO _{2
-TiO 2, SiO 2 -V 2 O} 5, SiO-Cr 2 O 2, SiO 2 -TiO 2 -MgO and the like. These various solid oxides and solid composite inorganic oxides may be used alone,
Two or more kinds of the solid oxides may be used together, or two or more kinds of the solid composite inorganic oxides may be used together, or the solid oxides and the solid composite inorganics. You may use together with an oxide simultaneously.

Among the above various solid oxides and composite inorganic oxides, SiO ₂ is particularly preferable.

Further, since these various solid oxidizers and solid composite inorganic oxides serve as a carrier for the catalyst, if a preferred form is defined from the viewpoint of the characteristics as a carrier, then the specific surface area (BET method) is Those having an average pore diameter of 10 to 800 m ² / g, an average pore diameter of 10 Å or more, and an average particle diameter of 0.1 to 1000 μm are preferable.

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

SinHmXl (1) SioRpXq (2) (wherein each of l, m, n, o, p and q is a positive number, and m + l = 2n + 2 and p + q = 2o
+2 is satisfied, R represents an alkyl group or an alkenyl group, and X represents any one of a fluorine atom, a chlorine atom, an iodine atom and an iodine atom. ) Specific examples of the silicon halide include, for example, Si.
Cl ₄ , SiCl ₆ , Si ₃ Cl ₈ , Si ₄ Cl ₁₀ , SiHCl ₃ , CH ₃ SiCl ₃ , (C
H ₃ ) ₂ SiCl ₂ , (CH ₃ ) ₃ SiCl, (CH ₃ ) ₃ SiCl, C ₂ H ₅ SiC
l ₃ , (C ₂ H ₅ ) ₂ SiCl ₂ , chlorinated compounds such as (C ₂ H ₅ ) ₃ SiCl, the chlorine atom in the chlorinated compound being a fluorine atom, a hydrogen atom,
There are various fluorides, sulphides and iodides substituted with iodine atoms. Among these, the chlorinated compounds are preferable, and SiCl ₄ , CH ₃ SiCl ₃ , and (CH ₃ ) ₂ SiC are particularly preferable.
l ₂ , (CH ₃ ) ₃ SiCl is preferred.

The amount of silicon halide in contact with the solid inorganic oxide component may be excessive with respect to the solid inorganic oxide component, usually 1 to 4 of the periodic table group II-IV element
The molar ratio is 100 times, preferably 1 to 50 times.

The temperature at the time of contact between the solid inorganic oxide component and the silicon halide is preferably in the range of 0 to 200 ° C. If the temperature at the time of contact is as high as 300 ° C., thermal decomposition of the silicon halide may occur, which is not preferable.

The solid inorganic oxide component and the silicon halide may be contacted as they are, or may be contacted in a hydrocarbon solvent such as hexane, heptane, benzene, toluene and xylene.

The contact time between the solid inorganic oxide component and the silicon halide is usually 5 minutes to 24 hours. Also,
The contact is preferably performed in an atmosphere of an inert gas such as nitrogen.

After the contact, it is preferable to wash the solid inorganic oxide component by decantation. This is because the washing treatment can favorably promote subsequent contact with alcohols if necessary. The above-mentioned hydrocarbon solvent can be used as the washing solvent.

Next, if necessary, the solid inorganic oxide component after contact with silicon halide and the alcohol are contacted.

When the solid inorganic oxide component after contacting with a silicon halide and the alcohol are contacted with each other, the titanium compound to be supported is prevented from being deactivated, and the reduction of titanium effective for polymerization can be prevented.

As the alcohols, monohydric alcohols and polyhydric alcohols can be used.

Examples of the monohydric alcohol include methanol,
Aliphatic saturated alcohols such as ethanol, propanol, isopropanol, butanol, and pentanol; aliphatic unsaturated alcohols such as allyl alcohol and crotyl alcohol; alicyclic alcohols such as cyclopentanol and cyclohexanol; benzyl alcohol and cinnamyl alcohol And the like; heterocyclic alcohols such as furfuryl alcohol; and the like. Examples of the polyhydric alcohols include ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, glycerin and the like. Among these, the aliphatic alcohols are preferable, and methanol, ethanol and propanol are particularly preferable.

Further, the amount of the alcohols contacted with the solid inorganic oxide component after contacting with the silicon halide is usually 1 with respect to the silicon halide reacted with the solid inorganic oxide component. ~ 100 times mole is sufficient.

The contact between the solid inorganic oxide component and the alcohol,
It is preferably carried out under an inert atmosphere such as nitrogen. The temperature at the time of contacting the solid inorganic oxide component and the alcohol may be in the range of normal temperature to reflux temperature, but is usually the reflux temperature. The contact time is not particularly limited, but is preferably 0.5 to 24 hours under reflux.

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

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

If the acroles remain in the solid matter, the magnesium alkoxide added in the next step reacts with the residual alcohols, which adversely affects the catalytic performance. Therefore, it is preferable that the separated solid matter is sufficiently dried.

Next, in the method of the present invention, the solid matter is brought into contact with the 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 donors and alkoxy titanium can be preferably used. Among the above hydrocarbons, electron donors and alkoxy titanium,
Alkoxy titanium is preferred.

Examples of the hydrocarbon include pentane, hexane,
Aliphatic hydrocarbons such as heptane, octane, decane, dodecane, tetradecane, kerosene, ligroin, petroleum ether; cyclopentane, methylcyclopentane, cyclohexane, methylcyclohexane, cyclooctane,
Alicyclic hydrocarbons such as cyclohexene; aromatic hydrocarbons such as benzene, toluene, xylene, ethylbenzene, cumene, cymene; halogenated hydrocarbons such as dichloroethane, dichloropropane, trichloroethylene, carbon tetrachloride, chlorobenzene, etc. Can be mentioned. Among these, hexane, heptane, and octane are preferable.

Further, as the electron donor, an aliphatic alcohol,
Aromatic alcohols, ethers, aldehydes, ketones, carboxylic acids, carboxylic acid anhydrides, acid halides, amines, amides, nitriles, isocyanates and the like can be mentioned. Among these, alcohols are preferable, and methanol, ethanol and the like are particularly preferable.

Examples of the alkoxytitanium include tetramethoxytitanium, tetraethoxytitanium, tetra-n-butoxytitanium, tetraisopropoxytitanium and the like, with tetran-butoxytitanium being particularly preferred.

Examples of the magnesium alkoxide include, for example, the general formula Mg (OR ¹ ) r (OR ² ) _2- r [wherein, R ¹ and R ² are alkyl groups having 1 to 10 carbon atoms, cycloalkyl groups, aryl groups] Is a group or an aralkyl group, R ¹ and R ² may be the same or different, and r is a positive number from 0 to 2. ] Can be represented. Such magnesium alkoxide, _{e.g., Mg (-OCH 3) 2,} Mg (-OC
_{2 H 5) 2, Mg (} -OC 3 H 7) 2, Mg (-OC 4 H 9) 2, Mg (-O
_{C 6 H 13) 2, Mg} (-OC 8 H 17) 2, Is mentioned. Among these, dialkoxy magnesium is preferable.

The preparation of the magnesium alkoxide-containing liquid cannot be unequivocally different depending on the types of the magnesium alkoxide, the hydrocarbon, the electron donor and the alkoxytitanium, but the magnesium alkoxide and the hydrocarbon, the electron donor and the alkoxytitanium are either Examples thereof include a method of mixing with one kind or a mixture of two or more kinds, a method of mixing with heating, and the like.

As a preparation method, for example, (1) when alcohol and a hydrocarbon as an electron donor are used, the alcohol, the hydrocarbon and the magnesium alkoxide are mixed using about 1 mol or more of the alcohol per mol of the magnesium alkoxide. Method, and when (2) tetraalkoxytitanium is used, the amount of tetraalkoxytitanium is 0.5 mol or more, preferably 0.5 to 10 mol, and particularly preferably 0.5 to 5 mol, per 1 mol of magnesium alkoxide. There is a method of mixing tetraalkoxy titanium and magnesium alkoxide.

The contact between the magnesium alkoxide-containing liquid thus obtained and the solid substance is 0 to 100 ° C, preferably 10 to 30 ° C.
It can be performed by mixing the magnesium alkoxide-containing liquid and the solid at the temperature of. Upon this mixing, the magnesium alkoxide-containing liquid was added to the solid matter in an amount of 0.01 to
It is preferable to mix them at a ratio of 1 part by weight.

The contact time between the magnesium alkoxide-containing liquid and the solid material is usually 5 minutes to 24 hours.

It is possible to obtain a catalyst carrier (a) for olefin polymerization by filtering a mixture of the magnesium alkoxide-containing liquid and the solid, but when a lower alcohol or a halogenating agent is added to the mixture, magnesium Since the catalyst carrier (a) for olefin polymerization in which the compound is sufficiently supported can be obtained, it is preferable to separate this by decantation.

As the lower alcohol, methanol, ethanol, propanol, butanol, pentanol or the like can be used.

When a magnesium alkoxide-containing liquid is prepared using tetraalkoxy titanium, the lower alcohol used is preferably an alcohol having an alkyl group having a carbon number smaller than that of the tetra alkoxy titanium.

Examples of the halogenating agent include silicon tetrachloride, trichlorosilane, monomethyldichlorosilane, dimethylchlorosilane, ethyldichlorosilane, n-propyldichlorosilane, vinyldichlorosilane, n-butyldichlorosilane, phenyldichlorosilane. Chlorosilane, benzyldichlorosilane, allyldichlorosilane, monomethylmonochlorosilane, monoethylmonochlorosilane, trimethylmonochlorosilane, monomethyltrichlorosilane, and other halosilanes; diethylaluminum chloride, ethylaluminum dichloride, ethylaluminum sesquichloride, dimethylaluminum chloride, Organics such as methyl aluminum dichloride, methyl aluminum sesquichloride, propyl aluminum dichloride, dipropyl aluminum chloride Rumi halides; thionyl chloride; chloroform, hexa-trichloroethane, carbon tetrachloride, carbon tetrabromide, iodide atoms, a halogenated hydrocarbon or Harongen carbon such as t- butyl chloride; AlC
Examples thereof include metal halides such as l ₃ , AlBr ₃ , SnCl ₄ , BCl ₃ , SbCl ₃ and ZnCl ₂ ; hydrogen halides such as hydrogen chloride; and halogens such as chlorine. Among these, halosilane is preferable, and tetrachlorosilane is particularly preferable.

The amount of the lower alcohol or the halogenating agent added is an amount sufficient to precipitate magnesium on the catalyst carrier for olefin polymerization.

In addition, it is not preferable that the magnesium alkoxide-containing liquid and the lower alcohol or the halogenating agent are simultaneously contacted with the solid matter. The reason for this is that the polymerization activity of the supported catalyst metal decreases.

The solid obtained as described above is, when the solid inorganic oxide is only the solid composite inorganic oxide with respect to the solid inorganic oxide component used as a carrier, or the solid oxide and the solid composite inorganic. When mixed with an oxide, as a magnesium atom, with respect to the total of each solid inorganic oxide component,
Those containing 0.1 to 20% by weight, particularly 0.5 to 10% by weight are preferable.

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

The preparation of the solid catalyst component (A), the preparation of the catalyst for olefin polymerization, and the polymerization of olefin with this catalyst will be described below.

The solid catalyst component (A) is preferably obtained by contacting the catalyst carrier (a) obtained by the method of the present invention, the electron donating compound (b) and the titanium halide compound (C), It can be obtained by bringing the reaction product of the carrier (a) and the electron-donating compound (b) into contact with the titanium halide compound (c).

Examples of the electron-donating compound (b) include organic acid esters, aliphatic carboxylic acid esters, aliphatic dicarboxylic acid diesters, aromatic monocarboxylic acid esters, aromatic dicarboxylic acid diesters, aromatic dicarboxylic acid monoesters, and the like. To be

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

Examples of the aromatic monocarboxylic acid ester include lower alkyl esters of benzoic acid such as methyl, ethyl, propyl and n-butyl, and n-butyl benzoate is particularly preferable.

Examples of the 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, methyl propyl terephthalate, methyl isobutyl terephthalate, ethyl propyl terephthalate, ethyl isobutyl terephthalate, propyl isobutyl terephthalate, dimethyl isophthalate, diethyl isophthalate, dipropyl isophthalate, diisobutyl isophthalate, methyl ethyl isophthalate, methyl propyl isophthalate , Methyl isobutyl isophthalate, ethyl propyl isophthalate, ethyl isobutyl isophthalate, propyl isobutyl isophthalate and the like. Among these, dipropyl phthalate, diisobutyl phthalate and the like are preferable.

As the titanium halide compound (c), those represented by the following general formula can be used.

Ti (OR ¹ ) _4- sXs (3) [wherein R ¹ is an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group, an aryl group or an aralkyl group, and s is 0.
It is a real number not less than 4 and not more than 4, and X represents a halogen atom. ] When the titanium halide compound (c) is specifically shown,
Titanium tetrahalides such as TiCl ₄ , TiBr ₄ , TiI ₄ ; Ti
_{(OCH 3) Cl 3, Ti} (OC 2 H 5) Cl 3, (n-C 4 H 9 O) TiCl 3, Ti
Trihalogenated alkoxy titanium such as (OC ₂ H ₅ ) Br ₃ ; T
_{i (OCH 3) 2 Cl 2} , Ti (OC 2 H 5) 2 Cl 2, (n-C 4 H 5 O) 2 TiCl 2,
Dihalogenated alkoxytitanium such as Ti (OC ₃ H ₇ ) ₂ Cl ₂ ;
_{Ti (OCH 3) 3 Cl,} Ti (OC 2 H 5) 3 Cl, (n-C 4 H 9 O) 3 TiCl,
Examples thereof include monohalogenated trialkoxy titanium such as Ti (OCH ₃ ) ₃ Br. These may be used alone or as a mixture. Of these, it is preferable to use a high halogen content 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 titanium halide compound (c) are usually 0.
The contact may be performed at -200 ° C, preferably 10-150 ° C for 2 minutes to 24 hours, preferably 1 to 5 hours.

The solid catalyst component (A) thus prepared preferably contains 0.1 to 20% by weight, and particularly preferably 0.5 to 10% by weight, of titanium atom.

Further, a polyolefin can be obtained by bringing an olefin into contact with the catalyst obtained from the solid catalyst component (A), the organoaluminum compound (B) and the electron donor (C) obtained as described above.

The organoaluminum compound (B) is not particularly limited and has the following general formula: AlR ² tX ₃ -t Al ₂ R ² X ₃ [wherein R ² is an alkyl group having 1 to 10 carbon atoms, It is a cycloalkyl group or an aryl group, t is a real number between 1 and 3, and X represents a halogen atom such as chlorine or bromine. ] Is represented. Specifically, trialkylaluminums such as trimethylaluminum, triethylaluminum, triisopropylaluminum, triisobutylaluminum, trioctylaluminum, etc., and dialkylaluminums such as diethylaluminum monochloride, diisopropylaluminum monochloride, diisobutylaluminum monochloride, dioctylaluminum monochloride. Monohalide and ethylaluminum sesquichloride are preferable, and a mixture thereof is also preferable.

The electron donor (C) is an organic compound containing oxygen, nitrogen, phosphorus or sulfur. Specifically, amines, amides, ketones, nitriles, phosphines, phosphoramides, esters, ethers, thioethers, thioesters, acid anhydrides, acid halides, acid amides, aldehydes , Organic acids, and organic silicon compounds having a Si—O—C bond.

More specifically, organic acids such as aromatic carboxylic acids such as benzoic acid and p-oxybenzoic acid; acid anhydrides such as succinic anhydride, benzoic anhydride and p-toluic anhydride; acetone, methyl ethyl ketone, Methyl isobutyl ketone,
C3 to C15 ketones such as acetophenone, benzophenone and benzoquinone; carbon number 2 such as acetaldehyde, propionaldehyde, octylaldehyde, benzaldehyde, tolualdehyde and naphthaldehyde
~ 15 aldehydes; 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 pivalate, dimethyl maleate, ethyl cyclohexanecarboxylate, methyl benzoate, ethyl benzoate, propyl benzoate, butyl benzoate, octyl benzoate, cyclohexyl benzoate, phenyl benzoate, benzoate Acid benzyl, methyl toluate, ethyl toluate, amyl toluate, ethyl ethyl benzoate, methyl anisate, ethyl anisate, ethyl ethoxybenzoate, ethyl p-butoxybenzoate, ethyl o-chlorobenzoate, ethyl naphthoate , Γ-butyrolactone, δ-valerolactone, coumarin, phthalide, ethylene carbonate and the like having 2 to 18 carbon atoms; acetyl chloride, benzyl chloride, toluic acid chloride, anisic acid chloride and the like having 2 to 2 carbon atoms
15 acid halides; methyl ether, ethyl ether,
Ethers having 2 to 20 carbon atoms such as isopropyl ether, n-butyl ether, amyl ether, tetrahydrofuran, anisole, diphenyl ether, ethylene glycol butyl ether; acid amides such as acetic acid amide, benzoic acid amide, toluic acid amide; tributylamine, N , N′-dimethylpiperazine, tribenzylamine, aniline, pyridine, picoline, amines such as tetramethylethylenediamine, nitriles such as acetonitrile, benzonitrile, trinitrile; tetramethylurea, nidrobenzene, lithium butyrate, etc. You can Examples of the organosilicon compound having a Si—O—C bond include alkoxysilane and aryloxysilane. Such examples include the general formula R ⁴ vSi (OR ⁵ ) _4- v [wherein R ⁴ represents an alkyl group, a cycloalkyl group, an aryl group, an alkenyl group, a haloalkyl group, an aminoalkyl group or halogen, R ⁵ represents an alkyl group, a cycloalkyl group, an aryl group, an alkenyl group or an alkoxyalkyl group. Further, v is 0 ≦ v ≦ 3. However,
The v R ⁴ and (4-v) OR ⁵ may be the same or different. ] The silicate ester represented by these can be mentioned. Other examples include siloxanes having an OR ⁵ group or silyl esters of carboxylic acids. Furthermore, as another example, a silicon compound having no Si-O-C bond and a compound having an O-C bond are pre-reacted or reacted during the polymerization of an α-olefin to have a Si-O-C bond. The one converted into an organosilicon compound can be given, for example,
It is possible to use SiCl ₄ and alcohol together.

Specific examples of the organosilicon compound having the above Si-O-C bond include trimethylmethoxysilane, trimethylethoxysilane, dimethyldimethoxysilane, dimethylethoxysilane, diphenyldimethoxysilane, methylphenyldimethoxysilane, diphenyldiethoxysilane, Ethyltrimethoxysilane, vinyltrimethoxysilane, methyltrimethoxysilane, phenyltrimethoxysilane, r-chloropropyltrimethoxysilane,
Methyltriethoxysilane, ethyltriethoxysilane, vinyltriethoxysilane, butyltriethoxysilane, phenyltriethoxysilane, r-aminopropyltriethoxysilane, chlorotriethoxysilane, ethyltriisopropoxysilane, vinyltributoxysilane, silica Ethyl acid, butyl silicate, trimethylphenoxysilane, methyltriaryloxysilane, vinyltris (β-methoxyethoxy) silane, vinyltriacetoxysilane, dimethyltetraethoxydisiloxane, and the like.

Among the various electron donors (C), preferred are esters, ethers, ketones, acid anhydrides,
Examples thereof include organic silicon compounds having a Si-O-C bond.
In particular, alkyl esters of aromatic carboxylic acids such as benzoic acid, p-methoxybenzoic acid, p-ethoxybenzoic acid, and toluic acid having 1 to 1 carbon atoms.
Alkyl esters of 4 and trialkoxysilanes are preferred, and aromatic ketones such as benzoquinone, aromatic carboxylic acid anhydrides such as benzoic anhydride, and ethers such as ethylene glycol butyl ether are also preferred.

The electron donor (C) may be the same as or different from the electron donating compound (b) used for preparing the solid catalyst component (A).

The composition of each component of the catalyst for olefin polymerization is usually such that the organoaluminum compound (B) has an aluminum / titanium atomic ratio of 1 to 1000, preferably 5 to 500, and the electron donor (C). For, the electron donor (C) (mol) / titanium (atom) ratio is 0.01 to 100.

The method of the present invention produces an olefin polymer by polymerizing an α-olefin in the presence of the catalyst.

The α-olefin has the general formula R ⁶ —CH═CH ₂ [wherein R ⁶ represents hydrogen or an alkyl group having 1 to 20 carbon atoms or a cycloalkyl group]. ],
Examples thereof include linear monoolefins such as ethylene, propylene, butene-1, pentene-1, and octene-1, branched monoolefins such as 4-methyl-pentene-1, and vinylcyclohexene.

The α-olefin used for the polymerization is not limited to a single type, and a plurality of types of α-olefins may be copolymerized to produce a random copolymer or a block copolymer.

In the 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, the methods and conditions conventionally used in the field of olefin polymerization technology can be employed.

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

The polymerization temperature at that time is in the range of 20 to 100 ° C., preferably 40 to 90 ° C., and the polymerization pressure is usually in the range of 1 to 100 Kg / cm ² G, preferably 5 to 50 Kg / cm ² G.

The polymerization reaction can be generally carried out by a solution polymerization method using an aliphatic, alicyclic, aromatic hydrocarbon or a mixture thereof as a solvent, and the solvent is, for example, propane, butane, pentane, hexane, heptane, cyclohexane. , Benzene, and the like, and mixtures thereof can be used. Further, a vapor phase polymerization method or a bulk polymerization method using a liquid monomer itself as a solvent can be applied.

The molecular weight of the olefin polymer produced in the method of the present invention varies depending on the reaction mode, the catalyst system, and the polymerization conditions, but can be controlled by adding, for example, hydrogen, an alkyl halide, a dialkyl zinc or the like, if necessary.

EFFECTS OF THE INVENTION According to the present invention, (1) a catalyst having a high catalytic activity and a long activity duration is used, so that a stable polymerization reaction can be achieved even when performing multi-stage polymerization. (2) Almost no solvent residue remains in the produced olefin polymer, so that the olefin polymer can be favorably molded and processed. (3) In the produced olefin polymer, a polymer fineness of 100 μm or less is obtained. It is possible to provide a useful method for producing an olefin polymer, which has various advantages such as almost no powder, and the olefin polymer can be transported in a powder form without causing clogging in piping. it can.

EXAMPLES Next, the present invention will be described more specifically by showing Examples and Comparative Examples of the present invention.

(Example 1) Preparation of catalyst carrier 35 g of calcined silicon oxide (manufactured by Fuji Davison, grade 952) and 175 ml of trimethylchlorosilane were placed in a glass container of 0.5 in which argon was substituted, and reacted for 12 hours while stirring under reflux. Let After that, 100 ml of n-heptane was used, and washing by dentation was repeated 3 times to dry.

Diethoxy magnesium (150mmo
l), n containing tetra-n-butoxytitanium (90 mmol)
-150 ml of heptane solution was added and contact was carried out at room temperature for 1 hour. Thereafter, 50 ml of isopropanol was added dropwise, the mixture was stirred at 80 ° C. for 1 hour, decantation was repeated 5 times with 100 ml of n-heptane, and dried under reduced pressure at 80 ° C. for 1 hour to obtain a white catalyst carrier. The catalyst carrier contained 3.1% by weight of magnesium atoms.

8.0 g of the catalyst carrier thus obtained was placed in a glass container of 0.5, and 50 ml of n-heptane and n-butyl benzoate were added.
3.6 mmol and 40 g of titanium tetrachloride were added. 1 of this mixture
Stir under reflux for hours. Then, the supernatant was removed by decantation, and the solid portion obtained was sufficiently washed with hot n-heptane to obtain a solid catalyst component. The catalyst contained 2.2% by weight of Ti.

Polymerization of Propylene 0.006 mg atom (in terms of titanium atom) of the solid catalyst component suspended in 50 ml of hexane in an autoclave substituted with argon, 1.5 mmol of triethylaluminum, P-
0.45 mmol of methyl toluate was added. After depressurizing the inside of the autoclave to remove argon, 310 g of propylene and 0.7 N 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 and purging with propylene, 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 / cm ^2.
The fine powder having a particle size of 100 μm or less was 0.4% by weight and was excellent in fluidity. The ratio (II) of boiling n-heptane extraction residual polymer of this powder was 96.2%. The chlorine content in this polymer analyzed by fluorescent X-ray analysis is 16 ppm.
Met.

(Comparative Example 1) The same procedure as in Example 1 was performed except that the reaction with trimethylchlorosilane was not performed and the solid catalyst component was 0.012 mg atom. The obtained polypropylene powder was 17.3 g and II was 95.9%. Further, the amount of chlorine in this polymer analyzed by fluorescence X-ray analysis was 195 ppm (Comparative Example 2) In Example 1, methyltrichlorosilane was used instead of trimethylchlorosilane, and butylethyl was used instead of diethoxymagnesium. The same procedure was performed using magnesium. The obtained polypropylene powder is 45 g,
II was 96.3%. 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 was carried out except that ethanol was used instead of isopropanol (protruding agent). The obtained polypropylene powder is 105 g, and its bulk density is 0.38.
0.3% by weight of fine powder of g / cm ³ and 100 μm or less, 97.0% of II
Met. Further, the amount of chlorine in this polymer analyzed by fluorescent X-ray analysis was 16 ppm.

(Example 3) The same procedure as in Example 1 was performed, except that tetrachlorosilane was used instead of isopropanol (protruding agent). The obtained polypropylene powder was 120 g, its bulk density was 0.41 g / cm ³ , fine powder of 100 μm or less was 0.2% by weight, II was 9
It was 7.3%. The amount of chlorine in this polymer analyzed by fluorescent X-ray analysis was 14 ppm.

(Comparative Example 3) The same procedure as in Example 1 was carried out except that n-heptane was distilled off under reduced pressure without using isopropanol (a propellant). The obtained polypropylene powder is 75 g,
Its bulk density was 0.29 g / cm ³ , fine powder of 100 μm or less was 25% by weight, and II was 96.9%. Further, the amount of chlorine in this polymer analyzed by fluorescent X-ray analysis was 25 ppm.

(Example 4) In the same manner as in Example 1 except that 2.0 mmol of diisobutyl phthalate was used instead of n-butyl benzoate of Example 1 and 0.15 mmol of triethoxysilane was used instead of methyl P-toluate of Example 1. I did. The obtained PP powder is 212 g, its bulk density is 0.42 g / cm ³ , and fine powder of 100 μm or less is 0.3% by weight,
II was 97.5%. In addition, the amount of chlorine in this polymer analyzed by fluorescent X-ray analysis was 8 ppm.

[Brief description of drawings]

FIG. 1 is a flow chart showing steps of producing the catalyst according to the present invention.

Claims (3)

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