JPS6342922B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a method for producing a catalyst using as a carrier a treated product obtained by mixing and co-pulverizing an inorganic powder and a liquid additive, and particularly relates to the preparation of a carrier by continuously carrying out mixing and co-pulverizing. Supported catalysts are often found in the production of polyolefins, but they are usually made by mixing and co-pulverizing an inorganic powder such as anhydrous magnesium chloride with a liquid additive, and then simultaneously or after co-pulverizing with a halogenated titanium compound, etc. Obtained by activation treatment. Conventionally, the above-mentioned mixing and co-pulverization has been carried out in the laboratory using a small homogeneous vibrating mill (e.g. ball void volume 0.6).
This is relatively easy to implement. However, large-scale batch vibration mills (e.g. ball cavity volume 250) necessary for industrialization
Therefore, when the above-mentioned mixed co-pulverization is carried out, an abnormal increase in the internal temperature occurs, and therefore, in order to lower the internal temperature,
Grinding must be frequently interrupted for cooling, and it takes a very long time to finally obtain the pulverized product, which is not practical. Furthermore, the obtained catalyst has low activity and contains many coarse particles, making it difficult to use in practice. In order to solve the above-mentioned problems in the process of industrializing a carrier catalyst for polyolefins, the present inventors developed a continuous vibratory mill, which has not been used for catalyst production in the past, but is advantageous in terms of heat removal. We tried mixed co-grinding. That is, when the liquid additive was added from one addition port, the pulverized raw material solidified and a normal pulverized product could not be obtained. We also attempted to block part of the flow in the continuous vibration mill, but no improvement was observed. We also attempted to add liquid additives in portions without blocking part of the flow, and although we were able to prevent the solidification of the pulverized material, the catalytic performance, such as the polymerization activity of polyolefin, was low, making it unsuitable for practical use. I didn't get it. Therefore, as a result of intensive studies to solve the above problems, the present inventors found that when mixing and co-pulverizing inorganic powder and liquid additives with a continuous vibrating mill, a part of the flow of the continuous vibrating mill is blocked. The present inventors have discovered that it is possible to industrially obtain a supported catalyst with extremely excellent catalytic performance such as polymerization activity by using a combination of adding a liquid additive in portions and adding a liquid additive in portions. In other words, the present invention applies to "Group A, Group A of the periodic table".
Inorganic powder consisting of one or more selected from the group consisting of halides, hydroxy halides, hydroxides, and oxides of Group A, Group B elements, and 5 weight per 100 parts by weight thereof. Aromatic hydrocarbons with more than 100 unsaturated substituents; halogenated hydrocarbons; aliphatic, aromatic or alicyclic alcohols, aldehydes, acids, acid anhydrides, acid halides and acid amides; aliphatic, aromatic or esters and orthoesters of alicyclic carboxylic acids and aliphatic, aromatic or alicyclic alcohols; carbonic acid esters; acetals; aliphatic or aromatic ethers, cyclic ethers; nitrogen-containing, sulfur-containing, or phosphorus-containing organic Compound;
In the production of a catalyst for polyolefin production using as a carrier a treated product obtained by contact-mixing and co-pulverizing one or more liquid additives selected from the group consisting of silicon compounds, the above-mentioned mixed co-pulverization is continuous pulverization. The process is carried out continuously using a device, and the flow of the processed material is partially blocked in the continuous grinding system to generate a stagnation amount of the processed material, and the above liquid additive is divided into multiple stages and supplied to the mixed co-pulverization system. A method for producing a carrier catalyst for producing polyolefin, characterized in that: The catalyst to which the present invention is applied is not particularly limited, but
Among these, catalysts for olefin polymerization are preferred. The olefins used here are ethylene, propylene, butene-1, butadiene, hexene-1, 4
-Methylpentene-1, styrene, etc., or two or more thereof, and may also contain a small amount of other unsaturated compounds. In the present invention, the inorganic powder refers to the periodic table A
It is a powder made of one or more selected from the group consisting of halides, hydroxy halides, hydroxides, and oxides of elements of Group A, Group A, Group A, and Group B. Typical compounds include magnesium, aluminum, manganese,
A powder consisting of one or more of halides, hydroxyhalides, hydroxides, oxides, etc. of zirconium, iron, etc., preferably magnesium halides, magnesium hydroxyhalides, magnesium oxide, aluminum halides. One or more of these. In the present invention, liquid additives are used, and their addition has effects such as improving the polymerization activity of the catalyst, improving the stereoregularity, or improving the bulk density of the polymer powder. In the present invention, a liquid additive is a compound (or mixture) whose melting point or temperature at which it can become fluid is 100°C or lower, and usually this temperature is 60°C.
The following compounds (or mixtures) are operationally preferred.
Liquid additives also include those that are solid by themselves but become liquid when mixed with other additives. Specifically, aromatic hydrocarbons having unsaturated substituents; halogenated hydrocarbons; aliphatic, aromatic or alicyclic alcohols, aldehydes, acids, acid anhydrides,
Acid halides and amides; esters and orthoesters of aliphatic, aromatic or cycloaliphatic carboxylic acids and aliphatic, aromatic or cycloaliphatic alcohols; carbonic acid esters; acetals; aliphatic or aromatic ethers, cyclic ethers ; Nitrogen-containing, sulfur-containing, or phosphorus-containing organic compound; One or more silicon compounds. As aromatic hydrocarbons with unsaturated substituents,
Styrene, α-methylstyrene, β-methylstyrene, dimethylstyrene, ethylstyrene, vinyltoluene, divinylbenzene, allylbenzene, stilbene, etc. Examples of halogenated hydrocarbons include carbon tetrachloride, carbon tetrabromide, methylene chloride, ethane dichloride, ethane hexachloride, ethane tetrabromide, vinyl chloride, perchloroethylene, chlorobenzene, dichlorobenzene,
α,α-dichlorotoluene, α,α,α-trichlorotoluene, etc. Examples of the alcohol include saturated aliphatic alcohols having 1 to 12 carbon atoms, unsaturated aliphatic alcohols having 2 to 12 carbon atoms, alicyclic alcohols having 4 to 12 carbon atoms, and benzyl alcohol. Examples of the aldehyde include acetaldehyde, propionaldehyde, octylaldehyde, benzaldehyde, tolualdehyde, and naphthaldehyde. Examples of acids include formic acid, acetic acid, propionic acid, oxalic acid, succinic acid, acrylic acid, maleic acid, phenol, benzoic acid, toluic acid, p-oxybenzoic acid, anisic acid, and the like. Examples of acid anhydrides include acetic anhydride, succinic anhydride,
These include benzoic anhydride and toluic anhydride. Examples of acid halides include acetyl chloride, benzyl chloride, toluic acid chloride, anisyl chloride, and the like. Examples of acid amides include acetic acid amide, benzoic acid amide, toluic acid amide, and ε-caprolactam. As esters, methyl formate, butyl formate,
Methyl acetate, ethyl acetate, propyl acetate, butyl acetate, amyl acetate, octyl acetate, vinyl acetate,
Allyl acetate, ethyl butyrate, cyclohexyl acetate,
2-ethylhexyl acetate, ethyl propionate,
Methyl butyrate, ethyl butyrate, ethyl valerate, methyl chloroacetate, ethyl dichloroacetate, methyl methacrylate, ethyl methacrylate, ethyl crotonate, ethyl hivalate, ethyl phenyl acetate, dimethyl maleate, dimethyl malonate, methyl acrylate, Ethyl acrylate, methyl cinnamate,
Octyl laurate, n-butyl crotonate, ethyl cyclohexanecarboxylate, N,N dimethylglycine ethyl ester, phthalide, coumarin,
Butyrolactone, valerolactone, methyl benzoate, ethyl benzoate, propyl benzoate, butyl benzoate, amyl benzoate, hexyl benzoate,
Octyl benzoate, 2-ethylhexyl benzoate, cyclopentyl benzoate, cyclohexyl benzoate, vinyl benzoate, allyl benzoate, phenyl benzoate, benzyl benzoate, 4-benzoate
Tolyl, methyl toluate, ethyl toluate,
Butyl toluate, amyl toluate, 2-ethylhexyl toluate, phenyl toluate, ethyl ethylbenzoate, ethyl 3,5-dimethylbenzoate, methyl anisate, ethyl anisate, propyl anisate, t-butyl anisate, anis Acid 2-
Ethoxyethyl ester, phenyl anisate, benzyl anisate, ethyl ethoxybenzoate, ethyl propoxybenzoate, ethyl butoxybenzoate, ethyl chlorobenzoate, methyl oxybenzoate, ethyl oxybenzoate, cyclohexyl oxybenzoate, oxybenzoic acid Phenyl, benzyl oxybenzoate, methyl aminobenzoate, ethyl fluorobenzoate, butyl fluorobenzoate, ethyl cyanobenzoate, propyl cyanobenzoate, methyl nitrobenzoate, methyl mercaptobenzoate,
Ethyl phenylbenzoate, ethyl t-butylbenzoate, methyl acetoxybenzoate, ethyl trifluoromethylbenzoate, methyl hydroxybenzoate, methyl acetylbenzoate, ethyl dimethylaminobenzoate, propyl dimethylaminobenzoate, methoxycarbonylbenzoic acid Ethyl, propyl formylbenzoate, ethyl carbamoylbenzoate, ethyl α-resorucinate, diethyl phthalate, ethyl hexahydrobenzoate, methyl naphthoate, ethyl naphthoate, propyl naphthoate,
These include butyl naphthoate, 2-ethylhexyl naphthoate, ethyl 4-methyl-1-naphthalenecarboxylate, ethyl 6-methoxy-1-naphthalenecarboxylate, and the like. Orthoesters include ethyl orthoformate,
These include methyl orthoacetate, ethyl orthoacetate, methyl orthobenzoate, ethyl orthobenzoate, methyl orthotoluate, ethyl orthotoluate, ethyl orthoanisate, propyl orthoanisate, methyl orthonaphthoate, and the like. Examples of carbonate esters include diethyl carbonate, dimethyl carbonate, diphenyl carbonate, and the like. Examples of the acetal include dimethyl acetal, diethylacetal, dimethyl formal, diethyl formal, and dipropyl benzoate. Ethers include methyl ether, ethyl ether, propyl ether, butyl ether, amyl ether, hexyl ether, octyl ether, ethyl butyl ether, vinyl methyl ether, ethyl allyl ether, propyl allyl ether, ethyl propenyl ether, methyl cyclopentyl ether, ethyl Cyclohexyl ether, allyl methyl cyclohexyl ether, anisole, diphenyl ether, ethyl phenyl ether, allyl phenyl ether, allyl phenyl ether, methyl phenyl ether, ditolyl ether, peratrol, phenetol, guaiacol, tetrahydrofuran, dioxane, dimethoxy Ethane, tetrahydrofurfuryl methyl ether, ethylene glycol mono- or dialkyl ether (alkyl carbon number 1 to
4) Ethylene glycol monocyclohexyl ether, ethylene glycol mono(methylcyclohexyl) ether, ethylene glycol monotrile ether, ethylene glycol mononaphthyl ether, ethylene glycol diphenyl ether, ethylene glycol ditolyl ether, ethylene glycol phenyl naphthyl ether, diethylene glycol mono or dialkyl ether (alkyl having 1 to 5 carbon atoms), diethylene glycol monocyclopentyl ether, diethylene glycol monocyclohexyl ether, diethylene glycol mono(methylcyclohexyl) ether, diethylene glycol monophenyl ether, diethylene glycol monotrile ether,
Diethylene glycol monoxyl ether, diethylene glycol mono(ethyl phenyl) ether, diethylene glycol dicyclobutyl ether, diethylene glycol dicyclohexyl ether, diethylene glycol phenyl tolyl diether, triethylene glycol mono or dialkyl ether (alkyl has 1 to 4 carbon atoms), tetraethylene glycol mono and dimethyl ether, 2-ethoxyethyl acetate, 2-propionic acid
butoxyethyl, 2-methoxyethyl benzoate,
These include 2-(ethoxyethoxy)ethyl acetate and 2-(butoxybutoxy)ethyl benzoate. Among nitrogen-containing compounds, amines include mono,
Di- and trialkylamines (1 to 4 carbon atoms), tribenzylamine, mono-, di- and triethanolamines, alkenediamines having 2 to 10 carbon atoms and their N, N, N', N' tetraalkyl substituted products, N ，
N,N',N'tetracyclohexylethylenediamine, cycloalkenediamine and its tetraalkyl substituted product, phenylenediamine and N,N,
N′,N′tetraalkyl substituted product, N,N dimethyl,
N',N'diphenylphenylenediamine, N,N
dimethyl, N′,N′diethyltolylenediamine,
N,N,N',N'tetramethylxylene diamine,
N, N, N', N'tetramethylbenzine, N, N,
N',N'tetraalkylnaphthylene diamine, aniline, pyridine, picoline, N,N'dimethylpyherazine, 1,2,4 trimethylpyherazine,
These include N,N dimethylpyheridine, 4,4'-methylenebis(N,N dimethylaniline), 4,4'butylidenebis(N,N dibutylaniline), diethylenetriamine, ethylenetetramine, and the like. Nitriles among nitrogen-containing compounds include acetonitrile, benzonitrile, tolnitrile, malononitrile, succinonitrile, adiponitrile, sebacinonitrile, neopentazinitrile,
Cyclobutanenitrile, cyclohexane dinitrile, decahydronaphthalenedinitrile, phthalonitrile, isophthalonitrile, terephthalonitrile, methylphthalonitrile, dicyandiphenyl, naphthalenedinitrile, dimethylnaphthalenedinitrile, xylene dinitrile, 2-phenyl These include glutaronitrile and tetrahydronaphthalenedinitrile. Other nitrogen-containing compounds include urea, tetramethylurea, phenyl isocyanate, tolylisocyanate, azobenzene, nitrobenzene, and the like. Sulfur-containing compounds include thionyl chloride, ethylthioalcohol, n-propylthioalcohol, thiophenol, diethylthioether, diphenylthioether, methylphenylthioether, ethylene sulfide, propylene sulfide, dimethylsulfone, methylethylsulfone, diethyl Sulfone, dibutyl sulfone, dihexyl sulfone, dioctyl sulfone,
Dialkyl sulfone with 2 to 36 carbon atoms such as dilauryl sulfone and distearyl sulfone; 3 carbon atoms such as methylvinyl sulfone, divinyl sulfone, diallyl sulfone, dipropenyl sulfone, dibutenyl sulfone, dihexenyl sulfone, and diundecenyl sulfone; ~22 alkenyl sulfones, methylcyclobutenyl sulfones, dicyclohexenyl sulfones, dicyclooctenyl sulfones, dicyclooctadienyl sulfones, etc., cycloalkenyl sulfones having 5 to 16 carbon atoms, methylphenyl sulfones, diphenyl sulfones, These include arylsulfones having 7 to 28 carbon atoms, such as tolylphenylsulfone, dinaphthylsulfone, dianthracenylsulfone, ditolylsulfone, and dixylylsulfone. Examples of phosphorus-containing compounds include phosphorus trichloride, phosphorus tribromide, phosphorus oxychloride, ethylphosphine, triethylphosphine, tributylphosphine, trioctylphosphine, triphenylphosphine, dimethylphosphite, dioctylphosphine,
Diphenylchlorophosphite, diethylchlorophosphite, diphenylbromophosphite,
Methyl dichlorophosphite, phenyl dichlorophosphite, trimethyl phosphite, triethyl phosphite, tripropyl phosphite,
Tributyl phosphite, trinonylphenyl phosphite, trioctyl phosphite, tridecyl phosphite, triphenyl phosphite,
diphenyl (2-chloroethyl) phosphite,
Tris (2-chloroethyl) phosphite, ethyl diethyl phosphinite, phenyl diphenyl phosphinite, ethyl phenylethyl phosphinite, ethyl diphenyl phosphinite, ethyl dibutyl phosphinite, diethyl ethyl phosphinite, diethyl phenyl phosphoonite,
Diethyl phosphorochloridate, diphenyl phosphorochloridate, ethyl phosphorodichloridate, phenyl phosphorodichloridate, triethyl phosphate, tributyl phosphate, triphenyl phosphate, ethyl dimethyl phosphinate, ethyl butyl phosphinate, ethyl These include diphenyl phosphinate, dimethyl methyl phosphonate, diethyl ethyl phosphonate, diphenylphenyl phosphonate, diphenyl 2-chloroethyl phosphonate, and the like. Silicon compounds include silicon tetrachloride, silicon tetrabromide, silicon tetraiodide, tetraethoxysilane, chlorotriethoxysilane, dichlorodiethoxysilane, diethyldiethoxysilane, phenyltriethoxysilane, methyltriacetoxysilane, and dichlorotriethoxysilane. These include chloroacetoxyethoxysilane, aryl silicate, etc. In the present invention, the amount of liquid additive used is inorganic powder.
5 parts by weight or more per 100 parts by weight, preferably
It is 15 parts by weight or more. If less than 5 parts by weight are used, a catalyst with effective performance will not be obtained. Although there is no particular upper limit on the amount, in order to have effective performance as a catalyst, it is desirable to use a large amount of liquid additive and to sufficiently contact and mix with the inorganic powder. The preferred upper limit is 60 parts by weight. In the present invention, as a mixing and co-pulverizing step, a pulverizing operation is performed in a state where an inorganic powder and a liquid additive coexist. However, one of the requirements is that the above-mentioned mixing and co-pulverization be carried out continuously using a continuous crusher. Continuous crushing processes are more advantageous than partial crushing processes because of their high productivity and stable quality. An example of such a continuous grinding device is a continuous vibration mill, a schematic diagram of which is shown in FIG. Continuous pulverization can be defined as the constant supply of raw materials and discharge of processed materials to a system in which powder is regularly pulverized. Therefore, the continuous co-grinding system according to the present invention has an inlet and an outlet. Furthermore, in the present invention, it is necessary to partially block the flow of the processed material in the continuous grinding system to generate a stagnation amount of the processed material. The material to be treated undergoes the pulverization process for a certain period of time (residence time) from the inlet to the outlet of the system, but in order for the catalyst to have the specified performance, it is necessary to maintain the pulverization system for a certain residence time. be done. In order to maintain a constant residence time in a continuous grinding system, it is sufficient to provide flow blocking means sufficient to ensure a specific residence amount for the amount of raw material supplied. Such clogging means include any means that generates a substantial amount of stagnation of the processed material within the continuous co-grinding system. For example, Figures 2 to 4
The required number of jamb plates (hatched lines indicate openings) shown in the figure may be provided at arbitrary positions from the inlet to the outlet of the system, or as shown in FIG. By moving the opening of the outlet 8 of 6 above the end plate 7, the overflow height can be changed. Therefore, by providing the opening at a high position on the end plate 7, a stagnation amount can be generated. can. For the jama plates shown in Figures 2 to 4 and the outlet opening shown in Figure 5, the area below the lowest point of the opening should be at least 20% of the total cross-sectional area, preferably 50%. That's all. Further, the area of the opening may be any size as long as it satisfies the above conditions, but it is preferably 5% or more in industrial production. Further, in the present invention, it is necessary that the liquid additive is supplied to the mixing and co-grinding system in multiple stages. It has not been theoretically elucidated why the performance of the catalyst according to the present invention is related to this requirement. A pulverized composition with good performance cannot be obtained. Continuous vibration mill 1 shown in Figure 1
Inorganic powder charging port 2 is connected to liquid additive addition ports 3 and 4.
However, a crushed material outlet 5 is also provided. Two or more stages are required for dividing the supply of the liquid additive, and the greater the number of stages, the better the effect. Hereinafter, the case where the present invention is applied to a polyolefin polymerization catalyst will be briefly described. The catalyst according to the present invention can be obtained by supporting a catalytically active component such as titanium, panadium, or zirconium compounds on the carrier obtained as described above. The method of supporting is not particularly limited, but representative examples include the following. The mode of support may be physical or chemical. (1) A method of co-pulverizing a catalytically active component with a carrier component: For example, titanium trichloride or titanium tetrachloride alone or mixed with other liquid additives are charged into a continuous vibration mill and co-pulverized. When a supported catalyst is prepared by the above-mentioned co-pulverization, it is preferable to adjust the amount of the titanium compound so that the amount of metallic titanium in the catalyst is in the range of 0.1 to 10 w%. (2) Method of heat treating the catalytically active component with the carrier component:
For example, a liquid catalytically active component such as titanium tetrachloride is directly mixed with a carrier component and subjected to heat treatment to be supported. The α-olefin polymerization reaction can be carried out in the presence or absence of a liquid diluent, ie, in the presence of a liquid monomer. The polymerization temperature may be selected appropriately, and is usually 200°C or lower. The polymerization pressure can also be appropriately selected, and is usually set in the range from normal pressure to several tens of atmospheres. When adding the catalyst components, three components are added: (a) the above-mentioned carrier catalyst, component (b) an organoaluminum compound such as dialkyl aluminum halide and trialkyl aluminum, and component (c) an electron donor. They may be added in any order. Furthermore, one or both of the components (b) and (c) may be partially added during the polymerization. When using a solvent in the polymerization reaction, it is important to use an inert solvent for the Ziegler catalyst. Examples of the solvent include the following. Saturated aliphatic hydrocarbons such as pentane, hexane, heptane, isooctane, butane, kerosene, etc.; saturated alicyclic hydrocarbons such as cyclopentane, cyclohexane, methylcyclohexane; and aromatics such as benzene, toluene, xylene, ethylbenzene. Hydrocarbons as well as mixtures thereof. Examples of the present invention are shown below. [Example 1] 1 Preparation of catalyst In a continuous vibration mill (hereinafter referred to as a continuous mill) having a ball space volume of 100 as shown in Fig. 1, a baffle plate ( Opening ratio 30%) (hereinafter referred to as Seki)
6 kg of anhydrous magnesium chloride per hour from the pulverized material charging port (hereinafter referred to as charging port) in a nitrogen atmosphere.
and 0.075 kg of anhydrous aluminum chloride, 0.63 kg of ethyl benzoate per hour was divided into two liquid additive addition ports (hereinafter referred to as addition ports), and diphenyl ether and carbon tetrachloride were added for 1 hour. 0.64Kg and 0.96Kg were mixed, respectively, and added to 18 addition ports and pulverized to obtain a uniform powdery preliminary composition from the pulverized material outlet (hereinafter referred to as pulverized composition). The continuous mill residence time of the milled composition was calculated to be 10 hours. The resulting pulverized composition was subjected to the following activation treatment. 300
Grind the above composition under nitrogen atmosphere in a ml round bottom flask.
20g of titanium tetrachloride and 100ml of titanium tetrachloride were taken out, stirred at 80°C for 2 hours, and then the supernatant liquid was removed by decantation. Next, 200 ml of n-heptane was added, the mixture was stirred at room temperature for 30 minutes, and the supernatant liquid was removed by decantation. The washing operation was repeated four times. Furthermore n-
200 ml of heptane was added to obtain a slurry of the composition supporting the titanium compound. 2 Polymerization of propylene In a SUS32 autoclave with an internal volume of 2, in a nitrogen atmosphere, 1 part of n-heptane, 50 mg of the above composition,
After charging 0.24 ml of diethyl aluminum monochloride, 0.07 ml of triethyl aluminum, and 0.07 ml of methyl p-toluate, the nitrogen in the autoclave was evacuated using a vacuum pump, and the hydrogen was reduced to a gas phase partial pressure of 0.3.
Kg/cm ² G was charged, and propylene was charged to set the pressure in the gas phase to 2 Kg/cm ² G. The contents of the autoclave were heated, and after 5 minutes the internal temperature was raised to 75°C, and the polymerization was continued for about 2 hours while charging propylene to maintain the polymerization pressure at 75°C and 7 kg/cm ² G. 0.0375 ml of triethylaluminum was additionally charged four times at 20 minute intervals from the start of polymerization. After cooling the autoclave, unreacted propylene was purged and the contents were taken out, filtered and dried under reduced pressure at 60°C to obtain 528 g of white powdery polypropylene powder. The ratio of the boiling n-heptane extraction residual polymer to this powdered polypropylene powder (hereinafter abbreviated as powder) is 96.5wt%, and the bulk specific gravity is 96.5wt%.
The intrinsic viscosity was 0.42 g/ml, and the intrinsic viscosity (measured with tetralin solvent at 135° C.) was 1.66 dl/g. On the other hand, 7.5 g of n-heptane soluble polymer (amorphous polypropylene) was obtained by concentrating the filtrate.
The ratio of boiling n-heptane extraction residual polymer to the total produced polymer (hereinafter abbreviated as total) is 95.1wt
It was %. The polymerization activity of the catalyst in this polymerization reaction is 4098g/g
-solid catalyst/hr, and the amount of polypropylene obtained was 10929g/g-solid catalyst. [Example 2] In a continuous mill having a ball space volume of 40, 0.5 kg of anhydrous magnesium chloride was charged per hour from the charging port in a nitrogen atmosphere using a bar of the same shape and the same opening ratio as in Example 1. Ethyl benzoate was mixed at 0.053Kg per hour at one addition port, and diphenyl ether and tetrabromoethane were mixed at 0.054Kg and 0.038Kg per hour, respectively, and added to three addition ports and pulverized. A uniform powder-like pulverized composition was obtained. The continuous mill residence time of the milled composition was calculated to be approximately 20 hours. This pulverized composition was subjected to activation treatment under the same conditions as in Example 1, and propylene polymerization was performed. The results are shown in Table 1. [Example 3] In the same continuous mill as in Example 2, 1.0 kg of anhydrous magnesium chloride and 0.025 kg of anhydrous aluminum chloride were charged per hour from the charging port in a nitrogen atmosphere, and 0.105 kg of ethyl benzoate was charged per hour. was added to one addition port, and 0.054 kg of diphenyl ether per hour was added to three addition ports and pulverized to obtain a uniformly powdered pulverized composition. This pulverized composition was subjected to activation treatment under the same conditions as in Example 1, and propylene polymerization was performed. The results are shown in Table 1. [Example 4] In the same continuous mill as in Example 2, 1 kg of anhydrous magnesium chloride was charged per hour from the charging port in a nitrogen atmosphere, and tetraethoxysilane and α,
α,α-Trichlorotoluene was mixed at 0.186 kg and 0.207 kg per hour, respectively, and added to three addition ports and pulverized to obtain a uniform powdered pulverized composition. This pulverized composition was subjected to activation treatment under the same conditions as in Example 1, and propylene polymerization was performed. The results are shown in Table 1. [Example 5] In the same continuous mill as in Example 2, 1 kg of anhydrous magnesium chloride was charged per hour from the charging port in a nitrogen atmosphere, and 0.093 kg and 0.187 kg of tetraethoxysilane and dichloroethane were charged per hour, respectively.
were mixed, added to three addition ports and pulverized to obtain a uniform powdered pulverized composition. This pulverized composition was subjected to activation treatment under the same conditions as in Example 1, and propylene polymerization was performed. The results are shown in Table 1. [Example 6] In the same continuous mill as in Example 2, 1 kg of anhydrous magnesium chloride was charged per hour in a nitrogen atmosphere, and ethyl orthoacetate was charged per hour.
0.088 kg was added to one addition port, and 0.25 kg of ethane dichloride per hour was added to three addition ports and pulverized to obtain a uniform powdered composition.
This pulverized composition was subjected to activation treatment under the same conditions as in Example 1 to carry out propylene polymerization. The results are shown first. [Comparative Example 1] Large batch vibration mill (hereinafter referred to as large mill),
For example, in a ball having a void volume of 250, 120 kg of anhydrous magnesium chloride, 1.5 kg of anhydrous aluminum chloride, 12.6 kg of ethyl benzoate,
Grinding was carried out by charging 12.8 kg of diphenyl ether and 19.2 kg of carbon tetrachloride, but the internal temperature rose even though the large mill was cooled from the outside with refrigerant, and grinding was frequently interrupted to cool down. It was necessary.
Small batch vibration mill, e.g. ball void volume 0.1
In the case of a large-sized mill, a catalyst carrier (pulverized composition) exhibiting the target performance can be obtained after a grinding time of about 30 hours, but in the case of a large mill, the grinding time required 100 to 150 hours (including cooling time). The pulverized composition obtained by pulverization in a large mill was subjected to activation treatment under the same conditions as in Example 1, and propylene polymerization was performed. The results are shown in Table 1, and only a polypropylene powder with low polymerization activity and many very coarse particles was obtained. [Comparative Example 2] In a continuous mill with a ball space volume of 40, 5.0 kg of anhydrous magnesium chloride was fed per hour from the charging port in a nitrogen atmosphere without using a baffle plate or the like to generate a stagnation amount (hereinafter referred to as "no baffle"). Charge,
Ethyl benzoate, diphenyl ether, carbon tetrachloride per hour 0.53Kg, 0.54Kg, 0.80 respectively
When pulverization was carried out by adding Kg into the mixture and adding it from one addition port, no pulverized material was obtained from the pulverized material discharge port, and when the inside of the continuous mill was inspected, the stagnant material was wet and hardened. . [Comparative Example 3] In the same continuous mill as in Example 2, 3.0 kg of anhydrous magnesium chloride and 0.15 kg of anhydrous aluminum chloride were charged per hour from the charging port in a nitrogen atmosphere,
0.32Kg, 0.32Kg, and 0.24Kg of ethyl benzoate, diphenyl ether, and carbon tetrachloride per hour, respectively.
When pulverization was carried out by adding Kg of the mixture through one addition port, the same condition as in Comparative Example 2 was obtained, and no pulverized material was obtained. [Comparative Example 4] In the same continuous mill as in Comparative Example 2, 6 kg of anhydrous magnesium chloride was charged per hour from the charging port in a nitrogen atmosphere, and ethyl benzoate was charged at a rate of 0.63 kg per hour.
Kg was divided into 2 addition ports, and diphenyl ether and tetrabromoethane were mixed at 0.64Kg and 0.45Kg per hour, respectively, and added to 18 addition ports and pulverized, resulting in a nearly uniform pulverized composition. I got it. The continuous mill residence time of the milled composition was calculated to be approximately 1 hour. This pulverized composition was subjected to activation treatment under the same conditions as in Example 1, and propylene polymerization was performed. The results are shown in Table 1.
Only a powder with a low polymerization activity and a large amount of coarse particles was obtained.

[Table] * Per amount of solid catalyst used

[Brief explanation of the drawing]

FIG. 1 is a schematic diagram of a continuous vibration mill used in the present invention. 1: Vibration mill, 2: Inorganic powder charging port, 3, 4:
Addition port for liquid additive, 5: Pulverized material discharge port. Figures 2 to 4 show examples of baffle plates inserted into the grinding system. The diagonal lines are openings. FIG. 5-1 is a front view of the vicinity of the outlet end of the vibrating mill shown in FIG. 1, and FIG. 5-2 is a side view thereof. 6: crushed material, 7: end plate, 8: outlet.

Claims (1)

[Claims] 1. An inorganic compound consisting of one or more selected from the group consisting of halides, hydroxyhalides, hydroxides, and oxides of elements of Group A, Group A, Group A, and Group B of the Periodic Table. powder and its
Aromatic hydrocarbons having 5 parts by weight or more of unsaturated substituents per 100 parts by weight; halogenated hydrocarbons; aliphatic, aromatic or alicyclic alcohols, aldehydes, acids, acid anhydrides, acid halides and acid amides ; aliphatic, aromatic or alicyclic carboxylic acids and aliphatic;
Esters and orthoesters of aromatic or alicyclic alcohols; carbonic esters; acetals; aliphatic or aromatic ethers, cyclic ethers; nitrogen-containing,
Sulfur-containing or phosphorus-containing organic compounds; For the production of polyolefin production catalysts using as a carrier a treated product obtained by contact-mixing and co-pulverizing a liquid additive consisting of one or more selected from the group consisting of silicon compounds. Then, the above-mentioned mixing and co-pulverization is carried out continuously using a continuous grinding device, and the flow of the processed material is partially blocked in the continuous grinding system to generate a stagnation amount of the processed material, so that the above-mentioned liquid additive is mixed and co-pulverized. A method for producing a carrier catalyst for producing polyolefin, characterized in that it is supplied to a pulverization system in multiple stages.