JPS6123206B2 - - 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 grinding titanium trichloride or a titanium trichloride composition (Japanese Patent Publication No. 35-14125, Japanese Patent Publication No. 39-24271, etc.), or by adding various compounds to these titanium compounds and co-pulverizing them (Japanese Patent Publication No. 39-1989). 24270, 39-24272, 43-10065, same
43-15620, 49-22315, JP-A-48-68497, same
48-29694, 48-38295, 49-531956, etc.) Furthermore, by modifying these pulverized products with an organic solvent or a mixture of this and a modifier (Japanese Patent Publication No. 49
-1947, 49-48638, 50-17319, 49-
48637, JP-A-48-64170, 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 with a wide particle size distribution that contains a large amount of fine particles have a similarly wide particle size distribution, and usually contain 10 to 30 fine particles of 50μ or less.
Including 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 filtration, centrifugation, etc., and losses due to dissipation increase in the drying process and pelletizing process.
Therefore, in order to prevent these, extra equipment is installed,
Since complicated manufacturing operations must be performed, improvements are desired. 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 disclosed, for example, in Japanese Patent Publications No. 49-1947, No. 49-48638, and Japanese Patent Publication No. 48-1979.
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. For the same purpose, the applicant previously prepared a titanium starting material of _the general formula AlR _n , X is hydrogen or halogen, m is 1 to 3) (an aspect of the operation referred to as contact operation in the present invention), and then an inert organic solvent or Modification treatment is carried out by contacting a mixture of the organic solvent and a modifier, and the modifier is a) an oxygen-containing, sulfur, phosphorus, nitrogen or silicon organic compound, b) an organic compound of a) above. Patent application No. 1, filed on April 1, 2013, relates to a method for producing a modified titanium component of an ethylene or α-olefin polymerization catalyst, which is selected from the group consisting of: c) an organoaluminum compound; and d) a Lewis acid, in combination with an aluminum halide.
51-67092 was filed. As a result of further studies, we discovered a method according to the present invention that can achieve almost the same effects as those of the above patent application. The method for producing a titanium catalyst component according to the present invention includes:
The titanium starting material is prepared in an inert organic solvent containing an organoaluminum compound having the general formula AlR _n X _3-n (where R, After contacting with a small amount of ethylene or α-olefin of 10% by weight or less, the titanium component is separated and pulverized, and then mixed with an inert organic solvent or a) oxygen-containing, sulfur,
phosphorus, nitrogen or silicon organic compounds, b) above a)
A modification treatment is carried out by contacting with a mixture of a combination of an organic compound and an aluminum halide, c) an organoaluminum compound, and d) a modifier selected from the group consisting of a Lewis acid. The present invention is characterized in that, before the modification treatment, the starting titanium component is brought into contact with a small amount of ethylene or α-olefin in an inert organic solvent containing the organoaluminum compound, and then the inert solvent is This prevents an increase in the fine particle content of the titanium component after the modification treatment and improves the particle size distribution. The term "modification treatment" as used herein means an operation in which the titanium component is brought into contact with an inert organic solvent or a mixture thereof with a modifier and then separated. Furthermore, in this text, the term "cleaning treatment" with an organic solvent means an operation in which the titanium component is brought into contact with an organic solvent and then the titanium component is separated. 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. Si
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 -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 titanium trichloride in 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. In _the present invention, the organoaluminum compound of the general formula AlR _n Examples include isoptylaluminium monochloride, diethylaluminum monobromide, and ethylaluminum sesquichloride. The amount used is per 1 atom of titanium in the starting material.
A range of 0.01 to 100 mol is preferred. The amount of ethylene or α-olefin contacted is about 10% by weight or less based on the starting material, and the lower limit is usually about 0.01% by weight. Preferably 0.1-10
% by weight. As the above α-olefin, lower α-olefins such as propylene and butene-1 are used. These need not be the same type of monomers used in the catalytic polymerization. Inert organic solvents used in this contact treatment include aliphatic, alicyclic, or aromatic hydrocarbons, halogen derivatives thereof, or mixtures thereof, such as hexane,
Heptane, 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 per 1 part by weight of the starting titanium component. Although the contact conditions are not particularly limited, it is necessary to carry out the contact in a state substantially free of oxygen, moisture, and the like. Generally, it is preferable to bring them into sufficient contact at a temperature in the range of 20 to 150°C under stirring. Further, the reaction may be carried out in the coexistence of a small amount of hydrogen. After the contact treatment, the solvent and the contact treated titanium component are separated by decantation or filtration.
Further, depending on the case, the solvent may be removed and dried by further heating under normal pressure or reduced pressure. Then, the contact-treated material is pulverized. The pulverization operation is carried out using a conventional pulverizer for pulverizing powder, such as a ball mill, in a state substantially free of oxygen, moisture, and the like. The temperature during grinding is not particularly limited, but
Generally, the grinding time is 1 in the range of -30℃ to 150℃.
Approximately 100 hours is appropriate. The thus obtained pulverized material 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, the pulverized material is washed with an organic solvent and separated, the 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 used depending on the starting materials and purpose, such as a method in which the material is separated after being brought into contact with a different type of organic solvent or a mixture of an organic solvent and a modifier, or a method in which the material is repeatedly brought into contact with a mixture of different types of organic solvents or a mixture of an organic solvent and a modifier and then separated. . Furthermore, another preferred embodiment of the present invention is to subject the emitted titanium component to a modification treatment before the contacting step, and to further subject the titanium component after co-pulverization to a modification treatment.
This allows the modification effect to be further improved. As the inert organic solvent used in this modification treatment, the same solvent as in the above contact treatment is used. 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 a temperature of 0 to 200°C. After treatment, the solvent and the 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 titanium trichloride 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 (additives) as well as the modifier. and the denaturing agent may be the same or different). (1) Organic oxygen-containing, sulfur, phosphorus, nitrogen, or silicon compounds: (1-1) Organic oxygen-containing compounds Ethers, ketones, and esters are used as organic oxygen-containing compounds. For ethers, the general formula R ¹ -O-R ²
(However, R ¹ and R ² are an alkyl group, an aralkyl group, a cycloalkyl group, an aryl group, or a halogen substituent thereof.) Saturated and unsaturated ethers, cyclic ethers, and polyethers are used. It will be done. For example, diethyl ether, di-n-propyl ether, dibenzyl ether, dicyclohexyl ether, diphenyl ether, ditolyl ether, methyl phenyl ether (omp
), diallyl ether, butenyl ether, di(4-chlorophenyl) ether, 2
- Chlorophenyl ether, tetrahydrofuran, propylene oxide, diethylene glycol dimethyl ether, diethylene glycol dipropyl ether, ethylene glycol dimethyl ether, ethylene glycol diphenyl ether, ethylene glycol ditolyl ether, and the like. General formula for ketones

Saturated or unsaturated ketones or cyclic ketones represented by [Formula] (where R ³ and R ⁴ represent an alkyl group, an aralkyl group, a cycloalkyl group, an aryl group, or a halogen substituent thereof), Ester ketones, such as acetone, diethyl ketone, methyl isobutyl ketone, methyl benzyl ketone, acetophenone, diphenyl ketone, dichlorohexanone, acetylacetone, allyl phenyl ketone, p-chlorophenyl methyl ketone, methyl tolyl ketone (omp
body), etc. General formula for esters

[Formula] (where R ⁵ and R ⁶ represent an alkyl group, an alkenyl group, an aralkyl group, a cycloalkyl group, an aryl group, or a halogen substituent thereof) A saturated or unsaturated ester cyclic ester Examples include methyl acetate, ethyl acetate, methyl acetoacetate, methyl methacrylate, cyclohexyl acetate, benzyl acetate, methyl benzoate, ethyl benzoate, ε-caprolactone, and ethyl chloroacetate. Among these, diethyl ether, diphenyl ether, ditolyl ether (omp form) 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 compound has the general formula R ⁷ -S-
Saturated or unsaturated thioethers or cyclic thioethers represented by R ⁸ (R ⁷ and R ⁸ are an alkyl group, an aralkyl group, a cycloalkyl group, an aryl group, or a halogen substituent thereof) For example, diethyl thioether, di-n-propyl thioether, dicyclohexyl thioether, diphenyl thioether, ditolyl thioether (omp form), methyl phenyl thioether, ethylphenyl thioether, propyl phenyl thioether, dibenzyl thioether, diallyl thioether , allyl phenyl thioether, 2-chlorophenyl thioether, ethylene sulfide, propylene sulfide, tetramethylene sulfide, and the like. Thiophenols and thioalcohols include saturated or unsaturated thiophenols represented by the general formula H-SR ⁹ (where R ⁹ is an alkyl group, an aralkyl group, a cycloalkyl group, an aryl group, or a halogen substituent thereof) thioalcohols such as ethylthioalcohol, n-propylthioalcohol,
n-butylthioalcohol, n-hexylthioalcohol, n-dodecylthioalcohol, cyclohexylthioalcohol, benzylthioalcohol, allylthioalcohol,
Examples include thiophenol, O-methylthiophenol, p-methylthiophenol, 2-chloroethylthioalcohol, p-chlorothiophenol, and the like. 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, thiophenol and the like. can be given. (1-3) Organic phosphorus-containing compound As the organic phosphorus-containing compound, compounds represented by the following general formulas to (XV) are used. a Phosphines represented by the general formula PR ¹⁰ ₃ () (R ¹⁰ 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-butylphosphine Examples thereof include ethylene, ethyldiphenylphosphine, n-propyl n-butylphenylphosphine, and ethylbenzylphenylphosphine. ^b Phosphinas halides represented by the general formula PR ¹¹ ₂ Examples include diethylphosphina chloride, diisopropylphosphina chloride, methylethylphosphina chloride, diphenylphosphina chloride, and ethyl phenylphosphina chloride. ^c Phosphonous dihalides represented by _the general formula PR ¹² dichloride,
Examples include methylphosphonas dibromide, ethylphosphonas dibromide, butylphosphonas dichloride, benzylphosphonas dichloride, cyclohexylphosphonas dichloride, phenylphosphonas dichloride, phenylphosphonas dibromide, and the like. d Phosphinites represented by the general formula PR ¹³ ₂ (OR ¹⁴ ) () (R ¹³ and R ¹⁴ in the general formula represent an alkyl group, an aralkyl group, or an aryl group) For example, ethyl diethyl phosphinite,
Examples include ethyldipropylphosphinite, ethyldiptylphosphinite, phenyldiphenylphosphinite, ethyldiphenylphosphinite, phenyldibenzylphosphinite, ethylmethylphenylphosphinite, etc. . e Phosphonites represented by the general formula PR ¹⁵ (OR ¹⁶ ) ₂ () (R ¹⁵ and R ¹⁶ in the general formula represent an alkyl group, an aralkyl group, or an aryl group.) Dimethyl ethyl phosphonite, diethyl ethyl phosphonite, Examples include diethylbutylphosphonite, diethylbenzylphosphonite, diethyl phenylphosphonite, diphenylmethylphosphonite, and diphenylethylphosphonite. f Phosphites represented by the general formula P(OR ¹⁷ ) ₃ () (R ¹⁷ 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, triβ-naphthyl phosphite, diphenylcyclohexyl phosphite, diphenylpropyl phosphite, and the like. ^{g Halogen phosphites represented by the general formula P(OR 18 )} ₂ Examples include phosphite, diethylchlorophosphite, di-n-butylchlorophosphite, dicyclohexylchlorophosphite, diphenylchlorophosphite, diphenylchlorophosphite, and diphenylchlorophosphite. h Dihalogen phosphites represented by _the general formula P( ^{OR 19 )} Phosphite, methylchlorofluorophosphite, ethyldichlorophosphite, allyldichlorophosphite, n-butyldichlorophosphite, phenyldichlorophosphite, p
-chlorophenyldichlorophosphite,
Examples include 2-chloroethyldichlorophosphite. i General formula P(NR ²⁰ ₂ ) ₃ (), P(NR ²¹ ₂
) ₂
( ), P(NR ²² ₂ )X ₂ (XI) Aminophosphines (R ²⁰ , R ²¹ and R ²² in the general formula represent 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 phosphorus tri(N-methylanilide), bis(dimethylamino)chlorophosphine, dimethylaminodifluorophosphine, Examples include diethylaminodichlorophosphine and (di-n-butylamino)dichlorophosphine. j Phosphates represented by the general formula P(O)(OR ²³ ) ₃ (XII) (R ²³ 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: Methyl dihydrodiene phosphate, ethyl dihydrodiene phosphate, n-butyl dihydrodiene phosphate, cyclohexyl dihydrodiene phosphate, phenyl dihydrodiene phosphate, p-chlorophenyl dihydrodiene phosphate, diethyl Phosphate, di-n-propyl phosphate, dibenzyl phosphate, diphenyl phosphate, di-α-naphthyl phosphate, dibiphenyl phosphate, triethyl phosphate, tri(n-butyl) phosphate, tri(n-amyl) ) phosphate, tricyclohexyl phosphate, tri(o
-chlorophenyl) phosphate, triphenyl phosphate, tri p-tolyl phosphate, tri m-tolyl phosphate,
Examples include tri-4-biphenyl phosphate and tri(α-naphthyl) phosphate. k Phosphorohalogenates represented by the general formula P(O)( ^OR24 ) _2X () ( ^R24 in the general formula represents an alkyl group, cycloalkyl group, or aryl group, and X represents a halogen atom.) For example, dimethyl phosphorochloridate,
Examples include diethylphosphorochloridate, diisopropylphosphorochloridate, dicyclohexylphosphorochloridate, diphenylphosphorochloridate, and the like. l Phosphorodihalogedates represented by the general formula P( ^{O )(OR 25} ₎ ,
Examples include ethylphosphorodichloridate, ethylphosphorochloride fluoridate, n-butylphosphorodichloridate, p-tolylphosphorodichloridate, and phenylphosphorochloridate. m General formula R ²⁶ ₃ P=O(), (R ²⁷ ₂ N
) _3P
Phosphine oxide and its derivatives represented by =O() (R ²⁶ and R ²⁷ in the general formula represent an alkyl group, an aralkyl group, a cycloalkyl group, or an aryl group) For example, 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. can be mentioned. n Phosphine sulfides represented by the general formula R ²⁸ ₃ P-S () (R ²⁸ in the general formula represents an alkyl group, an aralkyl group, or an aryl group.) For example, trimethylphosphine sulfide, triethylphosphine sulfide, Examples include tri-n-propylphosphine sulfide, tri-n-butylphosphine sulfide, triphenylphosphine sulfide, diethylphenylphosphine sulfide, and diphenylbenzylphosphine sulfide. Among these organic phosphorus-containing compounds, triphenylphosphine, triphenylphosphite, triphenylphosphine oxide, triphenylphosphate, triphenylphosphate, and triphenylphosphine are particularly preferred. (1-4) 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 R ²⁹ NH _3-o (where R ²⁹ is a hydrocarbon residue and n represents 1 to 3).
and nitrogen-containing heterocyclic compounds, such as triethylamine, tributylamine,
trihexylamine, triphenylamine,
N, N'-dimethylaniline, aniline, N
-Methylaniline, butylaniline, dibutylamine, pyridine, quinoline, 2-chloropyridine and the like. General formula R ³⁰ NCO for isocyanates
(wherein R ³⁰ represents a hydrocarbon residue) is used, such as phenyl isocyanate and tolyl isocyanate (omp form). As an azo compound, the general formula R ³¹ -N=N-
R ³² (wherein R ³¹ and R ³² represent hydrocarbon residues) is used, and for example, azobenzene and nitriles are represented by the general formula R ³³ CN (where R ³³ represents a hydrocarbon residue), such as Examples include acetonitrile and benzonitrile. (1-5) Organosilicon-containing compound As the organosilicon-containing compound, tetrahydrocarbon silane, its halogen or alkoxy derivative, chain or cyclic organopolysilane, siloxane polymer, and other organosilicon compounds are used. Tetrahydrocarbon silanes and their halogen derivatives have the general formula R ³⁴ _o SiX _4-o (however,
R ³⁴ is a hydrocarbon residue, X is a halogen atom, and n is 1-4. ), such as tetramethylsilane, trimethylphenylsilane, tetraphenylsilane, trimethylpinylsilane, ethyltrichlorosilane, diethyldichlorosilane, triethylchlorosilane, phenyltrichlorosilane, diphenyldichlorosilane, vinyl trichlorosilane,
Examples include diethyldifluorosilane. The alkoxy derivative of tetrahydrocarbon silane has the general formula R ³⁵ _o Si(OR ³⁶ ) _4-o (but
R ³⁵ and R ³⁵ are hydrocarbon residues, n is 1 to 3), and examples thereof include trimethoxymethylsilane, diethyldiethoxysilane, triphenylethoxysilane, and the like. Examples of the chain or cyclic organopolysilane include hexamethyldisilane, hexaphenyldisilane, and dodecamethylcyclohexasilane. The general formula for siloxane polymers is (However, R ³⁷ represents hydrogen, an alkyl group, or an aryl group.) Alkylsiloxane polymers, arylsiloxane polymers, alkylarylsiloxane polymers, and the like are used, such as octamethyltrisiloxane, octaethyltrisiloxane, and octaethyltrisiloxane. Examples include siloxane, dimethylpolysiloxane, ethylpolysiloxane, methylethylpolysiloxane, hexaphenylcyclosiloxane, diphenylpolysiloxane, diphenyloctamethylpolysiloxane, and methylphenylpolysiloxane. Examples of other organic silicon-containing compounds include hexamethylsilazane, triethylisocyacyasisilazane, triphenylisocyanatosilane, cyanomethyltrimethylsilane, and trimethylsilylacetone. (2) A combination of organic oxygen-containing, sulfur, nitrogen or silicon compounds represented by (1-1) to (1-5) and aluminum halide. Examples of aluminum halides include aluminum trichloride, aluminum tribromide, aluminum trifluoride, and aluminum triiodide, 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. Further, a complex or a reaction product of the above-mentioned organic compound and aluminum halide can be used, but diphenyl ether is particularly preferred in this case. Aluminum trichloride complex. Diphenyl ether. Aluminum tribromide complex, diethyl ether. Aluminum trichloride complex, 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, triphenyl phosphite. Aluminum trichloride complex, triphenyl phosphate aluminum trichloride complex tritolyl phosphate. Aluminum trichloride complex, TrisNN-dimethylphosphoramide. Examples include aluminum trichloride complex. 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 order to synthesize the above-mentioned complex or reaction product, it is preferable to produce the above-mentioned organic compound and aluminum halide under conditions where the molar ratio is close to 1:1, but if either one is present in excess and in free form, You may also use a reaction product that is (3) Organoaluminum compounds The general formula for organoaluminum compounds is
AlR′nX′ _3-o (where R′ is a hydrocarbon residue,
X′ represents hydrogen, halogen, or alkoxy group,
n is 1 to 2), such as diethylaluminum monochloride, diisopropylaluminum monochloride, diisobutylaluminum monochloride, dihexylaluminum monochloride, ethylaluminum sesquichloride, isopropylaluminum sesquichloride, isobutylaluminum sesquichloride, ethylaluminum Examples include dichloride, isobutylaluminum dichloride, diethylaluminium monobromide, diethylaluminum monofluoride, diethylaluminium monoiodide, and the like. (4) Lewis acids Examples of Lewis acids include titanium tetrachloride, boron fluoride, boron trichloride, silicon tetrachloride, vanadium tetrachloride, vanadium oxychloride, and phosphorus trichloride. The amount of these modifiers used is 0.001 to 100 parts by weight, preferably 0.01 to 50 parts by weight, per 1 part by weight of the pulverized material.
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 contact conditions between the mixture of organic solvent and modifier and the pulverized material are not particularly limited, but are generally 0 to 0.
Allow sufficient contact in a temperature range of 200℃ either by standing still or under stirring. Also effective are methods using a Soxhlet type extractor, countercurrent contact tower, etc. After the contact treatment, the solvent and the ground product are separated by decantation or filtration. Also, depending on the case,
Further, the solvent may be removed and dried by heating under normal pressure or reduced pressure. Furthermore, these operations may be repeated several times. In the modified titanium component prepared by the method of the present invention, the number of fine particles with a diameter of 5 μm or less is less than several percent by weight, and the width of the particle size distribution is also narrow. By (co)polymerizing olefins using this modified titanium component,
A (co)polymer with a narrow particle size distribution can be obtained. What is even more surprising is that in the (co)polymerization of olefins using the modified titanium component according to the present invention, the polymerization rate is significantly faster than that obtained by modification using conventional methods, and the steric properties of the resulting polymer are It has been found that this has the completely unexpected effect of extremely high regularity. The reason why the particle size of the modified titanium component is improved by the present invention is considered to be as follows.
The present invention is not limited to this theoretical explanation. First, when the starting materials are brought into contact with a small amount of ethylene or α-olefin in the presence of an organoaluminum compound, a small amount of polyethylene or polyα-olefin is produced by their polymerization. In the next pulverization process, the titanium component is atomized and agglomerated into granules, and at this time, a small amount of the above-mentioned polymer coexisting becomes a kind of linking agent between the particles, and the titanium component is agglomerated. It acts to prevent particle redispersion and atomization.
However, the reason why the modified titanium component of the present invention exhibits even better polymerization activity and stereoregularity is still not clear. The present invention will be explained below with reference to Examples. Example 1 (1) Production example of titanium component Titanium trichloride is a reduction product of titanium tetrachloride with metallic aluminum. A titanium trichloride composition (hereinafter abbreviated as AA type titanium trichloride) obtained by pulverizing an aluminum chloride eutectic (hereinafter abbreviated as A-type titanium trichloride, the composition is approximately Ticl ₃ .1/3 Acl ₃ ) ) as the starting titanium component 30
g, 300 ml of n-heptane, and 1.0 ml of diethylaluminum monochloride are charged into a 500 ml round bottom flask under nitrogen flow. Next, the contents of the flask were heated to 50℃ and while stirring, propylene gas was blown in at a rate of 20ml/min for 24 minutes. After that, stirring was continued at the same temperature for 0.5hr, the supernatant liquid was removed by decantation, and the A contact-treated titanium component was obtained by drying under reduced pressure at °C. Approximately 600ml of internal volume containing approximately 80 steel balls with a diameter of 12mm.
The contact-treated titanium component was charged into a vibratory mill under a nitrogen atmosphere and ground for 17 hours at room temperature. The crushed contents are separated from the steel balls under a nitrogen atmosphere,
Add 150ml of n-heptane to 30g of titanium component obtained.
After stirring for 20 minutes at the boiling point of heptane,
The n-heptane was removed by decantation. After performing this operation five times, 150 ml of heptane was added at the sixth time and used as a modified titanium component slurry. (2) Reference example (polymerization example): In a SUS-32 autoclave with an internal volume of 2,
Under a nitrogen atmosphere, 1 n-heptane, 0.45 g of the above modified titanium component, and 1.0 ml of diethylaluminum monochloride were charged. After the nitrogen in the autoclave was evacuated using a vacuum pump, hydrogen was charged at a gas phase partial pressure of 1.0 Kg/cm ² , and then propylene was charged to make the gas phase partial pressure 2 Kg/cm ² gauge. The contents of the autoclave were heated and the internal temperature was raised to 70°C after 5 minutes, and polymerization was continued at 70°C. During polymerization, propylene is continuously pressurized,
The internal pressure was maintained at 5 Kg/cm ² gauge. After 3.7 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 water.
After adding 200 ml and washing three times at 60°C, filtering and drying under reduced pressure at 60°C, 488 g of white polypropylene was obtained. The resulting polypropylene had an intrinsic viscosity of 1.60 dl/g (measured at 135°C with tetralin, the same applies hereinafter), a bulk specific gravity of 0.42 g/ml,
The boiling n-heptane extraction residue (hereinafter abbreviated as powder) was 96.0 wt%. Meanwhile, 22 g of amorphous polypropylene was obtained by evaporation of the liquid. The polymerization activity of the catalyst in this polymerization reaction was 306 g/g. hr (polypropylene production rate per gram of titanium component per hour, same below)
The ratio of the boiling n-heptane extraction residual polymer to the total polymer (hereinafter abbreviated as total) was 91.9 wt%. In addition, in the dry powder, fine particles with a particle size smaller than 200 mesh (hereinafter abbreviated as fine particles) are
7.0wt%, finer than 20mesh and
Particles coarser than 100mesh accounted for 78.0wt% of the total. Comparative Examples 1 to 3 AA type titanium trichloride used in the method of Example 1 (Comparative Example 1), the titanium component that was not contacted with propylene gas in Example 1 (Comparative Example 2), and the titanium component of Example 1 Table 1 shows the results of a test performed in the same manner as in Examples 1 and (2) using a titanium component (Comparative Example 3) that was not subjected to the washing operation in the same manner as in Example 1.

[Table] Example 2 30 using AA type titanium trichloride as the starting titanium component
300 ml of n-heptane and 1.0 ml of diethylaluminum monochloride were charged into a round bottom flask, and after charging propylene in the same manner as in Example 1,
Decantation and drying yielded a contact-treated titanium component. (This is considered the first step) 30 g of this contact-treated titanium component, diphenyl ether. Example 1: 6.9 g of aluminum chloride complex
Grind for 17 hours in the same way (this is the second step),
This was washed with n-heptane in the same manner as in Example 1 to obtain an activated titanium component (this is referred to as the third step). Table 2 shows the results of polymerization using 0.45 g of this activated titanium and 1.0 ml of diethylaluminum monochloride in the same manner as in Example 1 (2). Results obtained by omitting the washing in the method of Example 2 and performing the other procedures in the same manner as in Example 2 (Comparative Example 4), and results obtained by using the method of Example 2 but omitting the contact with propylene gas and performing the other procedures in the same manner as in Example 2. Table 2 shows the results obtained in the same manner as (Comparative Example 5). Examples 3 to 22 Examples in which various α-olefins shown in Table 3 were used in place of the propylene used in the first step in the method of Example 2, and diphenyl ether added during pulverization in the second step. Examples of using various components instead of aluminum chloride complex (when there are two or more components, use the first component and the second component), and using various organic solvents instead of n-heptane during cleaning in the third step. Examples used are shown in Table 3. In addition, the cleaning solvent was carried out at the boiling point when n-hexane, n-heptane, cyclohexane, benzene, or toluene was used, and at 100°C when monochlorobenzene or xylene was used. (The same applies to the following examples.) Also, as a control, the fine particle content of the produced polymer when polymerization is carried out using a titanium component obtained by omitting the contact with α-olefin in the first step are shown in Table 3.

【table】

【table】

[Table] Example 23 25 g of modified titanium component prepared in Example 1 and n-
Add 10 g of di-n-butyl ether to a slurry of 150 ml of heptane, stir at 70°C for 20 minutes, then remove the supernatant by decantation.
After adding 150 ml and stirring for 20 minutes at the boiling point of heptane, washing was performed by separating n-heptane by decantation. After performing this washing process five times, the sixth time was to use n-heptane 150
A new modified titanium slurry was obtained by adding ml. Reference example (polymerization example): Example 1 (2) using 0.35 g of this active titanium component
The polymerization of propylene was carried out in the same manner as the polymerization of . Polypropylene powder 463 with polymerization time 2.50hr
25 g of amorphous polypropylene were obtained. Intrinsic viscosity of polypropylene powder: 1.66dl/
g Bulk specific gravity 0.42g/ml, powder 96.1%, fine grain
It was 7.4wt%. Polymerization activity in this polymerization reaction was 558g/g. hr, all
It was 91.2%. Comparative Example 6 A titanium component was prepared in the same manner as in Example 23, except that AA type titanium trichloride was used as the starting material instead of modified titanium, and polymerization was carried out using it. After a polymerization time of 3.5 hours, 402 g of polypropylene powder and 28 g of amorphous polypropylene were obtained.
Intrinsic viscosity of polypropylene powder: 1.66dl/
g, bulk specific gravity 0.30g/ml, powder 95.0wt%,
The fine particles were 43.0wt%. In addition, the catalyst activity in the main polymerization reaction was 351 g/g. hr, the total amount was 88.8wt%. Examples 24 to 29 Modified titanium components were prepared in the same manner as in Example 23 using various modifiers in place of the modifier di-n-butyl ether in the modification treatment in the method of Example 23. Table 4 shows the results of polymerization using. For comparison, Table 4 shows the results of similar modification treatment using the AA type titanium trichloride used in Comparative Example 1 as the starting titanium component.

【displayed. Example 30 50 ml of titanium tetrachloride was added to the modified titanium slurry obtained in Example 23, and after stirring at 70°C for 20 minutes,
The supernatant liquid was removed by decantation, and then washed five times with 150 ml of n-heptane to obtain a new modified titanium slurry, which was used (0.35 g was used as the modified titanium component). It was used in polymerization experiments in the same manner as in 1(2). After a polymerization time of 2.1 hours, 518 g of polypropylene powder and 14 g of amorphous polypropylene were obtained. Intrinsic viscosity of polypropylene powder: 1.63dl/
g, bulk specific gravity 0.43g/ml, powder 97.5wt%,
The fine particles were 8.1wt%. Polymerization activity in this polymerization reaction was 724g/g. hr, all
It was wt%. Comparative Example 7 The titanium component obtained in Comparative Example 6 was treated with titanium tetrachloride in the same manner as in Example 30, and compared with Example 30. Polypropylene powder with polymerization time 2.50hr
387 g and 16 g of amorphous polypropylene were obtained.
Intrinsic viscosity number of polypropylene powder 1.53dl/
g, bulk specific gravity 0.29 g/ml, fine particles 53.7 wt%,
Polymerization activity in this polymerization reaction was 460g/g. hr, all
It was 92.8wt%. Examples 31-36 The titanium components prepared in Examples 24-29 were further treated with titanium tetrachloride in the same manner as in Example 30 to obtain modified titanium slurries. Using 0.35 g of this modified titanium component, polymerization was carried out in the same manner as in Example 1 (2). Table 5 shows the results. In addition, for comparison, the amount of fine particles and the value of bulk specific gravity of polypropylene powder when polymerized using a titanium component obtained by performing the same treatment using an AA type titanium trichloride composition as a raw material are also shown.

[Table] Example 37 (1) Production example of titanium component AA type titanium trichloride 40g, n- in a nitrogen stream
150ml heptane, 20g di-iso-amyl ether
was placed in a 300 ml round bottom flask, stirred for 20 minutes at the boiling point of heptane, and then the supernatant liquid was removed by decantation. 150 ml of n-heptane was added and the same washing process of stirring and decantation was repeated 5 times. Then n-heptane
Add 150ml to make a slurry, then add 1ml of diethylaluminum monochloride,
℃ for 24 minutes at a rate of 20 ml/min, stirred at the same temperature for 0.5 hours, removed the supernatant liquid by decantation,
℃ under reduced pressure to obtain a contact-treated titanium component. Next, this was pulverized for 2 hours using a vibrating mill in the same manner as in Example 1. 150 ml of n-heptane to 30 g of the above pulverized material,
20 g of di-iso-amyl ether was added, stirred for 20 minutes at the boiling point of n-heptane, the supernatant liquid was removed, and the washing process with 150 ml of n-heptane was repeated three times. Next, 150 ml of n-heptane and 50 ml of titanium tetrachloride were added and stirred at 70°C.
- Repeat the washing treatment with heptane 3 times, n-
150 ml of heptane was added to obtain a modified titanium component slurry. (2) Polymerization example: Example 1 using 0.25 g of the above modified titanium component.
Polymerization was carried out in the same manner as in (2), and 511 g of polypropylene powder and 6 g of amorphous polypropylene were obtained in a polymerization time of 2.2 hours. Intrinsic viscosity of the obtained polypropylene powder
1.55dl/g, bulk specific gravity 0.43g/ml, powder
The content was 97.4wt%, and the fine particles were 8.3wt%. Activity in main polymerization reaction: 940g/g. hr, all
It was 96.3wt%. Comparative Example 8 In the method of Example 37, the blowing of ethylene in the coexistence of diethylaluminum monochloride was omitted, and the di-iso-aluminum ether treatment was performed twice and the titanium tetrachloride treatment was performed, and the method of Example 1(2) was performed. Polymerization was carried out in the same manner. In a polymerization time of 2.5 hours, 410 g of polypropylene and 9 g of amorphous polypropylene were obtained. Intrinsic viscosity of polypropylene powder 1.60dl/g, powder
97.0wt%, fine particles 49.0wt%, polymerization activity 670
g/g. Cat.hr was 94.9wt% in total. Comparing this with Example 37, in the comparative example, there were many fine particles of the produced polymer, the bulk specific gravity was low, and the activity and total content were also low, indicating that the special treatment of the modified titanium component used in the present invention is effective. Recognize. Example 38 (1) Production example of modified titanium component Type A titanium trichloride 40g, diphenyl ether
3.7 g of aluminum chloride and 3.2 g of aluminum chloride were placed in a vibrating mill, pulverized for 40 hours, washed with n-heptane in the same manner as in Example 1, and then 150 ml of n-heptane and 20 g of di-iso-amyl ether were added and heated at 70°C. Stir for 20 minutes, wash 3 times with 150 ml of n-heptane, then add 150 ml of n-heptane and 1 ml of diethylaluminum monochloride Example 1
Similarly, propylene gas was injected. Next, the supernatant was removed by decantation and dried under reduced pressure at 50°C and 1 mmHg. Add 150 g of n-heptane to 25 g of the obtained pulverized product.
ml, add 20g of di-iso-amyl ether and make 70
After stirring at ℃ for 20 minutes, remove the supernatant liquid by decantation, and add 150 ml each of n-hepetane.
was washed three times with the boiling point of n-heptane. Next, 150ml of n-heptane and 50ml of titanium tetrachloride.
After stirring at boiling point of 70℃, add n-heptane.
It was washed five times with 150 ml to obtain a modified titanium component slurry. (2) Polymerization Example Example 1 using 0.20 g of the obtained modified titanium
Polymerization was carried out in the same manner as in method (2). Polypropylene powder 510 with polymerization time 2.2hr
5 g of amorphous polypropylene was obtained. The obtained polypropylene powder has an intrinsic viscosity of 1.55
dl/g, powder 97.7wt%, bulk specific gravity 0.43
g/ml, and the fine particles were 7.0 wt%. Polymerization activity in this polymerization reaction was 1170g/g. hr, all
It was 96.8wt%. Comparative Example 10 The titanium component was prepared and polymerized in the same manner as in Example 38, except that the blowing of propylene was omitted. 340 g of polypropylene powder and 7 g of amorphous polypropylene were obtained in a polymerization time of 2.4 hours, and the intrinsic viscosity of the polypropylene powder was 1.63.
dl/g, bulk specific gravity 0.29g/ml, powder 97.0wt
%, and the fine particles were 50.3wt%. Polymerization activity in this polymerization reaction was 723g/g. hr, all
It was 95.0wt%. Example 39 Copolymerization of propylene and ethylene was carried out in the same manner as in Example 1(2) using the catalyst prepared in Example 38 and using a mixed gas with propylene containing 1 mol% of ethylene instead of propylene. Ta. The bulk specific gravity of the obtained polypropylene powder was 0.42 g/ml.
The amount of fine particles was 5.7 wt%, indicating that the present invention is effective even in copolymerization reactions. Example 40 Bulk polymerization of propylene was carried out using the catalyst component prepared in Example 39 by the method shown below. That is, 0.10 g of the modified titanium component suspended in 30 ml of n-heptane and 0.8 ml of diethylaluminium monochloride were charged into a SUS-32 autoclave having an internal volume of 6 under a nitrogen atmosphere. After exhausting the nitrogen in the autoclave with a vacuum pump, add 2Nl of hydrogen,
2.5Kg of propylene was charged into the autoclave.
The contents of the autoclave were heated to raise the internal temperature to 60°C over 15 minutes, and polymerization was carried out at 60°C. After 5 hours, the autoclave was cooled, unreacted propylene was purged, and the contents were taken out and dried under reduced pressure at 60°C to obtain 930 g of polypropylene powder. The total content of the obtained polypropylene powder was 95.7 wt%, intrinsic viscosity 1.62 dl/g, bulk specific gravity 0.44 g/ml, and fine particles.
It was 1.0wt%. Activity in this polymerization reaction is 1860
g/g. It was hr. When polymerization was repeated using the catalyst prepared in Comparative Example 10, the bulk specific gravity of the polypropylene produced was
It was 0.33 g/ml, and the fine particles were 26.3 wt%. Example 41 (1) Production example of modified titanium component 25 g of the pulverized product, which is an intermediate product of the catalyst preparation in Example 38, 150 ml of n-heptane, 20 g of di-iso-amyl ether, and 20 g of titanium tetrachloride were mixed into 300 ml of
ml round bottom flask, stir at 70℃ for 20 minutes, remove the supernatant liquid by decantation, and remove the n-
A modified titanium slurry was obtained by washing with 150 ml of heptane five times. (2) Polymerization Example Using the modified titanium component prepared in (1),
Polymerization was carried out in the same manner as in Example 40. Total 95.8wt% of the obtained polypropylene powder, intrinsic viscosity 1.65dl/g, bulk specific gravity 0.44g/ml, fine particles
0.8wt%, and the polymerization activity was 1830g/g. It was hr.

Claims (1)

[Claims] 1 A titanium component which is titanium trichloride or a titanium trichloride composition has the general formula AIR _n X _3-n (R is an alkyl group or an aryl group, and X is a hydrogen atom or a halogen atom, respectively and m is 1 to 3), once contacted with ethylene or α-olefin in an inert medium in an amount not exceeding 10% by weight of the titanium component,
A method for producing an ethylene or α-olefin polymerization catalyst component, which comprises pulverizing the solid material and further contacting the pulverized material with an inert medium. 2. The inert medium that is further brought into contact with the pulverized material contains at least one of the following compounds: (a) an organic compound containing oxygen, sulfur, phosphorus, nitrogen, or silicon; (b) an organoaluminum compound; and (c) a Lewis acid. A method according to claim 1, characterized in that it comprises one of: