JPS6361009A - Polymerization of alpha-olefin - Google Patents

Abstract

PURPOSE:To produce fine powder of a polyolefin in high efficiency, by polymerizing an alpha-olefin in the presence of a catalyst produced from a Ti composite component containing Mg, Ti and halogen and an organic Al compound component. CONSTITUTION:An alpha-olefin is polymerized in the presence of a catalyst produced from (A) a composite component obtained by the co-crushing of a mixture consisting of at least 3 components comprising (i) an Mg compound [e.g. MgCl2, MgCl(OC6H5), etc.], (ii) a Ti compound [e.g. TiCl4, Ti(OC2H5)3Br, etc.] and (iii) >=150pts.wt. of an organic halogen compound (e.g. trichloromethane, tetrachloroethane, etc.) based on 100pts. of the component (i) and (B) an organic Al compound [e.g. triethylaluminum, LiAl(C2H5)4, etc.].

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to an α-olefin polymerization method that can efficiently produce fine polyolefin powder. More specifically, it is used in the molding field such as inorganic filler compound molding and powder molding processing, and in the field of additives such as mold release agents, anti-blocking agents, and resin modifiers to improve uniformity and other performance. The present invention relates to a method for producing polyolefin fine powder obtained by fz by a polymerization method.

In the present invention, the term "polymerization" may be used to include copolymerization, and the terms "polymer" and "polyolefin" may be used to include copolymers.

[Conventional technology]

Conventionally, polyolefin powders such as polyolefin and polypropylene have been used in the fields of powder molding processing such as compression molding, powder molding, and fluidized dipping, in the field of manufacturing polyolefin compositions containing inorganic fillers, and as mold release agents, antiblocking agents, and resins. It is used in the field of additives such as modifiers, and in all fields it is required to have excellent uniform dispersibility. Conventionally, methods for producing polyolefin powders used for these purposes include: - Mechanically crushing polyolefin pellets obtained by primary polymerization; and - Grinding a solution or melt of polyolefin obtained by primary polymerization. Known methods include adding polyolefin powder to a poorly soluble medium kept at a high temperature, stirring and dispersing it under high shear, and cooling it to obtain polyolefin powder, and directly obtaining polyolefin powder from the polymerization reaction system during polymerization. However, among these methods, the polyolefin powder obtained by the first mechanical pulverization method is not spherical in shape and has a large average particle size, making it difficult to obtain a uniform molding surface in the powder molding field. There are disadvantages such as the high density of inorganic fillers and poor uniform dispersibility.The shape of one polyolefin powder obtained by the second dissolution and dispersion method is spherical, but it aggregates during the cooling process during production. However, it becomes coarse particles with low bulk specific gravity, and tends to become porous, which is difficult in terms of strength in the field of powder molding processing.In the field of manufacturing compositions containing inorganic fillers, high filling properties and uniform dispersion are required as well as mechanically pulverized powder. In addition, in the method of directly producing polyolefin powder by polymerizing olefins, the average particle size of the obtained polyolefin powder is generally large, or even if the average particle size is small, the particle size distribution and bulk density cannot be controlled. As mentioned above, sufficient performance is required in both the powder processing and molding field, the manufacturing field of compositions containing inorganic fillers, and the field of additives such as mold release agents, anti-blocking agents, and resin modifiers. It was not possible to obtain a spherical fine powder of polyolefin that could exhibit the following properties.

In addition, in the conventional method of producing polyolefin by polymerizing olefin in the presence of a titanium-based Ziegler catalyst, a titanium-containing solid catalyst component and an organoaluminum compound catalyst obtained by co-pulverizing a magnesium compound, a titanium compound, and an organohalogen compound are used. Methods for polymerizing olefins in the presence of catalysts formed from the components are known from many prior documents [JP-A-51-5
No. 5387, No. 51-63887, No. 51-
No. 82385, No. 52-14538?3, No. 53-80382, No. 52-65592,
No. 52-42584, No. 54-10389, No. 54-132689, No. 55-3410, etc.]. However, in all of the methods described in these prior art documents, the particle size of the polyolefin produced is large, and it is difficult to use the polyolefin for applications in the molding field such as inorganic filler compounding molding, powder molding, mold release agents, antiblock agents, and resins. Even if it is used in the field of additives such as modifiers for automobiles, it has the disadvantage of poor uniform dispersibility.

[Problem that the invention seeks to solve]

In view of the above-mentioned situation with conventionally used polyolefin powders, the present inventors have found that in the field of powder molding processing, they have excellent surface appearance of molded products, are resistant to rough skin and whitening due to air bubbles, and are inorganic. In the field of manufacturing filler-containing compositions, it has excellent high-density filling properties and uniform dispersibility,
In the field of additives such as mold release agents, anti-blocking agents, and resin modifiers, we have investigated a method for directly producing polyolefin fine powder with excellent uniform dispersibility by devising an olefin polymerization method, and have identified The inventors have discovered that the above object can be achieved by polymerizing an α-olefin in the presence of a catalyst prepared according to the formulation described above, and have arrived at the present invention.

[Means and effects for solving the problems] According to the present invention, (A) (a) a magnesium compound, (b) a titanium compound, and (c) 150 parts by weight of the magnesium compound (a). A titanium composite component containing at least magnesium, titanium, and a halogen obtained by co-pulverizing a mixture of at least three components of an organic halogen compound in a range of not less than 1 part by weight, and (B) an organic aluminum compound component. Provided is a method for polymerizing α-olefins, which comprises polymerizing α-olefins in the presence of a catalyst.

The titanium catalyst component (A) used as a catalyst component in the method of the present invention includes (a) a magnesium compound, (
b) titanium compound and (c1 the magnesium compound (a
) is a titanium composite containing at least magnesium, titanium, and a halogen obtained by co-pulverizing at least three components of an organic halogen compound in a range of 150 parts by weight per 100 parts by weight of the titanium composite component. In addition to the above-mentioned three components, the titanium composite may contain a d+ electron donor component as necessary.In the titanium composite, each component is in close contact with or reacts with each other. , contains at least a magnesium compound and a titanium compound that are not substantially eliminated by hexane washing at room temperature.In addition, although its chemical structure is unknown, it contains magnesium atoms, titanium atoms, halogen atoms, and in some cases electron donors. It is thought that the two are strongly bonded by mutual bonding action.

In addition, depending on the manufacturing method, it may contain other metal atoms such as aluminum, silicon, tin, boron, germanium, calcium, and zinc, electron donors, or organic groups based thereon, and may further contain inorganic or organic inert diluents such as LiC1, CaC0, BaC1
,,Na,CO3,5rC1,,B,0. , Na2SO
2, Al2O3, Stow, 5IOz ・Ah03, T
iC]z, NaB40t, Ca (PO4)t, CaS
O4, A1. (SO2), ,CaC1,,ZnC1z
, polyethylene, polypropylene, polystyrene, etc. In addition, in order to impart high activity or high activity and high stereoregularity to the polymerization catalyst, an electron donor such as an organic acid ester, an organosilicon compound, or an ether is co-pulverized, and the electron donor or an organic group based thereon is prepared. May contain.

The halogen/titanium atomic ratio contained in the titanium composite component (A) is usually more than 4, preferably 5 or more, and more preferably in the range of 8 to 100, and the magnesium/titanium atomic ratio is usually 3 or more, preferably 5
When the titanium composite component contains an electron donor, the electron donor/titanium (mol/atomic ratio) is usually 0.2 to 6, preferably 0.4 to 3,
It is particularly preferably in the range of 0.8 to 2. The titanium composite component (8) is obtained by co-pulverizing the above-mentioned at least three components, and its average particle size is extremely small, usually in the range of 0.001 to 10 μm, preferably 0.05 to 5 μm. It is. Further, the specific surface area of the titanium composite component is usually 50 m/g or more, preferably 100 to 10QQn? /g, particularly preferably in the range of 100 to 600rrf/g, and the results of X-ray diffraction analysis show that the titanium composite component contains extremely fine crystals of magnesium compound regardless of the type of raw material magnesium compound. I know what you're doing.

In the method of the present invention, the magnesium compound (a
) is preferably a compound containing a halogen and/or an organic group. Specific examples of these include magnesium cybaride, alkoxy halide, allyloxy halide, hydroxy halide, dialkoxide, dialkylation, alkyl alkoxide, acyloxy halide, alkyl halide, aryl halide, dialkyl compound,
Examples include diaryl compounds and alkyl alkoxides. These may exist in the form of adducts with the electron donor described later. It may also be a composite compound containing other metals such as aluminum, tin, silicon, germanium, zinc, and boron. For example, it may be a composite compound of a metal halide, alkyl compound, alkoxy halide, allyloxy halide, alkoxide, alkoxide, etc. of metal such as aluminum and the above-mentioned magnesium compound. Alternatively, it may be a complex compound in which phosphorus, boron, silicon, etc. are bonded to magnesium metal via oxygen.

Of course, these may be a mixture of two or more.

The above-exemplified compounds can usually be represented by a simple chemical formula, but depending on the manufacturing method of the magnesium compound, they may not be represented by a simple formula, and these are usually considered to be a mixture of the above compounds. For example, a method in which magnesium metal is reacted with alcohol or phenol in the presence of halosilane, phosphorus oxychloride, or thionyl chloride;
Compounds obtained by decomposition with compounds having ester bonds, ether bonds, etc. can be considered to be mixtures of various compounds depending on the amount of reaction reagent used and the degree of reaction, but these are of course not applicable to the present invention. It can be used in Various methods are known for producing the above-mentioned magnesium compound, and any of these methods may be used. The magnesium compound may also be pretreated prior to use. For example, there is a method of separating the solid component by dissolving it alone or together with other metal compounds in ether or acetone and then evaporating the solvent or introducing it into an inert solvent.

Alternatively, a method may be adopted in which one or more magnesium compounds or this and other metal compounds are mechanically pulverized in advance.

Among these magnesium compounds, preferred are magnesium cybaride, allyloxy halide, allyloxy group, or composite compounds of these with aluminum, silicon, etc., more specifically MgC1z, MgBrz
, Mg1z, MgF2, MgC1 (OC6H5),
Mg(OCJs)z, MgCI(OC,H,-2-C
)1. ), Mg(OC,11,,-2-CH3)z
, (MgC1z)-(AI(OR), C1z-11
)-1(MgCh)x(Si(OR)-cCla-)
y, [wherein R is a hydrocarbon group such as an alkyl group or an aryl group, and 10 or 7 R's may be the same or different.

0≦3≦3.0≦, ≦4181. is an integer], etc.

Particularly preferred is MgC12.

There are various titanium compounds (g) used for preparing the titanium composite component (A), but they usually have the formula Ti(OR
) A tetravalent or trivalent titanium compound represented by Ji-* or Ti(OR)hXs-h (R is a hydrocarbon group, X is a halogen, O≦, ≦4.0≦1≦4) is suitable. . More specifically, titanium tetrahalides such as TiC1n, TiBr4, Ti14; Ti(OCH3)CH3
, Ti (OCJs) C1s, Ti (On-C4H,)
C1,,Ti (OCJs)Bri,Ti(OisoC
Jq) Trihalogenated alkoxytitanium such as Brs;
Ti(OCHs)zclg, Ti(OCzHshCl
z, Ti(On-CJq)zcl, Ti(OCz)I
s) dihalogenated alkoxy titanium such as zBrz;
Ti (OCH3)CoC1.

Ti(OCzHs)scISTi(On-CJw)sc
Monohalogenated trialkoxytitanium such as 1, Ti(OC,H,), Br: Ti(OCJs), Ti(On
Examples include tetraalkoxytitanium compounds such as -C4H1)4, allyloxy group-substituted halotitanium compounds, and tetraalkoxytitanium compounds. Others, TiC1
Examples include trihalogenated titanium such as 1, TiBr3, and Ti13, and trivalent titanium compounds in which some or all of these halogen groups are substituted with an alkoxy group or an allyloxy group. Preferred among these are tetravalent titanium compounds, and particularly preferred are titanium tetrachloride, tetraalkoxytitanium,
It is an alkoxyhalotitanium.

Further, specific examples of the organic halogen compound (b) used for preparing the titanium composite component (A) include halogenated hydrocarbons, halogen-containing carboxylic acid derivatives (esters, acid halides, etc.), halogenated ketones, etc. , halogenated ethers, halogen-containing silicon compounds, etc. More specifically, dichloromethane, trichloromethane, carbon tetrachloride, dichloroethane, trichloroethane, tetrachloroethane, dichloropropane, trichloropropane,
Halogenated hydrocarbons such as 1.4-dichlorobutane, tert-butyl trichloride, 2.3-dichlorobutane, tert-butyl chloride, 2.3-dichlorobutane, chlorobenzene, benzotrichloride, hexachlorocyclopentadiene, trichloroacetic acid Methyl, ethoxyethyl trichloroacetate, ethyl 2,3,4.4-tetrachloro-3-butenoate, methyl 2,3,4.4-tetrachloro-2-butenoate, perchlorocrotonyl chloride, butyl perchlorocrotonate Examples include halogen-containing carboxylic acid derivatives such as, halogenated ketones such as hexachloroacetone, and halogen-containing silicon compounds such as silicon tetrachloride and silicon trichloride. Among these organic halogen compounds, halogenated hydrocarbons are preferred, and trichloromethane, dichloromethane, tetrachloroethane, etc. are particularly preferred.

The electron donor (d) used as necessary in the preparation of the titanium composite component (A) includes water, alcohol, phenols, ketones, aldehydes, carboxylic acids, esters, ethers, acid amides, and the like. oxygen electron donor,
Nitrogen-containing electron donors such as ammonia, amines, nitriles, and isocyanates, compounds having a 5i-QC bond, and the like can be used. More specifically, methanol,
Alcohols with 1 to 18 carbon atoms such as ethanol, propatool, pentanol, hexanol, octatool, dodecanol, octadecyl alcohol, benzyl alcohol, phenylethyl alcohol, cumyl alcohol, isopropylbenzyl alcohol, phenol, cresol, xylenol, ethyl Phenols having 6 to 15 carbon atoms which may have a lower alkyl group such as phenol, propylphenol, cumylphenol and naphthol; ketones having 3 to 15 carbon atoms such as acetone, methyl ethyl ketone, methyl isobutyl ketone, acetophenone and benzophenone; , C2-C15 aldehydes such as acetaldehyde, propionaldehyde, octylaldehyde, benzaldehyde, tolualdehyde, naphthaldehyde, methyl formate, methyl acetate, ethyl acetate, vinyl acetate, propyl acetate, octyl acetate, cyclohexyl acetate, propionic acid Ethyl, methyl butyrate, ethyl valerate, methyl chloroacetate, ethyl dichloroacetate, methyl methacrylate, ethyl crotonate, ethyl cyclohexanecarboxylate, methyl benzoate, ethyl benzoate, propyl benzoate, butyl benzoate, octyl benzoate, Cyclohexyl benzoate, phenyl benzoate, benzyl benzoate, methyl toluate, ethyl toluate, amyl toluate, ethyl ethyl benzoate,
Methyl anisate, ethyl anisate, ethyl ethoxybenzoate, r-futhiolactone, δ-valerolactone, coumarin, phthalide, ethylene carbonate, etc. with 2 to 1 carbon atoms
8 organic esters, acid halides having 2 to 15 carbon atoms such as acetyl chloride, pencyl chloride, toluyl chloride, anisyl chloride, methyl ether, ethyl ether, isopropyl ether, butyl ether, amyl ether, tetrahydrofuran, anisole,
Ethers having 2 to 20 carbon atoms such as diphenyl ether, acid amides such as acetic acid amide, benzoic acid amide, toluic acid amide, methylamine, ethylamine, diethylamine, tributylamine, piperidine, tribenzylamine, aniline, pyridine, pyrroline, tetra Amines such as methylethylenediamine, acetonitrile,
Examples include nitriles such as benzonitrile and trinitrile, and compounds such as aluminum, silicon, and tin that have these functional groups in their molecules. 5t-0-
Examples of silicon compounds having a C bond include trimethylmethoxysilane, trimethylethoxysilane, dimethyldimethoxylane, dimethyljethoxysilane, diphenyldimethoxysilane, methylphenyldimethoxysilane, diphenyljethoxysilane, ethyltrimethoxysilane, methyltrimethoxysilane, Vinyltrimethoxysilane, phenyltrimethoxysilane, T-chloropropyltrimethoxysilane, methyltriethoxysilane, ethyltriethoxysilane, vinyltriethoxysilane, butyltriethoxysilane, phenyltriethoxysilane, T-aminopropyltriethoxysilane , chlorotriethoxysilane, ethyltriisopropoxysilane, vinyltributoxysilane, ethyl silicate, butyl silicate, trimethylphenoxysilane, methyltriaryloxysilane, vinyltris(β-methoxyethoxy)silane, vinyltriacetoxy silane,
Examples include dimethyltetraethoxydisiloxane and phenyldiethoxydiethylaminosilane. Particularly preferred among these are methyltrimethoxysilane, phenyltrimethoxysilane, methyltriethoxysilane, ethyltriethoxysilane, vinyltriethoxysilane, phenyltriethoxysilane, vinyltributoxysilane, and ethyl silicate. , diphenyldimethoxylane, methylphenylmethoxysilane and the like. Two or more types of these electron donors can be used.

In the method of the present invention, the following method can be adopted as a method for adjusting the titanium composite component (A).

(1) Magnesium compound (a), titanium compound (bl
A method of co-pulverizing a mixture containing three components: and an organic halogen compound (c).

(2) A method in which a mixture containing a magnesium compound (al) and an organic halogen compound (c) is co-pulverized, and then a titanium compound (b) is added and further co-pulverized.

(3) Magnesium compound (al and titanium compound mountain)
After co-pulverizing, an organic halogen compound (c
) and co-grinding.

(4) After pulverizing the magnesium compound, the titanium compound ('b) and the organic halogen compound (c1) are added simultaneously and co-pulverized, or both components are added one after another and co-pulverized.

+51 (A method in which the co-pulverized mixture of 11, (2), (3), and (4) is further subjected to a contact reaction treatment with the above-mentioned tetravalent titanium number, and then the solid portion is separated.

(A method in which the co-pulverized mixture of 61 (11, (2), (3), and (4)) is further subjected to a contact reaction treatment with the above-mentioned organic halogen compound (b), and then the solid portion is separated.

For example,

Regarding +11, (2), (3), and (4) above, the co-pulverized product can be subjected to polymerization without washing with an inert solvent, which is advantageous in preparing the catalyst.

In any of the above preparation methods, when an electron donor is used as a catalyst component, a method of adding the electron donor to any step of the above-mentioned preparation method and co-pulverization can be adopted, It is also possible to adopt a method in which it is added in the form of an adduct or complex with magnesium and co-pulverized, or it is also possible to adopt a method in which it is added in the form of an adduct or complex with a titanium compound and co-pulverized. Also,
During the co-pulverization treatment, the organic or inorganic inert diluent that may be contained in the titanium composite (A), a halogenating agent such as a silicon halogen compound, polysiloxane, and other silicon compounds, Additional components such as aluminum, germanium, tin, or part of a titanium compound may be present, but the electron donor may also be present in the form of an adduct (complex compound) of such a compound. good.

For co-pulverization in the method for preparing the titanium composite component (A), devices such as a rotary ball mill, a vibrating ball mill, and an impact mill can be used. Taking a zero-rotation ball mill as an example, examples include stainless steel m (SUS32), Internal volume 80
0. When 100 stainless steel (SUS32) balls with a diameter of 15 mm are housed in a ball mill cylinder with an inner diameter of 100 mm, and the amount of material to be processed is 20 to 40 g, the number of rotations is 12.
5 rpm for preferably 24 hours or more, preferably 4-layer
Co-pulverization is preferably carried out to the extent equivalent to a pulverization process of 8 hours or more, and the temperature of the pulverization process is usually about 0°C to 100°C. Note that washing the titanium composite with an inert solvent is optional.

Further, the titanium compound (b) used for co-pulverization in the preparation of the titanium composite component (^) is usually o, oos to 1.5 mol, preferably 0.01 to 1.0 mol, per 1 mol of the magnesium compound. , particularly preferably 0.
0.05 to 0.5 mol.

Furthermore, the proportion of the organic halogen compound (c) used during co-pulverization is 150 parts by weight per 100 parts by weight of the magnesium compound.
It is in the range of 200 to 50 parts by weight or more, preferably 200 to 50 parts by weight or more.
00 parts by weight, particularly preferably in the range from 250 to 3000 parts by weight.

As the organoaluminum compound component (B) used as a catalyst component in the method of the present invention, compounds having at least one hel-carbon bond in the molecule can be used, such as the following types of compounds: be able to.

(i) General formula (R')-A l (OR”)nHp
lq (Here, R1 and R2 are hydrocarbon groups containing usually 1 to 15 carbon atoms, preferably 1 to 4 carbon atoms, and may be the same or different from each other. X is a halogen, m
is an organoaluminum compound, ( ii) General formula M'Aj! (R')4 (where,
Ml is Lt, Na or K, R1 is the same as above)
Examples include complex alkylated products of Group 1 metals and aluminum represented by:

As the organoaluminum compounds belonging to the above (i),
Examples include:

General formula (R'), A f (OR") 3-a (where R1 and R1 are the same as above, 0m is preferably 1.
5≦m<3), an organic aluminide represented by the general formula (R'), Alx, -1 (where R1 is the same as above, X represents a halogen, m
is preferably O<m<3), an organoaluminum compound represented by the general formula (R'), %A 11 H3- (where R
1 is the same as above. m is preferably 2≦m<3), an organoaluminum compound represented by the general formula (R'), A 1 (OR2), XQ (where R1 and R2 are the same as above, and X represents a halogen); , Q<m≦3, O≦n<3, O≦p<3, and m
+n+p+q=3).

Among the aluminum compounds belonging to the above (i), more specifically, trialkylaluminum such as triethylaluminum and tributylaluminium, trialkenylaluminum such as triisoprenylaluminum, dialkylaluminum such as diethylaluminum ethoxide, diptylaluminum butoxide, etc. In addition to alkyl aluminum sesquialkoxides such as alkoxide, ethyl aluminum sesquiethoxide, and butyl aluminum sesquibutoxide, general formula (R')
Partially alkoxylated alkylaluminums, dialkylaluminum hydrides such as diethylaluminum chloride, diptylaluminum chloride, diethylaluminum bromide, ethyl Partially halogenated such as alkyl aluminum sesquihalogenides such as aluminum sesquichloride, butyl aluminum sesquichloride, ethyl aluminum sesquipromide, alkyl aluminum dihalides such as ethyl aluminum dichloride, propyl aluminum dichloride, butyl aluminum dibromide etc. dialkylaluminum hydrides such as diethylaluminum hydride, diptylaluminum hydride, partially hydrogenated alkyl aluminum dihydrides such as ethyl aluminum dihydride, probylaluminum dihydride, ethyl partially alkoxylated and halogenated alkylaluminiums, such as aluminum ethoxy chloride, butylaluminum butoxychloride, ethylaluminum ethoxybromide; and (i
) may be an organoaluminum compound in which two or more aluminum atoms are bonded to each other through oxygen atoms or nitrogen atoms. Such compounds include, for example,
(czHs) zA 10A l (cJs) z, (
c4H9) ZAloAJ (c4119)! , (c2
Examples include Hs)2AACA/(cztls)zaHs. Further, these exemplified compounds may be used in combination. Compounds belonging to (ii) above include LiA 1 (cJs) a, LiA j! (c7
Examples include HI s) a.

In addition, in the method of the present invention, in addition to the titanium composite component (A) and the organoaluminum compound component (B), an electron donor component (c) is added to the polymerization system as catalyst components. You can also do Fukagawa. Examples of the electron donor component (c) that can be used in this case include water, alcohol, phenols, ketones, aldehydes, carboxylic acids, esters, ethers, Examples include oxygen-containing electron donors such as acid amides, nitrogen-containing electron donors such as ammonia, amines, nitriles, and isocyanates, and organosilicon compounds having a 5t-0-C bond.

Specifically, α-olefinone used in the method of the present invention includes, for example, ethylene, propylene, 1-butene, 1-hexene, 4-methyl-1-pentene, 1-octene, 1-decene, 1-dodecene, etc. can be exemplified, and further exemplified can be a mixture of two or more of these components. Among these α-olefins, it is preferable to apply the method of the present invention to raw α-olefins that can produce crystalline polymers.

In the method of the present invention, the polymerization reaction can be carried out by either liquid phase Qfi polymerization or gas phase polymerization. When employing the liquid phase suspension polymerization method, hexane, heptane,
Although an inert solvent such as kerosene may be used as the reaction medium,
The α-olefin itself can also be used as the reaction medium. The amount of each catalyst component used is usually 0.0 per reaction volume IIt, when the titanium composite component (A) is converted into titanium atoms.
001 to 1.0 milligram atoms, preferably 0.0
01 to 1.0 milligram atom, and the organoaluminum compound component (B) is usually 100 to 0.01 milligram atom in terms of aluminum atom,
The electron donor (c) is preferably in the range of 10 to 0.1 milligram atoms, and the electron donor (c) added to the polymerization reaction system if necessary is usually 100 to 0.01 mol, preferably 10 to 0.1 mol. range. Further, the ratio of the titanium composite component (A) and the organoaluminum compound component (B) in the reaction system is usually 1 to 1000 in terms of the atomic ratio of aluminum atoms to titanium atoms (Af/Ti),
It is preferably in the range of 10 to 200, and when an electron donor component (c) is used, the ratio of the organoaluminum compound component (8) to the electron donor component (c) is 1 gram atom of aluminum. The number of moles of the donor component is usually in the range of 0.02 to 2 moles.

These catalyst components may be brought into contact during polymerization or may be brought into contact before polymerization, and an electron donor component (
When c) is used, only two arbitrary components of the catalyst components may be selected and brought into contact with each other, or a portion of each component may be brought into contact with the king or the king. The components may be brought into contact with each other before polymerization under an inert gas atmosphere or under an olefin atmosphere.

In the method of the present invention, the polymerization reaction is carried out in a hydrocarbon medium or a hydrocarbon diluent, and the hydrocarbon medium or hydrocarbon diluent may be a raw olefin;
The hydrocarbon medium, a part of which may be a raw material olefin, includes aliphatic hydrocarbons such as propane, butane, pentane, hexane, heptane, octane, decane, dodecane, kerosene, cyclohexane, methylcyclopentane, methyl Examples include aliphatic hydrocarbons such as cyclohexane, and aromatic hydrocarbons such as benzene, toluene, and xylene. In addition, ethiken chloride,
Examples include halogenated hydrocarbons such as chlorobenzene.

In the method of the present invention, when the polymerization reaction is carried out by a liquid phase suspension polymerization method, the temperature is usually 20 to 130°C.
°C, preferably in the range of 50 to 100 °C, and the pressure is usually 0 to 100 kg/cd-G.

It is preferably in the range of 2 to 60 kg/cd-G,
When the polymerization reaction is carried out by gas phase polymerization, the temperature is usually 20 to 120°C, preferably 50 to 10°C.
0, and the pressure is usually between 1 and 100 k
g/cJ-G, preferably 2 to 50 kg/c+a-
It is in the range of G. In the polymerization reaction, the molecular weight is controlled by
Although it can be controlled by changing polymerization conditions such as polymerization temperature and proportions of catalyst components, it is most effective to supply hydrogen to the polymerization reaction system.

In the method of the present invention, a polyolefin can be obtained by treating the reaction mixture after the polymerization reaction in a conventional manner. The polyolefin is a fine powder, and its average particle size is usually 1 to 80 μm, preferably 5 to 6 μm.
It is in the range of 0 μm, and its demand density is usually 0.10 to 0.50 g/ca! , preferably 0.15 to 0.
It is in the range of 40g/cd.

〔Example〕

Next, the present invention will be specifically explained using examples.

Example 1 [Preparation of titanium composite component] 17 g of anhydrous magnesium chloride, 8.7 mZ of tetra-2-ethylhexoxytitanium, and 50 mZ of 1,2-dichloroethane were placed in a stainless steel (SOS-32) type ball 2 with a diameter of 1511 In+ in a nitrogen atmosphere. , 8 kg, and an inner volume of 800 d and an inner diameter of 100 ffl and made of stainless steel (SUS-32), and were brought into contact with each other for 24 hours at an impact acceleration of 7 G. Next, 1.2 of 10011117 was added to the ball mill container under a nitrogen atmosphere.
- Add dichloroethane and further impact acceleration for about 1 hour at 7
After contacting with G, the contents were removed under nitrogen atmosphere.

[Overlapping]

Purified hexane 11 was charged into an autoclave having an internal volume of 21, and triethylaluminum 1.1 was charged under an ethylene atmosphere at room temperature.
A suspension containing 0++u++ol and the titanium composite component taken out from the ball mill container was charged in amounts of Q and Q1 mmol in terms of titanium atoms. The temperature was raised to 70°C, ethylene was introduced, the pressure was increased to 2 kg/cnlG, and polymerization was carried out for 1 hour.

After the polymerization was completed, the slurry containing the produced polymer was filtered and separated into a white powdery polymer and a liquid phase. The yield of white powdery polymer after drying was 91 g.

Table 1 also shows the particle size distribution of the white powdery polymer.

Example 2 [Preparation of titanium composite polymer component] The suspended co-pulverized product obtained in Example 1 was subjected to G4 under a nitrogen atmosphere.
After filtering using a glass filter to separate the solid portion, it was thoroughly washed with purified hexane. The obtained titanium composite component supported 1.7 wt% of titanium atoms.

[Overlapping]

Using the titanium composite component obtained by the above method, Example 1
Polymerization of ethylene was carried out in the same manner as described above.

Comparative Example 1 [Preparation of titanium composite component] 17 g of anhydrous magnesium chloride and 8.7 g of tetra-2-ethylhexoxytitanium were placed in a stainless steel (SLIS-32) type ball 2,8 k with a diameter of 151 mm in a nitrogen atmosphere.
The mixture was charged into a stainless steel (SUS-32) ball mill container with an internal volume of 800-1 and an internal diameter of 100 mm, containing
Contact was made for 24 hours with an impact acceleration of 7G. The co-pulverized product obtained under a nitrogen atmosphere was taken out and suspended in hexane.

Polymerization was carried out in the same manner as in Example 1. The results are shown in Table 1.

Comparative Example 2 The co-pulverized product obtained in Comparative Example 1 was mixed with 1,2-dichloroethane 15
After suspending in 0-, polymerization was carried out in the same manner as in Example 1. The results are shown in Table 1.

Comparative Example 3 [Preparation of titanium composite component] A titanium composite component was prepared in the same manner as in Example 1 of JP-A-57-21403. That is, 20 g of anhydrous magnesium chloride, 1.5 d of ethyl orthoacetate, and 3.5 d of 1,2-dichloroethane were added and pulverized for 40 hours. 10g of the above pulverized product in a 200@Z round bottom flask
After adding 50% of titanium tetrachloride and stirring at 80°C for 2 hours, the supernatant was removed by decantation, and then n
- Thoroughly washed with hebutane.

Using the titanium composite thus obtained, Example 1
Polymerization of ethylene was carried out in the same manner.

The results are shown in Table 1.

Examples 3 to 4 Experiments were conducted in the same manner as in Example 1, except that the Ti compounds and amounts shown in Table 2 were used instead of the tetra-2-ethylhex, sokidititanium-8,7Wi used in Example 1. The results are shown in Table 2.

Example 5 [Preparation of titanium composite component] 17 g of anhydrous magnesium chloride and 8.7 rILl of tetra-2-ethylhexoxytitanium were prepared in a nitrogen atmosphere in a diameter of 1
51 stainless steel (SO3-32) ball 2.8k
The sample was placed in a ball mill container made of stainless steel (SIIS-32) having an internal volume of 800 mZ and an internal diameter of 100 mm, and was brought into contact with it for 24 hours at an impact acceleration of 7 G. 200 rnl of 1,2-dichloroethane was added to the Osei ball mill vessel under a nitrogen atmosphere, and after further contact for 24 hours at an impact acceleration of 7 G, the contents were taken out under a nitrogen atmosphere. Polymerization was carried out in the same manner as in Example 1. The results are shown in Table 3.

Example 6 [Preparation of titanium composite component] 17 g of anhydrous magnesium chloride and 50 ml of 1,2-dichloroethane were placed in a stainless steel tube with a diameter of 151 mm in a nitrogen atmosphere.
A (SUS-32) type ball weighing 2.8 kg was placed in a Rumil container with an internal volume of 80 mm and an internal diameter of b, and was brought into contact with the ball at an impact acceleration of 7 G for 24 hours. Then, in a nitrogen atmosphere royal ball mill container for 20 min.
After adding 0 mZ of 1,2-dichloroethane and 8.7-tetra-2-ethylhexoxytitanium and contacting at an impact acceleration of 7 G for 24 hours, the contents were removed under a nitrogen atmosphere. Polymerization was carried out in the same manner as in Example 1.

The results are shown in Table 3.

Example 7.8 An experiment was conducted in the same manner as in Example 1, except that the 1,2-dichloroethane used in Example 1 was replaced with the compound and amount shown in Table 3. The results are shown in Table 4.

[Brief explanation of drawings]

FIG. 1 is a flowchart showing one example of the preparation of a catalyst for olefin polymerization according to the present invention.

Claims (1)

[Claims] (1) (A) (a) magnesium compound, (b) titanium compound and (c) 100% of the magnesium compound (a)
A titanium composite component containing at least magnesium, titanium, and a halogen obtained by co-pulverizing a mixture consisting of at least three components of an organic halogen compound in a range of 150 parts by weight or more based on the weight part, and (B) an organic A method for polymerizing an α-olefin, which comprises polymerizing an α-olefin in the presence of a catalyst formed from an aluminum compound component.