JPS5840567B2 - Manufacturing method of polymerization catalyst component - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing a titanium catalyst component of a Ziegler type catalyst.

The polymerization or copolymerization of ethylene or alpha-olefins using Ziegler-type catalysts is well known.

The most common Ziegler type catalyst consists of a catalyst component containing a titanium compound and an organic aluminum.

Grinding of titanium trichloride or titanium trichloride composition (% Kosho 3
5-14125, Japanese Patent Publication No. 39-24271), co-pulverization with various modifiers (Japanese Patent Publication No. 39-24270゜No. 39)
-24272, 43-10065, 43-1562
0° 49-22315, 48-68497, 48-29694, 48-38295, 49-53
196), and a modification treatment in which the pulverized product is brought into contact with an organic solvent or a mixture of this and a modifier and separated. , Japanese Patent Application Publication No. 1973-
64170) is also known to improve catalyst performance.

However, although these treatments partially improve catalyst performance, they are still insufficient; for example, polymerization activity improves but stereoregularity decreases, or both polymerization activity and stereoregularity improve. However, there are various drawbacks such as deterioration of particle size characteristics.

In particular, when a modification treatment such as solvent washing of the pulverized titanium component is performed, the titanium component particles become finer and their particle size distribution becomes wider, with fine particles of 5 microns or less having a weight of 1O2 or more.

On the other hand, ethylene or α-
In the (co)polymerization of olefins, the particle size of the (co)polymer product produced is strongly influenced by the particle size of the titanium catalyst component used.

That is, a polymer obtained by polymerization using a titanium component containing a large amount of fine particles and having a wide particle size distribution similarly has a wide particle size distribution and usually contains 10 to 30 square meters by weight of fine powder of 50 microns or less.

As described above, 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 filtration, centrifugation, etc., and losses due to dissipation increase in the drying process and pelletizing process. .

Therefore, in order to prevent these problems, it is necessary to provide extra equipment and perform complicated manufacturing operations, so there is a demand for improvement.

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 after improvement treatment.

The method for producing a titanium catalyst component according to the present invention includes (1) adding an inert organic solvent and a modifier to titanium trichloride or a titanium trichloride composition and performing a wet pulverization treatment; Washing and separation with a solvent, (3) Next, dry pulverization treatment, (4) Further, a modification treatment in which the pulverized product is brought into contact with an inert organic solvent or a mixture of this and a modifier and separated (5) ) In the above process, titanium trichloride or titanium trichloride composition is A small amount of ethylene or α-olefin of about 10 weight φ or less is added to the product, and the general formula AlRm
3-m (where R is an alkyl group or an aryl group, X is hydrogen or halogen, and m is 1 to 3)
By co-pulverizing with an organoaluminum compound represented by combined, (I[D organoaluminum compound and (lψ Lewis acid).

The starting material for preparing the titanium catalyst component in the present invention is 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, or Titanium tetrachloride S i -Hj
The titanium trichloride composition obtained by reduction with a compound having an @ bond or an organoaluminum compound includes titanium trichloride or all titanium trichloride compositions containing titanium trichloride as a main component.

Further, these titanium trichloride or titanium trichloride compositions may be used in finely pulverized form.

The above starting material is processed in accordance with the invention in stages as described below.

(1) Process of adding an inert organic solvent and a modifier to the titanium starting material and wet-pulverizing it: Wet-pulverizing enables efficient pulverization of the titanium starting material, prevention of agglomeration of the finely pulverized material, and the resulting good interaction with the modifier. contact is achieved.

Although the pulverization mechanism and the structure of the pulverized product have not yet been fully elucidated, the dissolution of soluble components produced during the treatment into the inert organic solvent is promoted.

Inert organic solvents used here include aliphatic, alicyclic or aromatic hydrocarbons, their halogen derivatives and mixtures thereof, such as hexane, heptane, cyclohexane, benzene, toluene, xylene, monochloro Benzene and the like are preferred.

The modifier added together with the inert organic solvent is as follows (i
) to (IVI).

([) Organic oxygen-containing, sulfur, phosphorus, nitrogen, or silicon compound (ia) Organic oxygen-containing compound/As the organic oxygen-containing compound, ethers, ketones, and esters are used.

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

), saturated or unsaturated ethers, cyclic ethers, or polyethers are used.

For example, diethyl ether, di-n-furoyl ether,
Dibenzyl ether, dicyclohexyl ether, diphenyl ether, ditolyl ether, methylphenyl ether, diallyl ether, futhynyl~
1 ether, di(4
Examples include 10-chlorophenyl ether, 2-chlorophenyl ether, tetrahydrofuran, propylene oxide, diethylene glycol dimethyl ether, diethylene glycol dimethyl ether, ethylene glycol dimethyl ether, ethylene glycol diphenyl ether, and ethylene glycol ditolyl ether.

Ketones include saturated or unsaturated ketones represented by the general formula R3-C-R4 (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, such as 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.

As esters, general formula R5-C-0R6 (however, R
5, R6 is an alkyl group, an alkenyl group, an aralkyl group,
cycloalkyl group, aryl group, or a halogen substituent thereof), saturated or unsaturated esters and cyclic esters, such as methyl acetate, ethyl acetate, methyl acetoacetate, methyl methacrylate,
These include cyclohexyl acetate, benzyl acetate, methyl benzoate, ethyl benzoate, ε-caprolactone, and ethyl chloroacetate.

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

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

The above sulfur compound is a saturated or unsaturated thioether represented by the general formula R7-8-R8 (where R7 and R8 are an alkyl group, an aralkyl group, a cycloalkyl group, an aryl group, or a halogen substituent thereof) kind,
Alternatively, cyclic thioethers are used, such as diethyl thioether, di-n-propyl thioether, dicyclohexyl thioether, diphenyl thioether,
ditolyl thioether, methylphenyl thioether,
Examples include ethylphenyl thioether, propylphenyl thioether, dibenzyl thioether, diallyl thioether, allyl phenyl thioether, 2-chlorophenyl thioether, ethylene sulfide, propylene sulfide, and tetramethylene sulfide.

Thiophenols and thioalcohols include saturated or unsaturated thiophenols represented by the general formula H-8R9 (where R9 is an alkyl group, an aralkyl group, a cycloalkyl group, an aryl group, or a halogen substituent thereof); Thioalcohols, such as ethyl-F-off'alcohol, n-propyl, thioalcohol, n-butylthioalcohol, n-hexylthioalcohol, n-dodecylthioalcohol, cyclohexylthioalcohol, benzylthioalcohol, Examples include ruthioalcohol, thiophenol, O-methylthiophenol, P-methylthiophenol, 2-chloroethylthioalcohol, P-chlorothiophenol, and nato.

Among these, particularly preferred are diethylthioether, di-n-propylthioether, dibenzylthioether, diphenylthioether, methylphenylthioether, ethylphenylthioether, tetramethylene sulfide, n-dodecylthioalcohol, thiophenol and the like.

(!-c) Organic phosphorus-containing compound The following general organic phosphorus-containing compounds are used: Compounds represented by formulas (I) to 0) are used.

b) Phosphine represented by the general formula P RA'(I) (
RIO in the general formula represents hydrogen, an alkyl group, an aralkyl group, a cycloalkyl group, or an aryl group.

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

) Phosphinus halides represented by the general formula Rg

) Examples include dimethylphosphinas bromide, diethylphosphinas chloride, diisopropylphosphinas chloride, methylethylphosphinas chloride, diphenylphosphinas chloride, ethylphenylphosphinas chloride, and the like.

7 Phosphonous cybarides represented by the general formula PR12X2 (ID (R12 in the general formula represents an alkyl group, an aralkyl group, a cycloalkyl group, or an aryl group, and X represents a halogen atom).

) e.g. methylphosphonas dichloride, Methylphosnath dibromide, ethylphos Suphonas dibromide, butylphosphona dichloride, benzylphosphonasc loride, cyclohexylphosphonasdi Chloride, phenylphosphonas dichloride Ride, phenylphosphonas dichloride I can give you things like de.

2) Phosphinites represented by the general formula PR3(OR14) (IV) (R13R14 in the general formula represents an alkyl group, an aralkyl group, or an aryl group) such as ethyl diethyl phosphinite, ethyl dipropylphosphinite, Examples include ethyldibutylphosphinite, phenyldiphenylphosphinite, ethyldiphenylphosphinite, phenyldibenzylphosphinite, and ethylmethylphenylphosphinite.

e) Phosphonites represented by the general formula PB15(OR'')2(V) (R15°R16 in the general formula represent an alkyl group, an aralkyl group, or an aryl group.

) Dimethylethylphosphonite, diethylethylphosphonite, diethylbutylphosphonite, diethylbenzylphosphonite, diethylphenylphosphonite, diphenylmethylphosphonite, diphenylethylphosphonite, and the like.

) Phosphites represented by the general formula P(OR17)3 (■) (R17 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, tridichlorohexyl phosphite, triphenyl Examples include phosphite, tri(P-tolyl) phosphite, tri-β-naphthyl phosphite, diphenylcyclohexyl phosphite, diphenylpropyl phosphite, and the like.

g) Halogenophosphites represented by the general formula P (OR'8 )2X (■) (R18 in the general formula represents an alkyl group, a cycloalkyl group, or an aryl group, and X represents a halogen atom.

) For example, dimethylchlorophosphite, diethylchlorophosphite, dipheny dichlorophosphite, dicyclohexyl Silchlorophosphite, diphenylc Rolophosphite, diP-tolylchloro Phosphite, etc. can be mentioned.

H) Dihalogenophosphites represented by the general formula P (OR19)

) For example, methyl dichlorophosphite, Methylchlorofluorophosphite, tildichlorophosphite, aryldik Rolophosphite, n-butyldichloro Phosphite, phenyldichlorophosph P-chlorophenyldichlorophore Sphite, 2-chloroethyldichloro Phosphites etc. can be given.

) General formula P (NR Akira 0) 3 (lX), P (NR Ku 1)
2X(X), P (N R12)X2(X[l
, R22 represents an alkyl group or an aryl group, and X represents a halogen atom.

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

n) Phosphates represented by the general formula P (0) (OR23) 3@ (R23 in the general formula represents hydrogen, an alkyl group, an aralkyl group, a cycloalkyl group, an aryl group, or a halogen-derived group thereof) For example, methyldi Hydrodiene phosphate, ethyl dihydrogen phosphate, n-butyl dihydrogen phosphate, cyclohexyl dihydrogen phosphate, phenyl dihydrogen phosphate, P-chlorophenyl dihydrogen phosphate, diethyl phosphate, dihydrogen phosphate, -7'lopyl phosphate, dibenzyl phosphate, diphenyl phosphate,
Diα-naphthyl phosphate, diphenyl phosphate, triethyl phosphate, tri(n-butyl) phosphate, tri(n-amyl) phosphate, tricyclohexyl phosphate, tri(0-chlorophenyl) phosphate, triphenyl phosphate, tri-P-tolyl phosphate , tri-m-tolyl phosphate, tri-4-biphenyl phosphate, tri(α-naphthyl) phosphate, and the like.

) General formula P (0) (OR24) 2
II) T: Phosphorochloridates shown (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.

(w) Phosphorochloridates represented by the general formula P(0)(OR25)X2 (R25 in the general formula represents an alkyl group or an aryl group, and X represents a halogen atom.

) For example, methyl phosphorodichloride ethyl phosphorodichloridate, ethyl phosphorodichloridate, Tylphosphorochloride fluoridate, n-butyl phosphorodichloridate, P -Tolyl phosphorodichloridate, Give nylphosphorodichloridate etc. I can do it.

W) General formula RB6p = o (xv), (RH7N
)3P=o(XVD Phosphine oxytos and derivatives thereof (R26°R27 in the general formula represent an alkyl group, an aralkyl group, a cycloalkyl group, or an aryl group.

) For example, trimethylphosphineoxy and tri-n-butylphosphine oxyto.

tribenzylphosphine oxide, tricyclohexylphosphine oxide, triphenylphosphine oxide, diallylphenylphosphine oxide, diphenylbenzylphosphine oxide, diphenyl-P-)lylphosphine oxide, tris-N,
Examples include N-dimethylphosphoramide, tris-N, and N-diethylphosphoramide.

(R23 in the general formula represents an alkyl group, an aralkyl group, or an aryl group.

) Examples include trimethylphosphine sulfide, triethylphosphine sulfide, tri-n-furobylphosphine sulfide, tri-n-butylphosphine sulfide, triphenylphosphine sulfide, dimethylphosphine sulfide, diphenylbenzylphosphine sulfide, and the like.

Among these organic phosphorus-containing compounds, triphenylphosphine, triphenylphosphite, triphenylphosphine oxyto, triphenylphosphate, tri-P-tolylphosphate, and the like are particularly preferred.

(i-d) Organic nitrogen-containing compound As the organic nitrogen-containing compound, amines, isocyanates, azo compounds, and nitrile compounds are used.

The amines have the general formula R2,' N R3-n (wherein R29 is a hydrocarbon residue and n is 1 to 3).

) and nitrogen-containing heterocyclic compounds, such as triethylamine, tributylamine, trihexylamine, triphenylamine, N,N'-dimethylaniline,
Examples thereof include aniline, N-methylaniline, butylamine, dibutylamine, pyridine, quinoline, and 2-tripyridine.

The general formula R''NC0 (where Boo represents a hydrocarbon residue) is used as the isocyanate, and examples thereof include phenyl isocyanate and tolyl isocyanate.

As an azo compound, the general formula n31- N=N -n32
(However, R31 and R32 represent a hydrocarbon residue) are used, such as azobenzene, and 2) IJ groups are represented by the general formula R33-ON (wherein R33 represents a hydrocarbon residue), such as Examples include acetonyl, IJ, and benzonitrile.

(1-e) 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 R<S t X4-n (where R34 is a hydrocarbon residue, X is a halogen atom, and n
indicates 1 to 4.

), such as tetramethylsilane, trimethylphenylsilane, tetraphenylsilane, trimethylvinylsilane, ethyltrichlorosilane, diethyldichlorosilane, triethylchlorosilane, phenyltrichlorosilane, diphenyldichlorosilane, vinyltrichlorosilane, diethyldifluorosilane. Examples include silane.

The alkoxy derivative of tetrahydrocarbon silane has the general formula R3,1iSi(OR”)4-n
(However, in R85 and R36, the hydrocarbon residue n is 1 to
3), examples of which include trimethoxymethylsilane, diethyljethoxysilane, and triphenylethoxysilane.

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

Examples of siloxane polymers used include alkylsiloxane polymers, arylsiloxane polymers, and alkylarylsiloxane polymers having skeletons represented by general formulas, alkyl groups, and aryl groups, such as octamethyltrisiloxane, Examples include octaethyltrisiloxane, dimethylpolysiloxane, ethylpolysiloxane, methylethylpolysiloxane, hexaphenylcyclosiloxane, dimethylpolysiloxane, diphenyloctamethylpolysiloxane, methylphenylpolysiloxane, and the like.

Examples of other organic silicon-containing compounds include hexamethylsilazane, triethylisocyadisilazane, triphenylisocyanatosilane, cyanomethyltrimethylsilane, and trimethylsilylacetone.

(ii) Combinations of organic oxygen-containing, sulfur, phosphorous, nitrogen or silicon compounds represented by (ia) to (ie) with aluminum halides. Examples of aluminum halides include aluminum trichloride;
These include aluminum tribromide, aluminum trifluoride, and aluminum misawadide, 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 molar ratio of organic compound and aluminum halide is 1:1
is standard, but either component may be added in excess.

In addition, a complex or a reaction product of the above organic compound and aluminum halide can be used, but in this case, diphenyl ether is particularly preferred.
Aluminum trichloride complex, diphenyl ether/aluminum tribromide complex, diethyl ether/aluminum trichloride chain, diethyl ketone/aluminum trichloride complex,
diphenylthioether/aluminum trichloride complex, phenylmethylthioether/aluminum trichloride complex,
Thiophenol/aluminum trichloride reaction product, diethylthioether/aluminum trichloride reaction product, triphenylphosphine/aluminum trichloride complex, triphenylphosphite/aluminum trichloride complex, triphenyl phosphate/aluminum trichloride complex, trichloride Examples include tolyl phosphate/aluminum trichloride complex, trisN, N-dimethylphosphoramide/aluminum trichloride complex, and the like.

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

In addition, in order to synthesize the above-mentioned complex or reaction product, the molar ratio of the above-mentioned organic compound and aluminum halide is 1:
It is preferable to produce the compound under conditions close to 1, but an excess of either one may be used as a complex or a reaction product.

01 [) Organoaluminum compound The organoaluminum compound has the general formula Ai'nX'8-n (where R' is a hydrocarbon residue, X' is hydrogen, halogen, or an alkoxy group, and n is 1
~2), for example, diethylaluminum monochloride, diisopropylaluminum monochloride, diisobutylaluminum monochloride dihexylaluminum monochloride, ethylaluminum sesquichloride, isopropylaluminum sesquichloride isobutylaluminum sesquichloride, ethylaluminum dichloride, isobutylaluminum Examples include dichloride, diethylaluminium monobromide, diethylaluminium monofluoride, diethylaluminium heptanoiodide, and the like.

OX/) Lewis acid Lewis acids include titanium tetrachloride, boron fluoride, boron chloride, silicon tetrachloride, vanadium tetrachloride, vanadium oxychloride, phosphorus trichloride, and the like.

The amount of organic solvent used is 0.1 to 100 parts by weight, preferably 0.3 parts by weight based on titanium trichloride or titanium trichloride composition.
-50 parts by weight.

The amount of the modifier used is 0.57-500 mol%, preferably 2% by mole based on titanium trichloride or titanium trichloride composition.
It is in the range of ~200 mol%.

These additions are usually made before the pulverization operation, but they may also be added during the pulverization process or in several portions.

The pulverization operation uses a conventional pulverizer for pulverizing powder, such as a ball mill, vibration mill, formal mill, jet mill, etc.
This is done in the absence of oxygen, moisture, etc.

The temperature during grinding 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 approximately 100 to 100 hours.

(2) Process of washing and separating the pulverized material with an inert organic solvent: Same as above to remove part or all of the excess modifier present in the wet pulverized material and the soluble components generated during the treatment. After washing with an inert organic solvent, the pulverized titanium component is separated by means such as decanting, filtration, and centrifugation.

The organic solvent, modifier, and other volatile components are evaporated by drying.

There are no particular restrictions on the method and conditions for drying, and the usual method of drying by heating under normal pressure or reduced pressure is common.

As a drying method, volatile components may be evaporated while drying before the next dry grinding step.

(3) Dry pulverization process: This dry pulverization process adjusts the particle size of the titanium component as described later.

There are no particular restrictions on the means and conditions for pulverization, but the method described in the pulverization step (1) above may be used depending on the purpose.

(4) Modification process of the pulverized product: After bringing the dry pulverized product into contact with the same organic solvent as above or a mixture of this and a modifier selected from the group consisting of (1) to (V) above. , separated from organic solvent.

In this modification treatment, a method of washing with an organic solvent, a method of washing with an organic solvent and then contacting and separating the mixture with a mixture of an organic solvent and a modifier, or a method of washing with a mixture of different types of organic solvents and/or a modifier, Various embodiments can be adopted depending on the starting materials or purpose, such as repeated contact and separation methods.

The organic solvent is used in an amount of 1 to 500 parts by weight based on the pulverized product, and the treatment is carried out at 0 to 200°C.

After the treatment, the solvent and the pulverized product are separated by filtration or the like.

In some cases, the solvent may be removed by heating under normal pressure or reduced pressure.
It may be dried or these operations may be repeated several times.

The amount of modifier used is 0.001 to 100 per pulverized material.
Parts by weight, preferably 0.01 to 50 parts by weight.

There is no limit to the mixing ratio of the organic solvent and modifier.

Determined according to their type.

The conditions for contacting the mixture of an organic solvent and a modifier with the pulverized product are not particularly limited, but generally they are brought into sufficient contact by standing at a temperature of 0 to 200°C or by being pressed in this manner.

Also effective are methods using a Soxhlet type extractor, a countercurrent contact tower, and the like.

After the contact, the pulverized product is separated in the same way as in the case of modification treatment using only an organic solvent.

(5) Co-pulverization step with an organoaluminum compound in the presence of a small amount of ethylene or α-olefin: the wet pulverization step of the above (1), the dry pulverization step of the above (3), or the above (2)
) at any stage after washing and separation and before drying,
Co-milling with an organoaluminum compound is carried out in the presence of a small amount of ethylene or α-olefin.

That is, in the wet pulverization step (1), the organoaluminum compound and ethylene or α-olefin are added to the pulverizer from the beginning, during the process, or after the end of the process, and the pulverization operation is continued.

In the case of the dry pulverization step (3) above, the organoaluminum compound and ethylene or α-olefin are added and co-pulverized from the beginning or during the process.

Further, in the washing and separation step using an organic solvent (2), an organoaluminum compound and ethylene or α-olefin are added to the titanium component before drying obtained by washing and separation and co-pulverized.

The above-mentioned co-pulverization treatment is mainly for adjusting the particle size of the titanium component, and the above-mentioned co-pulverization treatment performed in the wet-pulverization step of the above (1) or the stage after washing and separation of (2) is the subsequent dry-pulverization treatment of the above-mentioned (3). The co-pulverization process performed in conjunction with the pulverization step and in the dry pulverization step (3) above adjusts the particle size in one step.

The organoaluminum compound used in the co-pulverization process is represented by the general formula AIRmX3-m as described above, and includes, for example, triethylaluminum, triisobutylaluminum,
Examples include diethylaluminium monochloride, diimbutylaluminum monochloride, diethylaluminum monobromide, and ethylaluminum sesquichloride.

The amount used is preferably in the range of 0.01 to 100 mol per titanium atom in titanium trichloride or a titanium trichloride composition.

The amount of ethylene or α-olefin added at the time of co-milling is 0.000% relative to titanium trichloride or titanium trichloride composition.
The amount is 0.01% by weight or more, preferably 0.1-10% by weight, and lower α-olefins such as propylene and butene-1 are used as the α-olefin.

The addition may be carried out all at once, in portions or continuously during the grinding process.

These need not be the same type of monomer as the monomer polymerized using the catalyst component obtained by the method of the present invention, and ethylene, propylene, etc. are suitable.

Also, a small amount of hydrogen may be added at this time.

The co-pulverization means, conditions, etc. are selected from the range of conditions described in the processing step (1) depending on the purpose.

The amount of olefin used here is 0.0% relative to the starting material.
If the particle size adjustment effect of the present invention is less than 0.01% by weight, for example 0.005% by weight, the particle size adjustment effect of the present invention is not observed, but if the IO weight is □ or more, for example 1
In the case of 5% by weight, the particle size adjustment effect is recognized, but the size of the produced polymer becomes non-uniform, the shape of the produced polymer becomes poor, and the bulk specific gravity of the produced polymer decreases, which is not preferable. %, the catalyst components solidify during dry grinding and a powdered catalyst cannot be obtained.

In the modified titanium catalyst component prepared according to the present invention, the number of fine particles having a diameter of 5 μm or less is less than several percent, and the width of the particle size distribution is also narrow.

By (2) polymerizing olefins using this modified titanium component, it is possible to obtain (b) a polymer having an extremely low content of fine powder and a narrow particle size distribution.

Furthermore, compared to polymerization using conventional modified titanium catalysts, the polymerization rate of olefins using the modified titanium catalyst component according to the present invention is significantly faster, and the stereoregularity of the resulting polymer is extremely high. It turned out that this had an unexpected effect.

The reason why the particle size of the titanium catalyst component is adjusted according to the present invention is considered to be as follows, but the present invention is not limited to this theoretical explanation.

When the co-pulverization treatment with the organoaluminum compound in (5) above is carried out in the wet-grinding step in (1) or in the step after washing and separation in (2), a small amount of coexisting ethylene or α
- The olefin polymerizes to produce a very small amount of polyethylene or polyolefin, which is uniformly dispersed in the titanium component and becomes a bonding agent between particles in the subsequent dry grinding step (3), making it suitable for the grinding process. It is thought that the particles aggregate to a certain particle size.

Further, when the co-pulverization process (5) is performed in the dry-grinding step (3), the crushing and the mutual agglomeration of particles due to polymer production are performed in one step.

The titanium component thus aggregated is not redispersed or atomized in the subsequent modification step (4), and its particle size is maintained.

Therefore, the polymers obtained by polymerization of olefins using the titanium component prepared according to the present invention exhibit extremely excellent particle size characteristics.

In the polymerization of olefin using the titanium component obtained by performing the co-pulverization treatment in (5) according to the present invention, the polymerization rate is significantly faster than in the case where the co-pulverization treatment in (5) is not performed. This has the effect of extremely high stereoregularity of coalescence.

The reason for this effect is currently unknown.

Next, the present invention will be described with reference to examples.

Example 1 A vibratory mill equipped with a grinding pot having an internal volume of 600 mm and containing about 80 steel balls with a diameter of 12 mm is prepared.

In this pot, a titanium trichloride/aluminum chloride eutectic (hereinafter abbreviated as A-type titanium trichloride) obtained by reducing titanium tetrachloride with aluminum metal in a nitrogen atmosphere.
The composition is approximately T i Cl13・1/3AIC13)50
(This pulverized product is hereinafter abbreviated as AA-type ring titanium chloride).

Next, 150 ml of n-hebutane 1 1 di-n-butyl ether
(Add Bi' and perform wet pulverization for 3 hours.

After adding 2501 rll of n-hebutane to the obtained pulverized product and stirring at the boiling point of n-hebutane for 20 minutes,
After repeating the washing process twice to remove the supernatant by decantation, it was dried for 30 minutes at 60° C. under a reduced pressure of lmmHg.

After adding 1.0 TLl of diethylaluminium monochloride to 30 g of the dried composition and pulverizing it for 15 minutes, 200 mm of propylene gas was charged over 30 minutes while pulverizing, and pulverizing was continued for a further 3 hours.

The pulverized product was separated from the steel balls under a nitrogen atmosphere, and 150 ml of n-hebutane was added to 25 g of the obtained titanium component, stirred for 20 minutes at the boiling point of heptane, and then the n-hebutane was removed by decantation.

After performing this operation 5 times, at the 6th time, n-hebutane 1
50- is added and used as an activated titanium component suspension.

Reference Example 1 (Polymerization Example): In a 5US-32 autoclave with an internal volume of 21, 11 n-hebutane and 0.4 of the above activated titanium component were added under a nitrogen atmosphere.
0g and diethylaluminum monochloride 1. Oml
was loaded.

After exhausting the nitrogen in the autoclave with a vacuum pump,
1 Hydrogen was charged at a gas phase partial pressure of 1.0 kg/-, and then propylene was charged to set the pressure in the gas phase to 2 kg/history gauge.

The contents of the autoclave were heated, and after 5 minutes, the internal temperature was raised to 70°C, and the polymerization was continued at 70°C.

During polymerization, propylene is continuously pressurized to maintain an internal pressure of 5 kg.
/crj, kept at gauge.

After 2.05 hours, the amount of polymerized propylene reached about 500 g, so the introduction of propylene was stopped, unreacted gas was released, and 300 ml of methanol was added and stirred for 30** minutes to decompose the catalyst.

After cooling the autoclave, remove the contents and add 2001r water.
After adding Ll and washing three times at 60°C, filtrate and dry under reduced pressure at 60°C to obtain 520 g of white polypropylene.
I got it.

The resulting polypropylene had an intrinsic viscosity (measured at 135°C with tetralin, the same applies hereinafter) of 1.65, and a bulk specific gravity of 0.43.
g/ynll, boiling n-hebutane extraction residue (hereinafter abbreviated as Powder II) was 96.6%.

On the other hand, 15 g of non-quality polypropylene was obtained by evaporating the 0 liquid.

The polymerization activity of the catalyst in this polymerization reaction was 634 g/'j-hr
(polypropylene production rate per g of activated titanium per hour, the same applies hereinafter), and the boiling rate n for the total polymer
- Ratio of hebutane residual polymer (hereinafter abbreviated as total II)
was 93.8%.

Furthermore, in the dry powder, fine particles with a particle size smaller than 200 mesh (hereinafter abbreviated as fine particles) accounted for 7.0% of the total.

Comparative Examples 1 to 3 AA type ring titanium chloride comparative example used in the method of Example 1 ■) Catalyst in which propylene gas was not charged during dry grinding using the method of Example 1 (Comparative Example 2), and Table 1 shows the results of polymerization carried out in the same manner as in Reference Example 1 using the catalyst (Comparative Example 3) in which heptane was not washed in the reforming step using the method in Example 1 and in comparison with Example 1. show.

Example 2 30 g of A-type titanium trichloride, 3.9 g of aluminum chloride diphenyl ether complex, and 150 g of n-hebutane were milled for 40 hours in the same manner as in Example 1, and then washed in the same manner as in Example 1. , drying was carried out, and pulverization was carried out in the coexistence of fluoropylene and diethylaluminum monochloride.

Next, the pulverized product was separated, and 1 liter of n-hebutane was added to 2 Fl.
50m1. After adding 20 g of diisoamyl ether and stirring for 20 minutes at the boiling point of n-hebutane, the supernatant was removed by decantation and 50 ynl of n-hebutane was added.
was added, stirred for 20 minutes at boiling point, and the same washing process of removing the supernatant liquid was repeated four times.

Polymerization was carried out in the same manner as in Reference Example 1 using 0.30 g of the obtained activated titanium.

Polypropylene powder with polymerization time of 1.90 hr.51.
1. 17 g of non-quality polypropylene was obtained.

The intrinsic viscosity of the obtained polypropylene powder was 1.63.
, bulk specific gravity 0.43g/1rLl, powder ll96.
3%, and fine particles 6.5%.

Polymerization activity of catalyst in main polymerization reaction: 911'J/g・hr
and the total II was 93.5%.

Example 3 The catalyst of Example 1 was prepared in the same manner as in Example 1, up to the co-pulverization of titanium trichloride in the coexistence of diethylaluminium monochloride and propylene gas.

The pulverized product is separated from the steel balls in a nitrogen atmosphere, and the 2El
150 ml of n-heptane and 20 g of di-n-butyl ether were added to the mixture, and after stirring for 20 minutes at the boiling point of n-hebutane, the supernatant liquid was removed by decantation, and washing treatment with n-heptano 1501 rLl was performed three times.

Then 150 ml of n-hebutane. After adding 30 g of titanium tetrachloride and stirring for 20 minutes at the boiling point of n-hebutane,
The supernatant liquid was removed by decantation, and washing treatment with 150 ml of n-hebutane was performed three times, and the fourth time was
Add 150 TL of hebutane and use as an activated titanium component suspension.

Reference Example 1 was carried out using the obtained activated titanium fractions o and isy.
Polymerization was carried out in the same manner.

Polypropylene powder 50' with polymerization time 2.42hr
1 and 7 g of non-grade polypropylene were obtained.

The intrinsic viscosity of the obtained polypropylene powder was 1.59.
, bulk specific gravity 0.43F/T7Ll, powder ll97.
3%, and fine particles 7.2%.

Polymerization activity of catalyst in main polymerization reaction: 1421 g, Q・hr
and the total II was 96.0%.

Example 4 In the method of Example 3, a catalyst component was prepared by changing the stage of co-pulverization in the presence of diethylaluminum monochloride and propylene.

That is, in the process of preparing catalyst components in the order of (1) to (9) consisting of AA type titanium trichloride, following the wet grinding in (1), 1 rnl of diethylaluminum monochloride was added in (2), and 300 d of propylene was added. The same procedure as in Example 3 was carried out except that the dried material was charged while continuing wet pulverization for 3 hours, and the dried material was simply pulverized in step (5), and the polymerization was carried out in the same manner as in Reference Example 1. Shown in the table.

Example 5 A catalyst component was prepared in the method of Example 3 by changing the step of co-pulverization in the presence of diethylaluminum monochloride and propylene.

That is, in the process of preparing catalyst components in the order of (1) to (9) from AA type titanium trichloride*, after the washing step of (2), 150 ml of n-hebutane was added in (3). Add diethylaluminum monochloride l-, blow in propylene 300- over 3 hours while wet grinding, and carry out exactly the same as Example 3, except for simply grinding the dried product in (5), and the same as Reference Example 1. The results of polymerization are shown in Table 2.

Comparative Examples 4-7 Catalyst components of Example 4 as a comparison of Examples 3-5! In the process, when wet pulverization in the coexistence of diethylaluminum monochloride and propylene in (2) is omitted (Comparative Example 4), when the step (2X4X5) is omitted** (Comparative Example 5), Example Table 3 shows the polymerization results when only charging propylene was omitted in the dry grinding step in method 3 (Comparative Example 6) and when wet grinding was omitted in Example 3 (Comparative Example 7).

Examples 6 to 27 G-n- used during wet pulverization in the method of Example 1
Table 4 shows the results using various modifiers as shown in Table 4 in place of butyl ether.

Furthermore, in a series of experiments, as shown in Table 4, it was confirmed that the effects of the present invention can be observed even if the type and amount of olefin used during dry grinding in Example 1, the amount used, and the type of cleaning solvent are changed.

Note that when the cleaning solvent had a boiling point of 100°C or lower, the cleaning treatment was performed at the boiling point temperature, and when the cleaning solvent had a boiling point of 100°C or higher, the cleaning treatment was performed at 100°C.

Examples 29 to 33 Catalyst components were prepared in the same manner as in Example 3, except that various modifiers were used instead of di-n-butyl ether used in the first reforming step. The results of polymerization are shown in Table 5.

In a series of experiments, it was confirmed that the effect of the present invention was observed even if the type and amount of olefin used during the dry grinding in Example 3, the amount used, or the type of cleaning solvent were changed.

Examples 34 to 43 In the method of Example 3, catalyst components were prepared using various compounds as modifiers instead of di-n-butyl ether used in the wet grinding step and the first-stage reforming step, The polymerization results are shown in Table 6.

Further, the same experiment was conducted by changing the type and amount of the organoaluminum compound used during dry grinding in Example 3 as shown in Table 6, and the effects of the present invention were confirmed.

Reference Example 2 Bulk polymerization of propylene was carried out using the catalyst component synthesized in Example 3 by the method shown below.

That is, an activated titanium component suspended in 30 TL of heptane under nitrogen atmosphere in a 5 US-32 autoclave with an internal volume of 0.0! 1 and diethylaluminum monochloride were charged.

After exhausting the nitrogen in the autoclave with a vacuum pump,
The autoclave was charged with 1.5N hydrogen/2.5 kg propylene.

The contents of the autoclave were heated, and after 15 minutes, the internal temperature was raised to 70°C, and polymerization was carried out at 70°C.

After 5 hours, cool the autoclave and remove the contents.
It was dried under reduced pressure at 60° C. to obtain 1020 g of polypropylene powder.

II of the obtained polypropylene powder was 96.7%,
Intrinsic viscosity number 1.53, bulk specific gravity 0.46 g/ml.

At 0.5 wt% of fine particles,

Claims (1)

[Claims] 1. In the preparation of the titanium catalyst component of the Ziegler type catalyst, (1) an inert organic solvent and a modifier are added to titanium trichloride or a titanium trichloride composition, and a wet pulverization treatment is performed (2) then 3) The pulverized product is washed and separated with an inert organic solvent. 3) Next, a dry pulverization process is performed. (5) In the above process, the wet grinding step in (1) above, the dry grinding step in (3) above, or the washing in (2) above,
At any of the post-separation steps, a small amount of ethylene or alpha-olefin, up to about 10% by weight of the titanium trichloride or titanium trichloride composition, is added to form a compound of the general formula AlRmX.
3-m (where R is an alkyl group or an aryl group, X is hydrogen or )\logen, and m is 1 to 3). selected from the group consisting of (m) an oxygen-containing, sulfur, phosphorus, nitrogen or silicon organic compound, (ii) a combination of the above organic compound ([) and aluminum halide, (iii) an organoaluminum compound, and (IV) a Lewis acid. 1. A method for producing an ethylene or α-olefin polymerization catalyst component, characterized in that: