JPS591403B2 - Method for producing polymerization catalyst component - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing a modified titanium component of an ethylene or α-olefin polymerization catalyst.

The most common Ziegler type catalyst used for the polymerization of ethylene or α-olefins consists of a catalyst component containing a titanium compound and an organoaluminum compound. By crushing titanium trichloride or Ξ titanium chloride composition (Japanese Patent Publication No. 35-14125, Japanese Patent Publication No. 39-24271)
), and by adding various compounds to these titanium compounds and co-pulverizing them (Japanese Patent Publication No. 39-24270), 39-24272, 43-10065, 43-15
620, 49-22315, JP-A-48-68497
, 48-29694, 48-38295, 49-
53196, etc.) Furthermore, by modifying these pulverized products with an organic solvent or a mixture of this and a modifier (Japanese Patent Publications No. 49-1947, No. 49-48638, No. 50-1)
7319, 49-48637, JP-A-48-6417
0, etc.), it is well known that catalyst performance is improved. However, when such pulverization and reforming treatments are performed, the particle size distribution of the resulting titanium catalyst component generally becomes significantly wider, with fine particles of 5 microns or less accounting for 10% by weight or more.

In the polymerization or copolymerization of ethylene or α-olefins using a polymerization catalyst consisting of a titanium catalyst component and an organoaluminum compound, the particle size of the resulting polymer or copolymer is strongly influenced by the particle size of the titanium catalyst component used. box office.

That is, polymers or copolymers obtained using a titanium catalyst component containing a large number of fine particles and having a wide particle size distribution similarly have a wide particle size distribution.
Contains 0% by weight. When the particle size distribution of the produced polymer is wide, especially when the amount of fine powder increases, it becomes difficult to separate the produced polymer from the solvent by filtering, centrifugation, etc., and losses due to dissipation increase in the drying process and pelletizing process.

Therefore, it is necessary to provide extra equipment to prevent these problems and to perform complicated manufacturing operations, so there is a need for improvement. As mentioned above, many methods have been proposed to improve the performance of catalysts.

Among these methods, methods of modifying titanium trichloride raw materials with various modifiers are described, for example, in Japanese Patent Publications No. 49-1947 and No. 49-49.
-48638, JP-A-48-64170, etc. As shown in the comparative examples below, these methods are effective to some extent in terms of improving activity, but the titanium trichloride component becomes finer during the modification process, resulting in the disadvantageous results described above. This is a major drawback for industrial use. An object of the present invention is to provide a Ziegler type titanium catalyst component that has a narrow particle size distribution, has an extremely low content of fine particles, and exhibits highly active catalytic performance.

Another object of the present invention is to provide a method for producing a highly active titanium catalyst component in which the content of fine particles does not increase even when a modification treatment is performed.

The method for producing a titanium catalyst component according to the present invention uses titanium trichloride or a titanium trichloride composition in an amount of about 10% by weight.
The following small amount of ethylene or α-olefin is added to produce an organoaluminum compound represented by the general formula AlRrrlX8-m (wherein R is alkyl or aryl, X is hydrogen or halogen, and m is 1 to 3) co-pulverized with
Next, a modification treatment is carried out by contacting with an inert organic solvent or a mixture of the organic solvent and a modifier. A combination of the organic compound of 1) above and aluminum halide, 3) an organoaluminum compound, and 4)
selected from the group consisting of Lewis acids.

The feature of the present invention is that before carrying out the modification treatment,
The method involves co-pulverizing titanium trichloride or a titanium trichloride composition with the organoaluminium described above in the presence of a small amount of ethylene or α-olefin, thereby preventing an increase in the fine particle content of the pulverized titanium component after the modification treatment. The particle size distribution can be improved.

Here, the term "modification treatment" refers to an operation in which the co-pulverized titanium starting material is brought into contact with an inert organic solvent or a mixture thereof with a modifier, and then classified. Furthermore, in the present text, the term "washing treatment" with an organic solvent is used to mean a modification operation by contacting with an organic solvent. The starting materials in the method of the present invention are titanium trichloride obtained by reducing titanium tetrachloride with hydrogen, a eutectic of titanium trichloride and metal chloride obtained by reducing titanium tetrachloride with a metal, and titanium tetrachloride. All titanium trichloride compositions containing titanium trichloride or titanium trichloride as a main component, such as titanium trichloride compositions obtained by reduction with a compound having a Si-H bond or an organoaluminum compound.

Further, these titanium trichloride and the composition thereof may be used in finely pulverized form. It also includes a pulverized product obtained by co-pulverizing the above titanium trichloride or titanium trichloride composition with various additives described below. The amount of the additive added here is in the range of 0.5 to 100 mol%, preferably 2 to 70 mol%, based on titanium trichloride or the titanium trichloride composition. The addition is usually carried out before the pulverization operation, but it may also be added during the pulverization process or in several portions. General formula A used in co-grinding according to the present invention
lRrrlX3-. Examples of the organoaluminum compounds include triethylaluminum, triisobutylaluminum, diethylaluminum monochloride, diisobutylaluminum monochloride, diethylaluminium monobromide, and ethylaluminum sesquichloride. The amount used is titanium 1 in the starting material.
A range of 0.01 to 100 moles per atom is preferred. The amount of ethylene or α-olefin added during co-grinding is about 10% by weight or less based on the starting material, and the lower limit is usually about 0.01% by weight.

Preferably it is in the range of 0.1 to 10% by weight. α above
- Lower α-olefins such as propylene and butene-1 are used as the olefins. These need not be the same type of monomers used in the catalytic polymerization. The pulverization operation is carried out using a conventional pulverizer for pulverizing powder, such as a ball mill, vibration mill, tower mill, dinit mill, etc., in a state substantially free of oxygen, moisture, and the like.

The pulverization may also be carried out in the presence of a small amount of hydrogen.

The temperature during pulverization is not particularly limited, but is generally -30°C.
Appropriately, the temperature is in the range of 150°C to 150°C and the grinding time is about 1 to 100 hours. The co-pulverized product thus obtained is subjected to a modification treatment by contacting it with an inert organic solvent or a mixture of the organic solvent and a modifier.

In this modification treatment, there are methods in which the co-pulverized material is washed with an organic solvent and separated, a method in which the co-pulverized material is washed with an organic solvent and then brought into contact with a mixture of an organic solvent and a modifier, and separated; Various embodiments can be adopted depending on the starting materials and purpose, such as a method of contacting with a mixture of organic solvents and then separating, or a method of repeatedly contacting with a mixture of different organic solvents or a mixture of an organic solvent and a modifier and then separating. I can do it. Furthermore, another preferred embodiment of the present invention is to subject titanium trichloride or a titanium trichloride composition to a modification treatment before the co-pulverization step, and to further subject the titanium component after co-pulverization to a modification treatment.

This allows the modification effect to be further improved.
The inert organic solvent used in this modification process includes aliphatic, alicyclic, or aromatic hydrocarbons, their halogen derivatives, or mixtures thereof, such as hexane, heptane, and cyclohexane. ,
Benzene, toluene, xylene, monochlorobenzene and the like are preferably used.

The organic solvent is used in an amount of 1 to 500 parts by weight based on the co-pulverized material,
Process at temperatures between 0 and 200°C.

After the treatment, the solvent and the co-ground product are separated by decantation or filtration. Further, depending on the case, the solvent may be removed by further heating under normal pressure or reduced pressure and drying may be performed. Further, these washing and separation operations may be repeated several times. Further, the modifier used in the modification treatment by mixing with the organic solvent is selected from the group consisting of (1) to (4) shown below.

Incidentally, the additives to be co-pulverized in addition to the hihititanium trisalt or the titanium trichloride composition used as the starting material in the method of the present invention described above are also selected from the following group, similar to the modifier. (1) Organic oxygen containing, sulfur, phosphorus, nitrogen,
or silicon compound; (1-1) Organic oxygen-containing compound Ethers, ketones, and esters are used as the organic oxygen-containing compound.

As ethers, the general formula R1-0-R2 (however, Rl
, R2 is an alkyl group, an aralkyl group, a cycloalkyl group, an aryl group, or a halogen substituent thereof.

) Saturated unsaturated ethers or cyclic ether polyethers are used. For example, diethyl ether, di-n-propyl ether, dibenzyl ether, synchhexyl ether, diphenyl ether,
Ditolyl ether, methyl phenyl ether, diallyl ether, putenyl ether, di(4-chlorophenyl) ether, 2-chlorophenyl ether, atrahydrofuran, propylene oxide, diethylene glycol dimethyl ether, diethylene glycol dipropyl ether, ethylene glycol dimethyl ether, ethylene Examples include glycol diphenyl ether and ethylene glycol ditolyl ether.
0 ketones have the general formula R3-C-R
4 (where R3 and R4 represent an alkyl group, an aralkyl group, a cycloalkyl group, an aryl group, or a halogen substituent thereof), or cyclic ketones, ester ketones, or saturated or unsaturated ketones, For example, acetone, diethyl ketone, methyl isobutyl ketone,
Examples include methyl benzyl ketone, acetophenone, diphenyl ketone, cyclohexanone, acetylacetone, allyl phenyl ketone, p-chlorophenyl methyl ketone, methyl tolyl ketone, and the like.

0ゝ011 As esters, general formula R5-C-CR6 (however, R
5, R6 is an alkyl group, an alkenyl group, an aralkyl group,
cycloalkyl group, allyl group, or their halogen substituents) cyclic esters, such as methyl acetate, ethyl acetate, methyl acetoacetate, methyl methacrylate, cyclohexyl acetate, These include benzyl acetate, methyl benzoate, ethyl benzoate, e-caprolactone, and ethyl chloroacetate.

Among these, diethyl ether, diphenylene ether, ditolyl ether, 2-chlorophenyl ether,
Diethyl ketone, diphenyl ketone, methyl acetate, ethyl benzoate and the like are preferred.

(1-2) Organic sulfur-containing compound As the organic sulfur-containing compound, thioethers, thiophenols, and thioalcohols are used.

The above sulfur compounds include saturated or unsaturated thioethers represented by the general formula R7-S R8 (where R7 and R8 are an alkyl group, an aralkyl group, a cycloalkyl group, an aryl group, or a halogen substituent thereof); or cyclic thioethers, such as diethyl thioether, di-n-propyl 5
ruthioether, synchronohexylthioether, diphenylthioether, ditolylthioether, methylphenylthioether, ethyl phenylthioether, propylphenylthioether, dibenzylthioether, J diary'rethioether, allyl phenylthioether, 2-chlorophenylthioether , ethylene sulfide, propylene sulfide, tetramethylene sulfide, etc.

Thiophenols and thioalcohols have the general formula H
-SR9 (where R9 is an alkyl group, an aralkyl group, a cycloalkyl group, an aryl group, or a halogen substituent thereof) is a saturated or unsaturated thiophenol thioalcohol, such as ethylthioalcohol, n- Propylthioalcohol, n-butylthioalcohol, n-hexylthioalcohol, n-dodecylthioalcohol, cyclohexylthioalcohol, benzylthioalcohol, allylthioalcohol, thiophenol, O-methylthiophenol, p-methylthiophenol, 2-chloroethyl Examples include thioalcohol and p-chlorothiophenol.

Among these, particularly preferred are diethyl thioether, di-n-propyl thioether, dibenzyl thioether, diphenyl thioether, methyl phenyl thioether, ethyl phenyl thioether, tetramethylene sulfide, n-dodecyl thioalcohol,
Examples include thiophenol, etc.〇1-3) Organic phosphorus-containing compounds Examples of organic phosphorus-containing compounds include the following general formula (1
) to (XMI) are used.

a) Phosphines represented by the general formula PR (1) (RlO in the general formula is hydrogen, an alkyl group, an aralkyl group,
Indicates a cycloalkyl group or an aryl group.

) For example, ethylphosphine, diethylphosphine, phenylphosphine, diphenylphosphine,
Triethylphosphine, tri-n-furylphosphine, tri-n-decylphosphine, tribenzylphosphine, tricyclohexylphosphine, triphenylphosphine, tritolylphosphine, diethyl n-butylphosphine, ethyldiphenylphosphine, Examples include n-propyl n-butylphenylphosphine and ethylbenzylphenylphosphine.

b) Bosphinus halides represented by the general formula PR and X () (R'' in the general formula represents an alkyl group, a cycloalkyl group, or an aryl group, and X represents a halogen atom.

) For example, dimethylbosphinas bromide, diethylbosphinas chloride, diisopropylbosphinas chloride, methylethylbosphinastalolide, diphenylbosphinas chloride, ethylphenylbosphinas chloride, etc. can be mentioned.

c) Phosphonous dihalides represented by the general formula PRl2X2 () (Rl2 in the general formula represents an alkyl group, an aralkyl group, a cycloalkyl group, or an aryl group, and X represents a halogen atom) Example 5: methylphosphonas dichloride, Examples include methylphosphonas dipromide, ethylphosphonas dibromide, butylphosphonas dichloride, benzylphosphonas chloride, cyclohexylphosphonas dichloride, phenylphosphonas ditalolide, phenylphosphonas dibromide, and the like.

d) Bosfinates represented by the general formula PR Todoroki 3 (0R14) (IV) (Rl3 and R'4 in the general formula represent an alkyl group, an aralkyl group, or an aryl group) such as ethyldiethylbosphinate, ethyldipropyl Bosphinate, ethyldibutylbosphinate, phenyldiphenylbosphinate, ethyldiphenylbosphinate, phenyldibenzylphosphinite, ethylmethylphenylbosphinate and the like can be mentioned.

e) Phosphonites represented by the general formula PRl5(0R16)2) (R'5 and R16 in the general formula represent an alkyl group, an aralkyl group, or an aryl group.

) Dimethyl ethyl phosphonite, diethyl ethyl phosphonite, diethyl butyl phosphonite, diethyl benzyl phosphonite, diethyl phenyl phosphorite, diphenyl methyl phosphonite, diphenylethyl phosphonite, and the like.

f) Phosphites represented by the general formula P(0R17)3 (VD) (Rl7 in the general formula represents a hydrogen atom, an alkyl group, an aralkyl group, a cycloalkyl group, an aryl group, or a halogen substituent thereof.

) For example, dimethyl phosphite, diphenyl phosphite, dioctyl phosphite, trimethyl phosphite, tri(2 chloroethyl) phosphite, tri(n-butyl) phosphite, tribenzyl phosphite, tricyclohexyl phosphite, triphenyl phosphite, tri- (p-tolyl) phosphite, tri-β-naphthyl phosphite, diphenylcyclohexyl phosphite, diphenylpropyl phosphite, and the like.

g) Halogenophosphites represented by the general formula P(0R18)2X(4) (Rl3 in the general formula represents an alkyl group, a cycloalkyl group, or an aryl group, and X represents a halogeno atom).

) Examples include dimethylchlorophosphite, diethylchlorophosphite, di-n-butylchlorophosphite, synchhexylchlorophosphite, diphenylchlorophosphite, dip-trichlorophosphite, and the like.

h) Dihalogenophosphites represented by the general formula P (0R19)

) For example, methyldichlorophosphite, methylchlorofluorophosphite, ethyldichlorophosphite, allyldichlorophosphite, n-butyldichlorophosphite, phenyldichlorophosphite,
Examples include p-chlorophenyldichlorophosphite and 2-chloroethyldichlorophosphite.

1) General formula P(NR?0)3(), P(NR?1)2X
Aminophosphines represented by (X), P(NR?2)

) For example, tris(dimethylamino)phosphine, tris(diethylamino)phosphine, tris(
di-n-butylamino)phosphine phosphorustri (N
-methylanilide), bis(dimethylamino)chlorophosphine, dimethylaminodifluorobosphine? ? Examples include diethylaminodichlorophosphine, (di-n-butylamino)dichlorophosphine, and the like.

J) Phosphates represented by the general formula PO)(0R23)3(4) (R23 in the general formula represents hydrogen, an alkyl group, an aralkyl group, a cycloalkyl group, an aryl group or a halogen derivative group thereof) For example, methyl dihydrodiene phosphate, ethyl dihydrodiene phosphate, n-butyl dihydrodiene phosphate, cyclohexyl dihydrodiene phosphate, phenyl dihydrodiene phosphate, p-chlorophenyl dihydrodiene phosphate, diethyl phosphate, dihydrogen phosphate, n-propyl phosphate, dibenzyl phosphate, diphenyl phosphate, di-α-naphthyl phosphate, dibiphenyl phosphate, triethyl phosphate, nitri(n-
butyl) phosphate, tri(n-amyl) phosphate, tricyclohexyl phosphate, tri(0-chlorophenyno(ha) phosphate, triphenyl phosphate, triphenyl phosphate, trip p-tolyl phosphate, jtri m-tolyl phosphate, tri 4- Examples include biphenyl phosphate and tri(α-naphthyl) phosphate.

k) Phosphorohalogenates represented by the general formula PO(0R24)2X(Xl) (R24 in the general formula represents an alkyl group, a cycloalkyl group, or an aryl group, and X represents a halogen atom.

) Examples include dimethylphosphorochloridate, diethylphosphorochloridate, diisopropylphosphorochloridate, dicyclohexylphosphorochloridate, diphenylphosphorochloridate, and the like.

1) Phosphorodihalogedates represented by the general formula PO (0R25) Roridate, ethylphosphorochloride fluoridate, n-butylphosphorodichloridate, p-tolylphosphorodichloridate, phenylphosphorochloridate, and the like can be mentioned.

m) General formula Ri6P=O(W), (R?7N)3P-0
Phosphine oxides and derivatives thereof represented by (XVI) (R26 and R27 in the general formula represent an alkyl group, an aralkyl group, a cycloalkyl group, or an aryl group) such as trimethylphosphine oxide, tri-n-butylphosphine oxide, Tribenzylphosphine oxide, tricyclohexylphosphine oxide, triphenylphosphine oxide, diallylphenylphosphine oxide, diphenylbenzylphosphine oxide, diphenyl-p-tolylphosphine oxide, tris-N,N dimethylphosphoramide , Tris-N
, N-diethylphosphoramide, etc.

n) Phosphine sulfides represented by the general formula Rζ8P-S (R28 represents an alkyl group, an aralkyl group, or an aryl group in the general formula).

) For example, trimethylphosphine sulfide, triethylphosphine sulfide, tri-n-propylphosphine sulfide, tri-n-butylphosphine sulfide, triphenylphosphine sulfide, diethylphenylphosphine sulfide, diphenyl Examples include benzylphosphine sulfide.

Among these organic phosphorus-containing compounds, triphenylphosphine, triphenylphosphite, triphenylphosphine oxide, triphenylphosphate, triphenylphosphate, and triphenylphosphine are particularly preferred.

1-4) Organic nitrogen-containing compounds Examples of organic nitrogen-containing compounds include amines, isocyanates,
Azo compounds and nitrile compounds are used.

(As amines, the general formula Rλ9NH31 (however, R29
is a hydrocarbon residue, n represents 1 to 3, and a heterocyclic compound containing 0 and nitrogen is used, such as triethylamine, tributylamine, trihexylamine, triphenylamine, N,N'-dimethylaniline, aniline, N Examples include monomethylaniline, butylaniline, dibutylamine, pyridine, quinoline, and 2-chloropyridine.

The general formula R3ONCO (where R3O represents a hydrocarbon residue) is used as the isocyanate, and examples thereof include phenyl isocyanate and toluisocyanate.

As an azo compound, the general formula R3l-N=N-R32 (where R3l and R32 represent a hydrocarbon residue) is used, and for example, as azobenzene and nitriles, the general formula R3
It is represented by 3-CN (where R33 represents a hydrocarbon residue), and examples thereof include acetonitrile and benzonitrile.

1-5) Organic silicon-containing compound As the organic silicon-containing compound, tetrahydrocarbon silane, its halogen or alkoxy derivative, chain or cyclic organopolysilane, siloxane polymer, and other organic silicon compounds are used.

Tetrahydrocarbon silanes and their halogen derivatives have the general formula RIl4SiX4-n (where R34 is a hydrocarbon residue, X is a halogen atom, and n is 1 to 4).

), such as tetramethylsilane, trimethylphenylsilane, tetraphenylsilane, trimethylvinylsilane, ethyltrichlorosilane, diethyldichlorosilane, triethylchlorosilane, phenyltrichlorosilane, diphenyldichlorosilane, vinyltrichlorosilane , diethyldifluorosilane, etc.
As an alkoxy derivative of tetrahydrocarbon silane, the general formula R is also represented by 5Si(0R35)41 (wherein R35 and R36 are hydrocarbon residues, and n represents 1 to 3),
Examples include trimethoxymethylsilane, diethyldiethoxysilane, and triphenylethoxysilane.

Examples of the chain or cyclic organopolysilane include hexamethyldisilane, hexaphenyldisilane, and dodecamethylcyclohexasilane.

Examples of the siloxane polymer include an alkylsiloxane polymer having a skeleton represented by the general formula (where R37 represents hydrogen, an alkyl group, or an aryl group);
Arylsiloxane polymers, alkylarylsiloxane polymers, etc. are used, such as octamethyltrisiloxane, octaethyltrisiloxane, dimethylpolysiloxane, ethylpolysiloxane, methylethylpolysiloxane, hexaphenylcyclosiloxane, diphenylpolysiloxane, and diphenylpolysiloxane. Examples include enyl octamethyl polysiloxane, methyl phenyl polysiloxane, and the like.

Other organic silicon-containing compounds include, for example, hexamethylsilazane, triethylisocyansilazane, triphenylisocyanatosilane, cyanomethyltrimethylsilane, and trimethylsilylacetone.

). ) Combinations of organic oxygen-containing, sulfur, phosphorus, nitrogen or silicon compounds shown in (1-1) to (1-5) and aluminum halides, examples of aluminum halides include aluminum trichloride, aluminum tribromide, aluminum tribromide, Aluminum fluoride and aluminum triiodide are preferred, with aluminum trichloride being particularly preferred. These organic compounds and aluminum halide may be added separately, or may be used in the form of a mixture of the two. The standard molar ratio of the organic compound and aluminum halide is 1:1, but either component may be added in excess. In addition, complexes or reaction products of the above organic compounds and aluminum halides can be used, but in this case, particularly preferred are diphenyl ether/aluminum trichloride complexes and diphenyl ether/aluminum tribromide complexes. ,
Diethyl ether/aluminum trichloride complex, diethyl ketone/aluminum trichloride complex, diphenyl thioether/aluminum trichloride complex, phenyl methyl thioether/aluminum trichloride complex, thiophenol/aluminum trichloride reaction product, diethyl thioether/aluminum trichloride Reaction products, triphenylphosphine/aluminum trichloride complex, triphenylphosphine/aluminum trichloride complex, triphenylphosphate aluminum trichloride complex, tritolyl phosphate/aluminum trichloride complex, trisNN-dimethylphosphoramide/trichloride Examples include aluminum complexes.

The above complex can be synthesized by known methods, but most commonly, it can be easily synthesized by mixing aluminum trihalide and the above-mentioned organic compound at room temperature or by heating the mixture. Can be synthesized.

In addition, in order to synthesize the above complex or reaction product, the molar ratio of the above organic compound and aluminum halide is 1:1.
Although it is preferable to produce the compound under conditions close to , it is also possible to use an excess of either one in free form as a complex or reaction product.

(3) Organoaluminum compound The organoaluminum compound has the general formula AIR'NX'3-o (where R' is a hydrocarbon residue
' represents hydrogen, halogen, or an alkoxy group, and n is 1 to 2), such as diethylaluminum monochloride, diisopropylaluminium monochloride,
Diisobutylaluminum monochloride, dihexylaluminum monochloride, ethylaluminum sesquichloride, isopropylaluminum sesquitalolide, isobutylaluminum sesquichloride, ethylaluminum dichloride, isobutylaluminum dichloride, diethylaluminum monobromide,
Examples include diethylaluminum monofluoride and diethylaluminum monoiodide.

(4) Lewis acids Examples of Lewis acids include titanium tetrachloride, boron fluoride, boron chloride, silicon tetrachloride, vanadium tetrachloride, and phosphorus trichloride.

The amount of these modifiers used is 0.001 for the co-pulverized material.
-100 parts by weight, preferably 0.01-50 parts by weight.

There is no limit to the mixing ratio of the organic solvent and the modifier, but it is determined depending on the types of the organic solvent and the modifier.

The conditions for contacting the mixture of an organic solvent and a modifier with the co-pulverized material are not particularly limited, but generally they are brought into sufficient contact with each other at a temperature in the range of 0 to 200°C, either by standing still or under stirring. Also effective are methods using a Soxley type extractor, a cocurrent contact tower, and the like. After the contact treatment, the solvent and co-ground product are separated by decantation or filtration. Further, depending on the case, the solvent may be removed by further heating under normal pressure or reduced pressure to dry. Furthermore, these operations may be repeated several times. In the modified titanium trichloride or titanium trichloride composition prepared by the method of the present invention, the number of fine particles with a diameter of 5 μm or less is several percent by weight or less, and the width of the particle size distribution is also narrow.

By (co)polymerizing olefins using this modified titanium trichloride or titanium trichloride composition, it is possible to obtain a (co)polymer with an extremely low content of fine powder and a narrow particle size distribution. Furthermore, surprisingly, the polymerization rate is significantly faster in the (co)polymerization of olefins using the modified titanium trichloride (or its composition) according to the present invention, compared to that modified by conventional methods. It has also been found that the polymer obtained has extremely high stereoregularity, which is a completely unexpected effect. The reason why the particle size of the modified titanium trichloride catalyst component is improved by the present invention is believed to be as follows, but the present invention is not limited to this theoretical explanation.

When co-pulverizing starting materials and organoaluminum compounds,
Atomization and agglomeration granulation occurred simultaneously, and at the same time, a small amount of polyethylene or polyα-olefin was produced by the polymerization of coexisting ethylene or α-olefin, which became a kind of coupling agent between the particles and aggregated. It acts to prevent redispersion and atomization of titanium component particles. However, the reason why the modified titanium catalyst component of the present invention exhibits superior polymerization activity and stereoregularity is still not clear. The present invention will be explained below with reference to Examples.

Example 1 Internal volume of approximately 600 m1 containing approximately 80 steel balls with a diameter of 12 mm
Prepare a vibrating mill equipped with a grinding pot.

In the pot, a titanium trichloride/aluminum chloride eutectic (hereinafter referred to as type A) obtained by reducing titanium tetrachloride with metal aluminum in a nitrogen atmosphere
．． Composition: TiCl3・3A1C13) 309, abbreviated as titanium trichloride
was added and ground for 40 hours. (This pulverized product is abbreviated as AA type titanium trichloride in the following examples.) Next, 1.0 ml of diethylaluminium monochloride was added and pulverized for 15 minutes, and then 200 ml of propylene gas was charged.
Time crushed.

The pulverized contents were separated from the steel balls under a nitrogen atmosphere, 150 ml of n-heptane was added to the titanium component 309 obtained, and after stirring at the boiling point of heptane for 20 minutes, the n-heptane was removed by decantation. Ta.

After performing this operation 5 times, the 6th time was to use 150 heptane.
T1Le is added and used as an activated titanium component suspension. Reference Example (Polymerization Example): In a SUS-32 autoclave (inner volume: 210), 11.1% of n-heptane and 0.0% of the above activated titanium component were placed in a nitrogen atmosphere.
459 and diethylaluminum monochloride 1.0m
1 was charged.

After exhausting the nitrogen in the autoclave with a vacuum pump,
1.0 kg of hydrogen in gas phase partial pressure? Then, propylene was charged to set the pressure in the gas phase to 2 kT gauge.

The contents of the autoclave were heated, and after 5 minutes, the temperature of the contents was raised to 70°C, and the polymerization was continued at 70°C. During the polymerization, propylene was continuously fed under pressure to maintain the internal pressure at 5 kg/d gauge. After 3.5 hours, the amount of propylene polymerized is about 5
009, the introduction of propylene was stopped, unreacted gas was discharged, 300 methanol was added, and the mixture was stirred for 30 minutes to decompose the catalyst.

After cooling the autoclave, remove the contents and add 200ml of water.
After washing 3 times at 60℃ with
White polypropylene 4989 was obtained by drying under reduced pressure at 0°C.

The intrinsic viscosity of the obtained polypropylene (measured at 135°C with tetralin, hereinafter the same) was 1.63, and the bulk specific gravity was 0.4.
2 g/ml boiling n-heptane extraction residue (hereinafter referred to as Powder 11 (!:: abbreviated)) was 96.0%.

On the other hand, 229 amorphous polypropylene was obtained by evaporation of the sap. The polymerization activity of the catalyst in this polymerization reaction is 3309/
J-Hr (polypropylene production rate per g of activated titanium per hour, hereinafter the same), and the ratio of the boiling n-heptane extraction residue polymer to the total polymer (hereinafter the total 11
) was 91.9%.

Further, in the dry powder, fine particles with a particle size smaller than 200 mesh (hereinafter abbreviated as fine particles) accounted for 8.3 wt% of the total, and particles finer than 20 mesh and coarser than 100 mesh accounted for 71.0 wt0/0 of the total. Comparative example
1-3 AA type titanium trichloride prepared by the method of Example 1 (Comparative Example 1), catalyst component prepared by the method of Example 1 without charging propylene gas during pulverization (Comparative Example 2), and Example 1
Table 1 shows the results of polymerization carried out in the same manner as in the reference example of Example 1 using a catalyst component (Comparative Example 3) that was not washed with heptane by the method described in Example 1. .

Example 2 A mixture of 309% of type A titanium trichloride and 6.99% of aluminum chloride diphenyl ether complex was mixed with 40% of the mixture in the same manner as in Example 1.
Grinding was continued for 2 hours, then 300d of propylene and 1.0a of diethylaluminum monochloride were added and grinding continued for 2 hours.

The pulverized contents were washed with heptane in the same manner as in Example 1 to obtain an activated titanium component.

Using this, polymerization was carried out in the same manner as in the reference example of Example 1. Polypropylene powder 505f with polymerization time 2.10hr! , amorphous polypropylene 159 was obtained.

The polymerization activity was 550 g/fl-Hr, and the resulting polypropylene powder had an intrinsic viscosity of 1.67 and a bulk specific gravity of 0.
439/WLIl powder 1197.0%, total 1
1 was 94.3%.

The fine particles of the dry powder accounted for 7.3% of the total.

Comparative Example 4 In Example 2, the second stage of pulverization in the coexistence of propylene and diethylaluminum monochloride was omitted, and the catalyst preparation and polymerization were otherwise carried out in the same manner as in Example 2.

With a polymerization time of 2.32 hours, polypropylene 4849 and amorphous polypropylene 169 having an ultimate particle size of 1.58, a powder of 1196.3%, and a bulk specific gravity of 0.409/ml were obtained.

Polymerization activity in this polymerization experiment: 4789/9 Hrl total 11
It was 93.2%. Also, the fine particles of dry powder are 28.
It was 7wt%. Comparing this result with Example 2, the method of the present invention significantly reduces the number of fine particles and improves polymerization activity.
It is clear that all 11 and 11 are improved.

Examples 3 to 74 Catalysts were prepared in the method of Example 2 by adding various components shown in Table 2 instead of the diphenyl ether/aluminum chloride complex used as the additive in the first grinding step.

Table 2 shows the results of polymerization carried out in the same manner. Experiments were also conducted in which various α-olefins were used in place of propylene in the second step of pulverization, as shown in Table 2, and in which various organic solvents were used in place of n-heptane in the washing step.
The cleaning temperature was the boiling point when n-hexane, n-heptane, cyclohexane, benzene, or toluene was used as the solvent, and 100°C when the solvent was monochlorobenzene or xylene (the same applies to the following examples). As a control, Table 2 shows the fine particle content of the resulting polymer when polymerization was carried out using a titanium component obtained by omitting the second pulverization step.

Example 75 In the method of Example 1, AA type TlCl3
Modification treatment was carried out using dibutyl ether as a modifier using a pulverized product obtained by pulverizing in the same manner as above in the coexistence of ethylaluminum monochloride and propylene.

That is, pulverized product 259, n-heptane 150'Rll
After adding 109 g of di-n-butyl ether and stirring for 20 minutes at the boiling point of heptane, the supernatant liquid was removed by decantation. Next, 150 m' of n-heptane was added, stirred for 20 minutes, and n-heptane was removed by decantation.
The washing process was carried out by separating the heptane. After performing this washing process 5 times, in the 6th time, 150 m of n-heptane was used.
1 was added to obtain an activated titanium component suspension. Reference Example (Polymerization Example) Propylene polymerization was carried out in the same manner as in the polymerization example of Example 1 using this activated titanium component of 0.359.

Polypropylene powder 480 with polymerization time 2.33hr
9. Amorphous polypropylene 259 was obtained. Polypropylene powder intrinsic viscosity number 1.65 bulk specific gravity 0.43
9/M. ll powder 1} 96.0%, fine particles 9.30/
It was o.

Polymerization activity in this polymerization reaction: 6199/9・Hr. ．． Total 11
It was 91.2%. Comparative Example 5 In the method of Example 75, the pulverization in the coexistence of diethylaluminium monochloride and propylene was omitted, and AA type TiCl3 was used as a raw material and modified with di-1-butyl ether.

Activity in polymerization reaction 4609/9hr1 total 1190.0%
The fine particles are 45.0%, and the bulk specific gravity of the powder is 0.30.
It was 9/ml.

The polypropylene powder produced in this experiment has an extremely increased number of fine particles and a low bulk specific gravity, so the polymer concentration is approximately 35%.
The polymerization rate significantly decreased near 0.09/l-heptane, demonstrating the effectiveness of the method of the present invention.

Examples 76 to 99 In the method of Example 75, various olefins and organoaluminum compounds as shown in Table 3 were used in place of the propylene and diethylaluminium monochloride used in the pulverization step, and a modifying agent di-1 in the modification treatment was used. Table 3 shows the results of experiments conducted using various modifiers in place of -butyl ether.

Example 100 50 ml of titanium tetrachloride was added to the activated titanium suspension obtained in Example 75 and stirred at 70°C for 20 minutes.
The supernatant was removed by decantation and then washed 5 times with 150 ml of n-heptane to obtain a new activated titanium suspension.

This was used in a polymerization experiment in the same manner as the reference example of Example 1 (using 0.359 as the activated titanium component). After a polymerization time of 1.98 hours, polypropylene powder 15089 and amorphous polypropylene 129 were obtained. Polypropylene powder intrinsic viscosity number 1.60 bulk specific gravity 0.439/Ml
The powder was 1198.00A01 fine particles 9.80A).

The polymerization activity in this polymerization reaction was 7559/9 and the total Cat-Hr was 1195.8%.

Comparative Example 6 The titanium catalyst component obtained in Comparative Example 5 was treated with titanium tetrachloride in the same manner as in Example 100, and compared with Example 100.

Polypropylene powder 408 with polymerization time of 2.33 hours
9. Amorphous polypropylene 179 was obtained.

Polypropylene powder has the highest intrinsic viscosity of 1.60 and bulk specific gravity of 0.30f! /Mll fine particles were 50.8%, and the total polymerization activity in the main polymerization reaction was 5219/9·Hrl 1193.0%.

Comparing this result with the result of Example 100, it is found that if the pulverization step in the coexistence of the organoaluminum compound and olefin in the preparation of the titanium catalyst component used in the present invention is omitted, the number of fine particles of the main polymer increases greatly, and the bulk increases. It is clear that the specific gravity also decreases, which is a major drawback as a polymerization catalyst.

Examples 101 to 107 The catalyst components prepared in Examples 76, 82, 83, 86, 92, 95, and 97 were further treated with titanium tetrachloride in the same manner as in Example 100 to obtain an activated titanium suspension.

Table 4 shows the results of polymerization using 0.35 f1 of this activated titanium component in the same manner as in the reference example of Example 1. For comparison, the amount of fine particles and the bulk specific gravity of polypropylene powder polymerized using a catalyst component in which the pulverization in the coexistence of diethylaluminium monochloride and propylene was omitted are also shown.

Example 108 Type AA titanium trichloride 409, n-heptane 150ml, di-n-butyl ether 107111 were stirred for 20 minutes at the boiling point of heptane, and then the n-heptane was removed by decantation.

n-heptane 150T! Add 11 and stir in the same manner,
After repeating the decantation washing process 5 times,
It was dried by heating at 0° C. for 20 minutes under a reduced pressure of 500 Hg.
The obtained dried product 309 was placed in a vibration mill and 1.0 m of diethylaluminum monochloride was added in the same manner as in Example 1.
1 for 15 minutes, then 200 ml of ethylene was added and the mixture was crushed for 3 hours. Pulverized product and n-heptane 150
Add 20ml of m11 di-n-butyl ether, stir for 20 minutes at the boiling point of n-heptane, remove the supernatant, and add n-butyl ether.
The washing treatment with 150 ml of heptane was repeated three times.

Next, n-heptane 150TLe1 titanium tetrachloride 50ml
After stirring at 70°C for 20 minutes, washing with n-heptane was repeated 3 times.
ml was added to obtain an activated titanium component suspension. Reference example (
Polymerization Example) Polypropylene powder 5139 and amorphous polypropylene 59 were obtained by carrying out polymerization in the same manner as in the reference example of Example 1 using 0.25 g of the above activated titanium component, and in a polymerization time of 2.0 hr.

The intrinsic viscosity of the obtained polypropylene powder was 1.58.
, bulk specific gravity 0.439/Mll powder 1198.0%
, the fine particles were 8.9%.

Activity in main polymerization reaction 10369/9・Hrl total 1197
．． It was 0%.

Comparative Example 7 Same as the reference example of Example 108, except that the method of Example 108 omitted the pulverization treatment in the coexistence of an organoaluminum compound and ethylene, and performed the di-n-butyl ether treatment twice and the titanium tetrachloride treatment. Polymerized to.

Polypropylene 357f with polymerization time of 2.5 hours! , amorphous polypropylene 109 was obtained.

Polypropylene powder intrinsic viscosity number 1.55, bulk specific gravity 0.29, powder 1197.0%, fine particles 52.3%
and polymerization activity 5879/g・Hrl total 1194.4
It was 010.

A high-performance catalyst cannot be obtained by simply repeating the reforming process in this way.

Comparative Example 8 The catalyst components were prepared and polymerized in the same manner as in Example 108, except that diethylaluminum monochloride and ethylene were not added and the catalyst was ground.

Polypropylene powder 4079 with polymerization time of 2.5 hours
, amorphous polypropylene 109 was obtained.

The intrinsic viscosity of polypropylene powder is 1.61, the bulk specific gravity is 0.301, the powder is 1197.3%, the fine particles are 48.7%, and the polymerization activity is 6671/l-Hrl, total 1195.0%.
It was hot.

Comparing this with Example 108, in Comparative Example, there are many fine particles of the produced polymer, the bulk specific gravity is low, and the activity and total 11 are also low, indicating that the special crushing operation of the titanium catalyst component of the present invention is effective.

Example 109 AA type titanium trichloride 409, diphenyl ether 3.7
g, 3.2 g of aluminum chloride was placed in a vibrating mill pot, pulverized for 40 hours, washed with n-heptane in the same manner as in Example 2, then 150 ml of n-heptane, 20 ml of diisoamyl ether were added, and stirred at 70°C for 20 minutes. After washing three times with 150 d of n-heptane, at 50°C.
It was dried under reduced pressure at 1 ml/LHg.

30g dry matter, 1 diethylaluminum monochloride
．． After adding 0ml of propylene and grinding for 15 minutes, add 30ml of propylene.
0d was charged over 1 hour while being pulverized, and pulverization was continued for 2 hours.

150ml of n-heptane was added to the obtained pulverized product 251.
After adding 20 ml of diisoamyl ether and stirring at 70°C for 20 minutes, the supernatant liquid was removed by decantation.
Washed twice.

Next, add 150 ml of n-heptane and 50 ml of titanium tetrachloride, stir at 70°C for 20 minutes, and then add n-heptane to n-heptane.
- Washed five times with boiling heptane to obtain an activated titanium component suspension.

Reference Example (Polymerization Example): Polymerization was carried out in the same manner as in the Reference Example of Example 1 using the obtained activated titanium 0.209.

Polypropylene powder 5239 with polymerization time of 2.0 hr.
, amorphous polypropylene 49 was obtained.

The obtained polypropylene powder has a limiting viscosity number of 1.57.
, powder 1198.10A), bulk specific gravity 0.439/
The Mll fine particles were 7.3%. The polymerization activity in this polymerization reaction was 13209/9 hr and a total of 1197.40/o.

Comparative Example 9 The catalyst component was prepared and polymerized in the same manner as in Example 109, except that the second pulverization in the catalyst component production process of Example 109 was carried out without the addition of diethylaluminum monochloride and propylene. .

Polypropylene powder 3589 with polymerization time of 2.3 hours
, amorphous polypropylene 7f! was obtained, the intrinsic viscosity of the polypropylene powder was 1.57, and the bulk specific gravity was 0.309.
/Mll powder was 1197.39%, and the fine particles were 48.7%.

Polymerization activity in this polymerization reaction: 7939/g・Hrl total: 195
．． It was 49.

Examples 110 to 116 (reference example) Example rows 2, 7, 73, 83, 100, 108 and 109
Bulk polymerization of propylene was carried out using the catalyst component synthesized in the following method.

That is, a predetermined amount of activated titanium component suspended in 30 ml of heptane and 0.8 ml of diethylaluminum monochloride were charged into a 610 SUS-32 autoclave with an internal volume of 610 under a nitrogen atmosphere. After evacuating the nitrogen in the autoclave using a vacuum pump, hydrogen and 2N11 propylene 2.5k9 were charged into the autoclave. The contents of the autoclave are heated to an internal temperature of 60°C after 15 minutes.
The temperature was raised to 60°C, and polymerization was carried out at 60°C. After 5 hours, the autoclave was cooled, the contents were taken out and dried under reduced pressure at 60°C to obtain polypropylene.

The experimental results are shown in Table 5. For comparison, Table 4 also shows the fine particles and bulk specific gravity of polypropylene powder obtained by polymerization using a catalyst component prepared without the coexistence of an organoaluminum compound and olefin during catalyst component crushing.

Example 117 Titanium tetrachloride 200rnM,. Put n-hexane 1007TLe into a No. 11 round bottom flask equipped with a stirrer, cool it to 0°C, drop a solution of 220mM diethylaluminum monochloride and 200ml n-hexane over 2 hours, stir at room temperature for 3 hours, and then add to the top. The clear liquid was removed by decantation, washed three times with 300 ml of n-hexane at room temperature, and then heated at 50°C at 1 mmH.
g and dried under reduced pressure.

Titanium trichloride composition 309 thus obtained by the reduction reaction
was charged into a vibrating mill pot and pulverized for 20 hours,
1.0 ml of triethylaluminum was added and pulverized for 15 minutes, and 200 ml of ethylene was added and pulverization was continued for 3 hours.

After adding the obtained pulverized product 259, 150 ml of n-hexane and 20 ml of di-1s0-butyl ether and stirring for 20 minutes, the supernatant liquid was removed by decantation.
Washing was performed five times using 150 ml of n-hexane at a temperature of the boiling point of n-hexane to obtain an activated titanium component suspension, which was used to polymerize ethylene.

Reference Example (Polymerization Example): 1 ml of heptane, 0.109 ml of the above activated titanium, and 0.5 ml of diethylaluminum monochloride were charged into an autotale having an internal volume of 21 ml under a nitrogen atmosphere.

After exhausting the nitrogen in the autoclave with a vacuum pump,
Hydrogen was charged at a partial pressure of 2.0 kg/d, and then ethylene was charged to bring the pressure in the gas phase to 4 kg/(7 LG). After 20 minutes of heating the contents of the autoclave, the internal temperature rose to 9.
Polymerization was continued at 0°C.

During polymerization, ethylene is continuously pressurized to maintain an internal pressure of 9.5K.
g/CmG. After 2.5 hours of polymerization, the introduction of ethylene was stopped, unreacted gas was discharged, and 300 ml of methanol was added and stirred for 30 minutes to decompose the catalyst.

The contents of the autoclave were taken out, washed three times with 200 ml of water, filtered, and dried under reduced pressure at 60°C to obtain white polyethylene powder 5209.

The resulting polyethylene had an intrinsic viscosity of 2.23 and a bulk specific gravity of 0.
．． 439/Mll fine particles was 5.3%, and the activity in the main polymerization was 20809/9·Hr.

Example 118 (Reference Example) Using the catalyst prepared in Example 109, copolymerization of ethylene and propylene was carried out by blowing a mixed gas with propylene containing 1 m01% of ethylene instead of propylene.

The bulk specific gravity of the obtained polypropylene powder is 0.42
The amount of fine particles was 6.0%, indicating that the present invention is also effective in copolymerization reactions.

Claims (1)

[Claims] 1. Titanium trichloride or a titanium trichloride composition is prepared by adding a small amount of ethylene or α-olefin of about 10% by weight or less to the titanium trichloride or titanium trichloride composition to form a titanium trichloride or a titanium trichloride composition with the general formula AlR_mX_3_-_m(
Here, R is an alkyl group or an aryl group, X is hydrogen or a halogen, and m is 1 to 3). and a modifier, and the modifier is 1)
Oxygen-containing, sulfur, phosphorus, nitrogen or silicon organic compounds, 2)
A method for producing a modified titanium component of an ethylene or α-olefin polymerization catalyst selected from the group consisting of a combination of an organic compound and an aluminum halide in 1) above, 3) an organoaluminum compound, and 4) a Lewis acid. 2. Claim 1, wherein the titanium trichloride or titanium trichloride composition is subjected to the above modification treatment before the co-pulverization step, and the titanium component after co-pulverization is further subjected to the above modification treatment. A method for producing the modified titanium component described. 3. The method for producing a modified titanium component according to claim 1, wherein the titanium trichloride or titanium trichloride composition is pulverized in the presence or absence of additives. 4 The above additive is from the group consisting of 1) an oxygen-containing, sulfur, phosphorous, nitrogen or silicon organic compound, 2) a combination of the above 1) organic compound and aluminum halide, 3) an organoaluminum compound, and 4) a Lewis acid. A method for producing a modified titanium component according to claim 3, which is selected.