JP3338174B2 - Gas phase polymerization of olefins - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[Background of the Invention]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a gas phase polymerization method for olefins having good operation stability.

More specifically, the present invention controls the static electricity at the time of introducing a catalyst powder into a polymerization tank, thereby reducing the adhesion of the catalyst powder to an introduction pipe or a polymerization tank.
The present invention relates to a gas-phase polymerization method for olefins that enables stable operation by suppressing generation of a coarse polymer due to abnormal polymerization in a polymerization tank.

[0003]

[Summary of the Invention]

[0004]

The problems to be solved by the present invention are various operational troubles in the production of an olefin polymer by a gas phase method, for example, clogging of a catalyst introduction pipe at the time of introduction of a catalyst, and a problem in a polymerization tank. An object of the present invention is to provide a stable gas-phase polymerization method without formation of a coarse polymer due to catalyst adhesion.

[0005]

[Specific description of the invention]

[1] Solid catalyst component <Summary> Solid catalyst components used in the present invention include Ti, Mg and Cl.
Is a solid catalyst component obtained by subjecting to a prepolymerization step comprising contacting a solid component containing as an essential component with at least one unsaturated hydrocarbon monomer.

Here, known solid components containing Ti, Mg and Cl as essential components can be used. Here, "to make an essential component" means that in addition to the three components listed, other purposeful elements may be contained, and each of these elements exists as a purposeful arbitrary compound. And that these elements may be present as bonded to each other.

Preferred examples of such a solid component include the following.

For example, Japanese Patent Application Laid-Open Nos. 53-45688 and 5
Nos. 4-3894, 54-31092 and 54-39
No. 483, No. 54-94591, No. 54-11848
No. 4, No. 54-131589, No. 55-75411
Nos. 55-90510, 55-90511, 55-127405, 55-147507, and 5
Nos. 5-155003, 56-18609, 56-
Nos. 70005, 56-72001, 56-869
No. 05, No. 56-90807, No. 56-155206
Nos. 57-3803, 57-34103, 5
Nos. 7-92007, 57-121003 and 58-
Nos. 5309, 58-5310, 58-5311
No. 58-8706, No. 58-27732, No. 5
8-32604, 58-32605, 58-6
No.7703, No.58-117206, No.58-127
Nos. 708, 58-183708, 58-1837
No. 09, No. 59-149905, No. 59-14990
No. 6 Each publication.

Further, there may be mentioned those obtained by treating these with a tungsten or molybdenum compound, specifically, WCl ₆ , MoCl ₅ , or the like. <Essential components> Examples of the magnesium compound serving as a magnesium source used in the present invention include magnesium halide, dialkoxymagnesium, alkoxymagnesium halide, magnesium oxyhalide, dialkylmagnesium, magnesium oxide, magnesium hydroxide, magnesium carboxylate and the like. Is raised. Among these magnesium compounds, magnesium halide, dialkoxymagnesium, and alkoxymagnesium halide are preferred. The halogen of the halide is preferably chlorine and bromine, and the alkoxy is preferably lower alkoxy having 1 to 4 carbon atoms.

A titanium compound serving as a titanium source has a general formula Ti (OR ¹ ) _4-n X _n (where R ¹ is a hydrocarbon residue, and preferably has about 1 to 10 carbon atoms). , X represents a halogen, and n represents a number satisfying 0 ≦ n ≦ 4.). Specific examples of preferred compounds include TiCl ₄ , TiBr ₄ , Ti
(OC ₂ H ₅ ) Cl ₃ , Ti (OC ₂ H ₅ ) ₂ Cl ₂ ,
_{Ti (OC 2 H 5) 3} Cl, Ti (O-iC 3 H 7) C
_{l 3, Ti (O-nC} 4 H 9) Cl 3, Ti (O-nC
_{4 H 9) 2 Cl 2,} Ti (OC 2 H 5) Br 3, Ti
(OC ₂ H ₅ ) (OC ₄ H ₉ ) ₂ Cl, Ti (O-nC
_{4 H 9) 3 Cl, Ti} (O-C 6 H 5) Cl 3, Ti
_{(O-iC 4 H 9)} 2 Cl 2, Ti (OC 5 H 11) Cl
₃ , Ti (OC ₆ H ₁₃ ) Cl ₃ , Ti (OC
_{2 H 5) 4, Ti (} O-nC 3 H 7) 4, Ti (O-n
_{C 4 H 9) 4, Ti} (O-iC 4 H 9) 4, Ti (O-
nC ₆ H ₁₃ ) ₄ , Ti (O-nC ₈ H ₁₇ ) ₄ , Ti [O
CH ₂ CH (C ₂ H ₅ ) C ₄ H ₉ ] ₄ , and the like.

Further, a molecular compound obtained by reacting an electron donor described later with TIX ′ ₄ (here, X ′ represents a halogen) can be used. Specific examples of such molecular compounds include TiCl ₄ .CH ₃ COC ₂ H ₅ , Ti
Cl ₄ · CH ₃ CO ₂ C ₂ H ₅ , TiCl ₄ · C ₆ H ₅
NO ₂ , TiCl ₄ .CH ₃ COCl, TiCl ₄ .C
_{6 H 5 COCl, TiCl 4 ·} C 6 H 5 CO 2 C
₂ H ₅ , TiCl ₄ .ClCOC ₂ H ₅ , TiCl _4.
C ₄ H ₄ O, and the like.

Among these titanium compounds, preferred are TiCl ₄ , Ti (OC ₂ H ₅ ) ₄ , Ti (OC
₄ H ₉ ) ₄ and Ti (OC ₄ H ₉ ) Cl ₃ .

In addition, the general formula Ti (OR ² ) _3-p X _p (where R ² is a hydrocarbon residue, preferably having 1 carbon atom)
X is a halogen, p is O
<P ≦ 3. ) Can also be used. Preferred specific examples of such a titanium compound include TiCl ₃ , TiBr ₃ , Ti (OC
_{H 3) Cl 2, Ti (} OC 2 H 5) there are ₂ or the like Cl.

Further, titanocene compounds such as dicyclopentadienyldichlorotitanium, dicyclopentadienyldimethyltitanium and bisindenyldichlorotitanium can be used.

The halogen source is usually supplied from the above-mentioned magnesium and / or titanium halides, but other halogen sources such as aluminum halides, silicon halides and phosphorus halides It can also be supplied from a known halogenating agent. It is also possible to use an ester as an electron donor (described later in detail) in the form of its acyl halide (for example, phthalic acid chloride) and use its halogen as a halogen source. The halogen contained in the catalyst component may be fluorine, chlorine, bromine, iodine or a mixture thereof, with chlorine being particularly preferred. <Optional Component (Part 1)> As described above, the solid component used in the present invention may further contain various optional components in addition to the above essential components. So, for example,
When this solid component is produced for stereoregular polymerization of an α-olefin having 3 to 12 carbon atoms, particularly propylene,
It can be prepared using an electron donor as an internal donor. What is obtained using such an electron donor forms one embodiment of the preferred solid component of the present invention.

The electron donor (internal donor) usable for the production of the solid component includes oxygen-containing electron donors such as alcohols, phenols, ketones, aldehydes, carboxylic acids, esters of organic acids or inorganic acids. , Ethers, acid amides, acid anhydrides, nitrogen-containing electron donors such as ammonia, amines, nitriles, and isocyanate donors.

More specifically, (a) methanol, ethanol, propanol, pentanol, hexanol,
Octanol, dodecanol, octadecyl alcohol, benzyl alcohol, phenylethyl alcohol,
Alcohols having 1 to 18 carbon atoms such as cumyl alcohol and isopropylbenzyl alcohol, (ii) phenol, cresol, xylenol, ethyl phenol,
C6 to C25 phenols which may have an alkyl group such as propylphenol, cumylphenol, nonylphenol, and naphthol; and (C) C3 to C15 phenols such as acetone, methyl ethyl ketone, methyl isobutyl ketone, acetophenone and benzophenone. Ketones, (d) acetaldehyde, propionaldehyde,
C2 to C15 aldehydes such as octyl aldehyde, benzaldehyde, tolualdehyde, naphthaldehyde, methyl (fo) formate, methyl acetate, ethyl acetate, vinyl acetate, propyl acetate, octyl acetate, cyclohexyl acetate, cellosolve acetate, propionic acid ethyl,
Methyl butyrate, ethyl valerate, ethyl stearate, methyl chloroacetate, ethyl dichloroacetate, methyl methacrylate, ethyl crotonate, ethyl cyclohexanecarboxylate, methyl benzoate, ethyl benzoate, propyl benzoate, butyl benzoate, benzoic acid Octyl, cyclohexyl benzoate, phenyl benzoate, benzyl benzoate, cellosolve benzoate, methyl toluate, ethyl toluate, amyl toluate, ethyl benzoate, methyl anisate, ethyl anisate, ethyl ethoxy benzoate,
C2-C2 such as diethyl phthalate, dibutyl phthalate, diheptyl phthalate, γ-butyrolactone, α-valerolactone, coumarin, phthalide, ethylene carbonate, etc.
Organic acid esters 0, inorganic acid esters such as silicate esters such as (f) ethyl silicate and butyl silicate,
And (g) the following general formula _{^{R 3 R 4 3-q Si}} (OR 5) q ( where hydrocarbon residues R ³ to 20 carbon atoms, preferably 3 to 20 carbon atoms, more preferably 4 ~ 12,
An aliphatic hydrocarbon residue in which the carbon atom adjacent to the silicon atom, that is, the α-carbon, has a secondary or tertiary, more preferably a tertiary branch, wherein R ⁴ is the same as or different from R ³ A chain or cyclic aliphatic hydrocarbon residue having 1 to 20, preferably 1 to 12 carbon atoms, R ⁵ is a hydrocarbon residue having 1 to 6, preferably 1 to 4 carbon atoms, q is 1 ≦ q ≦ 3), specifically, methyltrimethoxysilane, dimethyldimethoxysilane, ethyltrimethoxysilane, i-propyltrimethoxysilane, i-butyltrimethoxysilane, t-butyltriethoxysilane, t-butylmethyldimethoxysilane, di-t-butylmethoxylane, t-butylmethyldiethoxysilane, t-amylmethyldiethoxysilane, vinyltriethoxysilane Emissions, phenyltriethoxysilane, diphenyldimethoxysilane, dicyclohexyl dimethoxysilane, cyclohexyl dimethoxysilane, 2
-Silicon compounds such as norbornanetriethoxysilane, 2-norbornanemethyldimethoxysilane, dicyclopentyldimethoxysilane, cyclopentyltriethoxysilane, (g) acetyl chloride, benzoyl chloride, toluic acid chloride, anisic acid chloride, phthaloyl chloride, and phthaloyl isochloride 2 to 15 carbon atoms such as
Acid halides having 2 to 20 carbon atoms, such as methyl ether, ethyl ether, isopropyl ether, butyl ether, amyl ether, tetrahydrofuran, anisole and diphenyl ether;
(Ii) acid amides such as acetic acid amide, benzoic acid amide and toluic acid amide, (nu) methylamine, ethylamine, diethylamine, tributylamine, piperidine,
Tribenzylamine, aniline, pyridine, picoline,
Amines such as tetramethylethylenediamine,
Examples thereof include nitriles such as acetonitrile, benzonitrile, and tolunitrile.

Two or more of these electron donors can be used. Electron donors preferably used in preparing a catalyst component for the polymerization of olefins having 3 or more carbon atoms, particularly propylene, in which stereoregular polymerization is important, include organic acid esters and organic acid halides, and are represented by the above general formula. It is an organosilicon compound.

The use amount of each of the above components can be arbitrary as long as the effects of the present invention can be recognized.
The following ranges are preferred.

The amount of the titanium compound used is 1 × 10 ^-4 to 1 in molar ratio with respect to the amount of the magnesium compound used.
000, preferably 0.01 to 10. When a compound for that purpose is used as a halogen source, the amount used is 1 × 10 5 in molar ratio with respect to the amount of magnesium used irrespective of whether the titanium compound and / or the magnesium compound contains halogen or not. ^{-2 to} 1000, preferably 0.1 to 10
0.

The amount of the electron donating compound used is in the range of 1.times.10.sup.- ³ to 10, preferably 0.01 to 5, in a molar ratio with respect to the amount of the magnesium compound. . <Preparation of solid component> The solid component is prepared by using the above-mentioned titanium source, magnesium source and halogen source, and if necessary, the above-mentioned or other components such as an electron donor, for example, by the following production method. Manufactured. (A) A method in which a magnesium halide and a titanium-containing compound are brought into contact with an electron donor as required. (B) A method in which alumina or magnesia is treated with a phosphorus halide compound, and a magnesium halide, an electron donor, and a titanium halide-containing compound are brought into contact therewith. (C) A method of contacting a titanium halide compound and / or a silicon halide compound with a solid component obtained by contacting a magnesium halide with a titanium tetraalkoxide and a specific polymer silicon compound.

As the polymer silicon compound, a compound represented by the following formula is suitable.

[0023]

Embedded image (Where R ⁶ is a hydrocarbon residue having about 1 to 10 carbon atoms,
γ indicates the degree of polymerization such that the viscosity of the polymer silicon compound becomes about 1 to 100 centistokes. Among them, methyl hydrogen polysiloxane, ethyl hydrogen polysiloxane, phenyl hydrogen polysiloxane, cyclohexyl hydrogen polysiloxane, 1,3,5,7-tetramethylcyclotetrasiloxane, 1,3,5 7,9-pentamethylcyclopentasiloxane and the like are preferable. (D) A method of dissolving a magnesium compound with a titanium alkoxide and an electron donor, and bringing the titanium compound into contact with a solid component precipitated with a halogenating agent or a titanium halide compound. (E) A method in which an organomagnesium compound such as a Grignard reagent is allowed to react with a halogenating agent, a reducing agent, and the like, and then contacted with an electron donor and a titanium compound as necessary. (F) A method of contacting an alkoxymagnesium compound with a halogenating agent and / or a titanium compound in the presence or absence of an electron donor. (G) In any one of the above, a method in which an optional component described below is present.

Among these, the methods (c) and (g) are preferred.

The contact temperature is about -50 to 200 ° C, preferably about 0 to 100 ° C. As a contact method,
Examples thereof include a mechanical method using a rotary ball mill, a vibration mill, a jet mill, and a medium stirring / pulverizing machine, and a method of bringing into contact by stirring in the presence of an inert diluent. Examples of the inert diluent used at this time include aliphatic or aromatic hydrocarbons, halohydrocarbons, and polysiloxanes.

At the time of such contact, other components other than the above components, such as methyl hydrogen polysiloxane, ethyl borate, aluminum triisopropoxide, aluminum trichloride, Silicon chloride, tetravalent titanium compound,
It is also possible to coexist a trivalent titanium compound or the like (details will be described later).

In this manner, a solid component for a Ziegler catalyst containing titanium, magnesium and halogen as essential components is obtained. <Optional Component (Part 2)> As described above, the component used in the present invention contains the essential components (Ti, Mg, and halogen), and may contain an electron donor as an optional component. However, the following can be further used as an optional component.

That is, the solid components are SiCl ₄ , CH
₃ Silicon compounds such as SiCl ₃ , polymer silicon compounds such as methyl hydrogen polysiloxane, Al (Oi
C ₃ H ₇ ) ₃ , AlCl ₃ , AlBr ₃ , Al (OC _{2
H 5) 3, Al (OCH} 3) 2 aluminum compounds such as Cl and _{BCl 3, BBr 3, B (} OCH 3) 3, B
Boron compounds such as (OC ₂ H ₅ ) ₃ and B (OC ₆ H ₅ ); tungsten compounds such as WCl ₆ and WCl ₅ ;
Other components such as molybdenum compounds such as oCl ₅ and MoBr ₅ can be used in combination, and these are silicon, aluminum,
It may be left in the solid component as a component such as boron, tungsten and molybdenum.

The amount of the silicon, aluminum, boron, tungsten and molybdenum compounds used is 1 × 10 ^-3 to 1 in terms of a molar ratio with respect to the above-mentioned magnesium compound.
00, preferably 0.01 to 10.

Further, in the present invention, an organic metal compound of a Group I to III metal of the periodic table can be used, if necessary, in the production of the solid component.

As an organometallic compound, the compound has at least one organic group-metal bond. As the organic group in that case, about 1 to 10 carbon atoms, preferably 1 to
About 6 hydrocarbyl groups are typical. Representative metals in this compound are lithium, magnesium, aluminum and zinc, especially aluminum.

The remaining valences (if any) of the metal of the organometallic compound wherein at least one of the valences is filled with an organic group are hydrogen, halogen, hydrocarbyloxy (hydrocarbyl is About 1 to 10 carbon atoms, preferably about 1 to 6 carbon atoms) or the metal (specifically, -O-Al (CH ₃ )-in the case of methylalumoxane) via an oxygen atom, and the like. You.

Specific examples of such organometallic compounds include (a) organolithium compounds such as methyllithium, n-butyllithium and tertiarybutyllithium, (b) butylethylmagnesium, dibutylmagnesium and hexylethylmagnesium. , Butylmagnesium chloride,
Organic magnesium compounds such as tert-butylmagnesium bromide, (c) organic zinc compounds such as diethyl zinc and dibutyl zinc, (d) trimethylaluminum, triethylaluminum, triisobutylaluminum, tri-n-
Hexylaluminum, diethylaluminum chloride, diethylaluminum hydride, diethylaluminum ethoxide, ethylaluminum sesquichloride,
Organic aluminum compounds such as ethylaluminum dichloride and methylaluminoxane can be mentioned. Among these, an organic aluminum compound is particularly preferable. Even more preferred are organoaluminum halide compounds.

The amount of the organometallic compound used is 0.01 to 100, preferably 0.1 to 100, in terms of the metal atom ratio (metal / titanium) of the organometallic compound to the titanium component constituting the solid component.
1 to 30. <Preliminary polymerization> The solid catalyst component of the present invention comprises the aforementioned Ti, M
It is obtained by subjecting a solid component containing g and Cl as essential components to a prepolymerization step comprising contacting at least one unsaturated hydrocarbon monomer.

The unsaturated hydrocarbon monomer used in the prepolymerization is an ethylenically unsaturated hydrocarbon compound such as an olefin or a diene compound. Such ethylenically unsaturated compounds include those having 2 to 20 carbon atoms, preferably 2 to 12 carbon atoms,
More preferably, it is a linear α-olefin having 2 to 4 carbon atoms, and a branched α-olefin having 5 to 20 carbon atoms, preferably 5 to 12 carbon atoms (the branched chain is preferably one having 1 to 4 carbon atoms. The position of the branched chain is preferably at a carbon atom adjacent to a carbon atom having a double bond), a vinyl group-containing aromatic compound, a linear or cyclic diene compound having 4 to 20, preferably 6 to 12 carbon atoms. and so on. Preferred specific examples of such a compound include, for example, ethylene, propylene, 1-butene, 2-butene, isobutylene, 1-pentene, 2-pentene, 2-methyl-1-butene, 3-methyl-1-butene, 1-hexene, 2-hexene, 3-
Hexene, 2-methyl-1-pentene, 3-methyl-1
-Pentene, 4-methyl-1-pentene, 2-methyl-
2-pentene, 3-methyl-2-pentene, 4-methyl-2-pentene, 2-ethyl-1-butene, 2,3-dimethyl-1-butene, 3,3-dimethyl-1-butene,
2,3-dimethyl-2-butene, 1-heptene, 1-octene, 2-octene, 3-octene, 4-octene,
1-nonene, 1-decene, 1-undecene, 1-dodecane, 1-tridecane, 1-tetradecane, 1-pentadecane, 1-hexadecane, 1-heptadecane, 1-octadecane, 1-nonadecane, styrene, α-methyl- Styrene, divinylbenzene, 1,2-butadiene, isoprene, hexadiene, 1,4-hexadiene, 1,5
-Hexadiene, 1,3-pentadiene, 1,4-pentadiene, 2,3-pentadiene, 2,6-octadiene, cis-2, trans4-hexadiene, trans 2, t
rans 4-hexadiene, 1,2-heptadiene, 1,
4-heptadiene, 1,5-heptadiene, 1,6-heptadiene, 2,4-heptadiene, dicyclopentadiene, 1,3-cyclohexadiene, 1,4-cyclohexadiene, cyclopentadiene, 1,3-cycloheptadiene , 1,3-butadiene, 4-methyl-1,4-
Hexadiene, 5-methyl-1,4-hexadiene,
1,9-decadiene, 1,13-tetradecadiene and the like can be mentioned. Among these, a linear α-olefin, a vinyl group-containing aromatic compound and a non-conjugated diene compound are preferred, and ethylene, propylene, styrene and divinylbenzene are particularly preferred.

Usually, these unsaturated hydrocarbon monomers are polymerized by contact with a solid component together with an organoaluminum compound as required.

The prepolymerization conditions are not particularly limited, but generally the following conditions are suitable.

[0038] The polymerization temperature is preferably from 0 to 100 ° C, more preferably from 10 to 90 ° C. As the polymerization amount, it is preferable to polymerize 0.001 to 50 g of olefins per 1 g of the solid component, and it is more preferable to polymerize 0.1 to 10 g of olefins.

At the time of prepolymerization, an organoaluminum compound can coexist. As the organoaluminum compound component which may be used, a compound generally known as a Ziegler-type catalyst organoaluminum compound can be used. As specific examples, the compounds described in the section of the description of the organoaluminum compound described below can be used.

The amount of the organoaluminum component used during the prepolymerization is determined by the ratio of Al / Al to the Ti component in the solid component (A).
0.2 to 20 is preferable in terms of Ti (molar ratio), and 0.5 to 1
0 is more preferred.

The polymerization method is not particularly limited, but generally,
It is performed using a slurry polymerization method or a gas phase polymerization method, and continuous polymerization or batch polymerization is applied. As the solvent in the case of slurry polymerization, hydrocarbons such as butane, pentane, hexane, heptane, cyclohexane, benzene, and toluene are used. Further, at the time of prepolymerization, hydrogen may be allowed to coexist for controlling the molecular weight.

Since the obtained solid catalyst component is supplied as a powder, it is usually dried. Drying conditions at this time are also arbitrary, but drying is generally performed at a temperature lower than the melting point of the polymer, preferably at a temperature of 0 to 80 ° C. It is preferable to dry so that the residual solvent at this time is 10 wt% or less, preferably 5 wt% or less. <Dynamic Charge> One feature of the present invention is that the dynamic charge Q (unit: μC / g) of the solid catalyst component is −1 ≦
It is to use a solid catalyst component in which the amount of static electricity of the solid catalyst component is controlled so that Q ≦ 1.

The dynamic charge Q mentioned here is not a static charge in a static state but a dynamic charge in a dynamic state generated at the time of powder transfer, for example, transfer to a polymerization tank. .
Specifically, it is defined as the amount of static electricity that the solid catalyst component takes when 20 g of the solid catalyst component flows through a stainless steel pipe having an inner diameter of 2 mm at a linear velocity of 20 m / s. Such an amount of static electricity can be easily measured by a Faraday cage or the like.

In general, a catalyst which has undergone prepolymerization has poor conductivity, and generates static electricity by colliding or rubbing against the inner surface of a pipe such as iron. This value is a large negative charge of -1 μC / g or less. Such a catalyst tends to adhere to the piping and the polymerization tank, and thus tends to reduce the operation stability of the apparatus.

The present invention is intended to solve such a problem, and aims to achieve this object mainly by using a solid catalyst component having a controlled amount of static electricity.

In order to control the amount of static electricity of the solid catalyst component in such a state to a predetermined value, a substance having a positive charge is brought into contact with the solid catalyst component and the substance is impregnated or adhered to the solid catalyst component. Can be. The contact method is arbitrary, such as a gas phase, a liquid phase, and a solid phase, and is appropriately selected depending on a substance having a positive charge.

One of the techniques for this purpose is, specifically, an organic or organic material having an electrostatic charge Q ′ of +10 to 5000 μC / g and an average particle diameter of 1 μm or less measured by a blow-off method for iron powder. A method of attaching an inorganic ultrafine solid component to the solid catalyst component can be exemplified.

Here, the amount of static electricity Q 'of the ultrafine solid component by the blow-off method is preferably +50 to 2,000.
μC / g, particularly preferably 100-1500 μC / g,
It is. The average particle diameter of the ultrafine solid component is an average value of particle diameters in a certain direction observed by an electron microscope, preferably 50 Å to 0.5 μm, particularly preferably 100 Å to 0.2 μm. . The solid component of the ultrafine particles is preferably a non-basic inorganic oxide such as an oxide of Si or Ti, and more preferably an oxide of Si. "Blow-off method" is a method used for measuring the triboelectric charge amount of powders such as toners. After mixing ultrafine solids and carrier particles (iron powder),
This is a method in which only the ultrafine solid is blown off (blown) with a high-pressure gas, the amount of charge remaining on the carrier granules is measured by a Faraday cage, and the amount of reverse charge is determined as the amount of static electricity.

Preferred specific examples of the ultrafine solid component satisfying such conditions include an inorganic oxide surface-treated with an aminosilane coupling agent, and silica gel produced under aqueous conditions. Among them, particularly preferred are aminosilane coupling agents such as γ-aminopropyltriethoxysilane, N-β (aminoethyl) γ-aminopropyltrimethoxysilane,
-Β (aminoethyl) γ-aminopropylmethyldimethoxysilane, SiO ₂ compound surface-treated with N-phenyl-γ-aminopropyltrimethoxysilane and the like.

Upon contact of the ultrafine solid component with the solid catalyst component, the mixing ratio of the two is determined by the dynamic charge Q (unit: microcoulomb (μ)
C) / g) is within the range of -1 ≦ Q ≦ 1. Generally, the weight ratio of the ultrafine solid component to the solid catalyst component is in the range of 0.001 to 0.5, preferably in the range of 0.005 to 0.1.
In addition, these mixing methods may be any methods as long as the effects of the present invention are recognized, and may be an inert gas (preferably a sufficiently purified one), for example, a method of mixing under a nitrogen gas atmosphere, an inert solvent, For example, a method of mixing in the presence of a hydrocarbon solvent such as hexane and heptane is preferable.

The mixing can be performed by a method of stirring, a method of mixing with a mill such as a vibration mill, a rotary ball mill, or the like, a method of mixing with a shaking machine, and the like. The mixing time is preferably about 1 minute to 100 hours, particularly about 5 minutes to 10 hours. [2] an organic aluminum compound the solid catalyst component and an organoaluminum compound to be combined at the time of olefin polymerization, specifically, the general formula R ⁷ _3-s
AlX _s or _{^{R 8 3-t Al (OR}} 9) t ( wherein, R
⁷ and R ⁸ each have the same or different carbon number of 1
20 hydrocarbon residues or hydrogen atoms, R ⁹ is a hydrocarbon residue, X is a halogen, s and t are each 0 ≦ s
<3, 0 <t <3). Specifically, (a) trialkylaluminums, for example, trimethylaluminum, triethylaluminum, triisobutylaluminum, trihexylaluminum, trioctylaluminum and tridecylaluminum, and (b) alkylaluminum halides, for example, diethylaluminum monochloride,
(C) dialkylaluminum hydrides such as diisobutylaluminum monochloride, ethylaluminum sesquichloride and ethylaluminum dichloride, such as diethylaluminum hydride and dibutylaluminum hydride;
Aluminum alkoxides, such as, for example, diethyl aluminum ethoxide and diethyl aluminum phenoxide. Among them, trialkylaluminum is preferred, and those having a hydrocarbon group having 1 to 4 carbon atoms are particularly preferred.

These organoaluminum compounds can be used in combination of two or more in each group and / or between each group. For example, a combination of triethylaluminum and diethylaluminum alkoxide, a combination of diethylaluminum monochloride and diethylaluminum ethoxide, a combination of ethylaluminum dichloride and diethylaluminum ethoxide, a combination of triethylaluminum and diethylaluminum ethoxide and diethylaluminum monochloride, Is raised. [3] Gas phase polymerization of olefin The present invention relates to gas phase polymerization of olefin.
The gas phase polymerization is a method in which polymerization is performed in a gaseous monomer without using a solvent substantially. Specifically, the method is carried out by a method in which the produced polymer particles are caused to flow by a monomer stream to form a fluidized bed, or a method in which the produced polymer particles are stirred in a reaction tank by a stirrer. <Olefin Monomer and Product Polymer> The olefin polymerized by the catalyst system of the present invention has a general formula of R ⁰ —CH ＝ CH ₂
(Where R ⁰ is a hydrogen atom or a hydrocarbon residue having 1 to 10 carbon atoms and may have a branched group). Specifically, there are olefins such as ethylene, propylene, butene-1, pentene-1, hexene-1, and 4-methylpentene-1. Preferred are ethylene and propylene. In these polymerizations, up to 50% by weight, preferably 2%, based on ethylene.
Copolymerization of the olefin with ethylene up to 0 weight percent can be carried out, with 30
Up to weight percent of the above olefins, especially ethylene,
And propylene can be copolymerized. Also,
Copolymerization with other copolymerizable monomers (eg, vinyl acetate, diolefin, etc.) can also be performed.

Typical examples of the polymer obtained according to the present invention include:
(A) homopolymers such as ethylene and propylene, (b)
Random copolymers of ethylene and propylene, ethylene and butene-1, ethylene and hexene-1, ethylene and octene-1, propylene and butene-1, propylene and hexene-1, and (c) propylene and ethylene or propylene Of ethylene and propylene,
Block copolymers and the like. <Polymerization conditions> The polymerization temperature is about 30 ° C to 150 ° C, preferably about 50 ° C to 100 ° C, and the polymerization pressure is usually 1 to 5
It is in the range of 0 kg / cm ² G. In the polymerization, the MF is adjusted using a molecular weight modifier such as hydrogen, if necessary.
It is also possible to control R.

[0054]

The following examples serve to illustrate the invention in more detail. Therefore, the present invention is not limited to the following examples.

In the following Examples, the static electricity Q of the solid catalyst component was measured by placing 20 g of the solid catalyst component in a stream of N ₂ and placing a stainless steel tube having an inner diameter of 2 mm and a length of 2 m in a N ₂ stream.
₂ Flow at a flow velocity (linear velocity) of 20 m / s, and directly place the powder in a N ₂ atmosphere in a Faraday cage (Advantest TR841).
The charge was measured after receiving 1). The static electricity Q 'of the ultrafine solid was 100 g of iron powder and 0.1 g of the ultrafine solid component.
Was mixed at 90 rpm for 10 minutes using a Turbula mixer, and then mixed using a 300-mesh screen.
Blow-off was performed for 1 minute with a Kg / cm ² N ₂ gas stream, and the charge was measured with a powder charge amount measuring device (Toshiba Chemical, “TB-200”).

On the other hand, the catalyst deposition amount was 10 cc of the solid catalyst component.
Was filled in a 300 cc stainless steel container under an N ₂ atmosphere, and shaken for 3 minutes with a shaker. Then, the contents were discarded in an inclined manner, and the weight of the remaining deposits of the catalyst was measured. <Example-1> Production of solid catalyst component n was dehydrated and deoxygenated in a flask sufficiently purged with nitrogen.
200 ml of heptane are introduced and then MgCl ₂ 0.2
_{Mol, Ti (O-nC 4 H} 9) 4 was 0.4 mol introduction,
The reaction was performed at 95 ° C. for 2 hours. After completion of the reaction, the temperature was lowered to 40 ° C., and then 24 ml of methylhydropolysiloxane (of 20 centistokes) was introduced.
Allowed to react for hours. The resulting solid component was washed with n-heptane.

Then, into a flask sufficiently purged with nitrogen,
The solid component synthesized as described above was introduced in an amount of 0.12 mol in terms of Mg atom, and n-heptane was further added to 200 cc. Then, at 25 ° C., 13 mmol of ethylaluminum dichloride was added dropwise in 20 minutes, and 0.39 mole of SiCl _{4 was} added dropwise in 20 minutes to react for 3 hours. Then, the temperature was raised to 90 ° C., and further 3 hours. Reacted. The reaction product is n-
Washed thoroughly with heptane.

Next, 0.066 mol of ethyl aluminum dichloride (15 wt% heptane solution) was added dropwise and reacted at 35 ° C. for 2 hours. The reaction product was sufficiently washed with n-heptane and dried under reduced pressure. This had a Ti loading of 4.20% by weight.

In a 1.5-liter stainless steel autoclave with stirring blades sufficiently purged with nitrogen, 500 ml of sufficiently purified n-heptane and the solid catalyst component 1 obtained above were added.
6 grams introduced and triisobutylaluminum 3
2 grams were introduced. Then, 1.5 kg / cm ² G of hydrogen was added.
After that, ethylene was introduced at 80 ° C. at a rate of 0.43 liter / min for 2 hours to perform prepolymerization.

The product was thoroughly washed with n-heptane and dried under reduced pressure to obtain a solid component. The polymerization amount of ethylene is
It was 3.4 grams / gram solids.

The average particle size of the catalyst component was 34.9 microns.

Mixing with Ultrafine Particle Solid Component 70 g of the above solid catalyst component and silica “Aerosil RA200H” manufactured by Nippon Aerosil Co., Ltd. (Q ′ = 350 μC / g) were placed in a 1-liter stainless steel container sufficiently substituted with N _2.
1.3 g of Nippon Aerosil TiO ₂ (“TP-2
5 ") 1.3 g was added and mixed with a vibration mill for 1 hour.
Q of the obtained solid catalyst component was −0.2 μC / g. Further, the angle of repose was 54 degrees, the bulk density was 0.40 g / cc, and the catalyst adhesion amount was 0.03 g / 10 cc.

Gas phase polymerization of ethylene Using a gas phase polymerization apparatus having the same internal volume of 800 liters as the gas phase polymerization apparatus described in JP-A-54-148093,
Ethylene and butene are copolymerized at 80 ° C. with the present catalyst at an ethylene partial pressure of 7 kg / cm ² and a butene / ethylene molar ratio of 0.1.
008, at a hydrogen / ethylene molar ratio of 0.43, 750 ppm of triethylaluminum per produced polymer and the solid catalyst component obtained above so that the produced polymer amount becomes 10 kg / hour, respectively, and an average residence time of 3 hours Was used for copolymerization. The results were as shown in Table 1. <Example-2> RA200H was replaced with RP13 in Example-1.
0H (SiO ₂ manufactured by Nippon Aerosil Co., Ltd., Q ′ = 200 μC)
/ G), except that the solid catalyst component was produced in the same manner. Its Q was -0.3 µC / g, the angle of repose was 57 ° and the bulk density was 0.38 g / cc. The catalyst adhesion amount was 0.05 g / 10 cc.

Further, a polymerization operation was carried out in the same manner as in Example-1. The obtained results were as shown in Table 1. <Comparative Example-1> Silica "RA200H" in Example-1
A solid catalyst component was produced in the same manner except that was not used. Its Q was -2.0 µC / g, the angle of repose was 50 °, the bulk density was 0.51 g / cc, and the catalyst adhesion amount was 0.20 g / cc.

The polymerization was carried out in the same manner as in Example 1. The obtained results were as shown in Table 1.

[0066]

[Table 1]

[0067]

According to the present invention, the catalyst is effectively prevented from adhering to the catalyst introduction tube or the polymerization tank, and the clogging of the catalyst introduction tube and abnormal polymerization in the polymerization tank are suppressed. The fact that stable operation is possible is as described above in the section of [Summary of the Invention].

────────────────────────────────────────────────── ─── Continuation of front page (72) Inventor Hajime Takahashi 1 Toho-cho, Yokkaichi-shi, Mie Mitsubishi Yokkaichi Co., Ltd. Yokkaichi Research Institute (56) References JP-A-7-247308 (JP, A) Hei 6-199927 (JP, A) Special table Sho-63-500176 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) C08F 4/60-4/70 C08F 2/34

Claims (4)

(57) [Claims] 1. A solid catalyst component obtained by subjecting a solid component containing Ti, Mg and Cl as essential components to at least one unsaturated hydrocarbon monomer to a prepolymerization step, and an organoaluminum compound A method comprising the steps of: contacting at least one α-olefin in a gas phase with a catalyst comprising
Contacting the solid catalyst component with the solid catalyst
Impregnated or adhered to the component, the dynamic charge Q which takes the solid catalyst component (unit is [mu] C / g) is -1 ≦ Q ≦
A gas phase polymerization method for olefins, characterized by using a solid catalyst component in which the amount of static electricity of the solid catalyst component is controlled to be 1. 2. The method according to claim 1, wherein the solid catalyst component is an ultrafine solid having an electrostatic charge of +10 to 5000 μ / g and an average particle size of 1 μm or less measured by a blow-off method with respect to iron powder. The gas-phase polymerization method for an olefin according to claim 1, wherein 3. The method of claim 2, wherein the ultrafine solid is a SiO ₂ compound surface-treated with an aminosilane coupling agent. 4. An aminosilane coupling agent comprising: γ-aminopropyltriethoxysilane, N-β (aminoethyl) γ-aminopropyltrimethoxysilane, N-β
The olefin gas phase polymerization method according to claim 3, which is selected from (aminoethyl) γ-aminopropylmethyldimethoxysilane and N-phenyl-γ-aminopropyltrimethoxysilane.