JPH0368045B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a method for producing a crystalline copolymer consisting of propylene, ethylene, and an α-olefin having 4 or more carbon atoms. More specifically, the present invention relates to a method for obtaining a copolymer having excellent heat-sealability and suitable for film use in a high yield, while further reducing the amount of undesirable soluble copolymer by-products. Polypropylene has excellent physical properties and is used for a wide variety of purposes. For example, it is widely used in the field of packaging films, but in order to improve heat sealability at low temperatures in this type of application, 1 to 5% by weight of ethylene is usually copolymerized and propylene/ethylene copolymerized. It is generally provided as a combination. Polypropylene film modified as described above has the advantage of better transparency and scratch resistance than low-density polyethylene film, which is also used as a packaging film, but it also has poor heat sealability at low temperatures. It's on. In order to further improve heat-sealability, there is a method of increasing the amount of ethylene copolymerized, but in this case, the proportion of soluble copolymer that is of no use value increases, and the yield of the desired copolymer decreases. There is a disadvantage in that the value decreases. Moreover, in slurry polymerization, the properties of the slurry during polymerization deteriorate, and the polymerization may even become difficult. In order to avoid such disadvantages, a method of copolymerizing propylene with ethylene and α-olefin having 4 or more carbon atoms using a conventional titanium trichloride catalyst has been proposed in JP-A-49-35487 and JP-A-49-35487. Showa 51-79195
This method has been proposed in various publications such as No. 16588 and Japanese Patent Application Laid-open No. 16588/1983. According to these proposals, it can be said that the production rate of solvent-soluble polymer is reduced compared to the case of binary copolymerization of propylene and ethylene, but it is still lower compared to the case of homopolymerization of propylene. The proportion of solvent-soluble polymers produced is large;
In particular, as the amount of copolymerization of ethylene and/or _C4 or higher α-olefin increases, this tendency becomes even more pronounced. The present inventors have discovered a specific solid titanium catalyst component, an organometallic compound catalyst component, and an organometallic compound catalyst component that produce approximately the same proportion of solvent-soluble polymers during propylene homopolymerization as compared to the titanium trichloride catalyst proposed above. When a supported catalyst formed from an electron donor catalyst component is used for the copolymerization of propylene, ethylene, and an α-olefin having 4 or more carbon atoms, the predicted results will be lower than when using the titanium trichloride catalyst in the proposal. In addition, we found that it was possible to further reduce the amount of soluble polymers and to obtain significantly superior results in terms of yield of the desired copolymer and catalyst efficiency, and proposed this method in JP-A-54-26891. . Although a remarkable improvement was observed through the use of the catalyst specifically disclosed in this publication, if a copolymer with a considerably high ethylene content is to be produced, it is necessary to make a slurry by forming a porridge-like polymer. Problems remained, such as that it became difficult to continue polymerization due to deterioration of properties, and that solid polymers could not be obtained in sufficiently high yields. If it is not possible to increase the ethylene content to obtain a copolymer with a low melting point, the only way to obtain a copolymer with a low melting point is to increase the content of an α-olefin having 4 or more carbon atoms. is smaller and the rate of copolymerization is also slow, so it was not a good idea to increase the content of the α-olefin more than necessary. The present invention was made in view of these circumstances, and its purpose is to produce a copolymer with a higher ethylene content with improved operability and even better yields. . That is, in the present invention, in the presence of a Ziegler type olefin polymerization catalyst, propylene, ethylene and α having 4 or more carbon atoms are
- Random copolymerization of olefins with a propylene content of 85 to 98 mol% and an ethylene content of 1 to 98 mol%
10 mol%, α-olefin content of carbon number 4 or more is 1 to 10 mol%, and crystallinity is 40% by weight.
(A) contains magnesium, titanium, halogen and an electron donor as essential components, and has an average particle size of 1 to 200μ and a geometric standard deviation of particle size distribution of 2.1
(B) an organoaluminum compound catalyst component; and (C) an electron donor catalyst component. The highly active and highly stereoregular solid titanium-based catalyst component (A) used in the present invention contains magnesium, titanium, halogen, and an electron donor as essential components, and has a magnesium/titanium (atomic ratio).
is larger than 1, preferably 3 to 50, particularly preferably 6 to 30, halogen/titanium (atomic ratio) is preferably 4 to 100, particularly preferably 6 to 40, electron donor/titanium (molar ratio) is preferably It is in the range of 0.1 to 10, particularly preferably 0.2 to 6. The specific surface area is preferably 3 m ² /g or more, more preferably about 40 m ² /g or more, and even more preferably 100 m ² /g to 800 m ² /g.
It is. Usually, titanium compounds are not removed by simple means such as washing with hexane at room temperature. Regardless of the raw material magnesium compound used for catalyst preparation, the X-ray spectrum should preferably show a microcrystalline state of the magnesium compound, or should preferably be significantly higher than that of an ordinary commercially available magnesium dihalide. It is in a microcrystalline state. In addition to the above-mentioned essential components, other elements, metals, functional groups, etc. may be included. Furthermore, it may be diluted with an organic or inorganic diluent. The solid titanium catalyst component (A) has an average particle size of 1 to 200μ, preferably 3 to 100μ, particularly preferably 6 to 50μ, and a geometric standard deviation of particle size distribution of less than 2.1, preferably 1.9 or less, more preferably is less than 1.7. Here, the particle size distribution of the titanium catalyst component particles can be measured by a light transmission method. Specifically, the catalyst component is diluted to a concentration of around 0.01 to 0.5% in an inert solvent such as decalin, placed in a measurement cell, illuminated with a narrow light, and passed through the liquid in a settled state with particles. The particle size distribution is determined by continuously measuring the light intensity.
Based on this particle size distribution, the standard deviation σg is determined from the lognormal distribution function. Note that the average particle diameter of the catalyst is indicated by the weight average diameter, and the measurement of the particle size distribution is calculated by performing sieving in the range of 10 to 20% of the weight average particle diameter. The solid titanium catalyst component (A) has the ability to produce highly stereoregular polymers with high catalytic efficiency. For example, when homopolymerizing propylene under the same conditions, isotacticity (boiling It has the ability to produce 3,000 g or more, particularly 5,000 g or more, more preferably 10,000 g or more of polypropylene having a n-heptane insoluble content of 92% or more, especially 96% or more, per millimole of Ti. Preferably, it has a spherical shape, such as a true sphere, an elliptical sphere, or a granular shape. By using a titanium catalyst component that satisfies these various requirements, a copolymer with a high ethylene content can be produced with good operability and at a high yield. A titanium catalyst component (A) that satisfies all of these conditions can be prepared by forming a magnesium compound having an average particle size and particle size distribution, and more preferably a shape within the above-mentioned range, and then preparing the catalyst. It can be obtained by a method in which a liquid magnesium compound and a liquid titanium compound are brought into contact with each other to form a solid catalyst having the particle properties as described above. Such methods are described, for example, in Japanese Patent Application Laid-Open Nos. 55-135102, 55-135103, and
It is disclosed in Japanese Patent Application No. 56-811, No. 56-67311, Japanese Patent Application No. 181019-1980, etc. A few examples of these methods will be briefly described. (1) A magnesium compound/electron donor complex with an average particle diameter of 1 to 200μ and a geometric standard deviation of particle size distribution σg of less than 2.1 is combined with an electron donor and/or a reaction aid such as an organoaluminum compound or a halogen-containing silicon compound. With or without pretreatment with a halogenated titanium compound, preferably titanium tetrachloride, which forms a liquid phase under the reaction conditions. (2) A liquid magnesium compound that does not have reducing ability and a liquid titanium compound are reacted in the presence of an electron donor to form particles with an average particle size of 1 to 200μ,
Solid components with a geometric standard deviation σg of particle size distribution less than 2.1 are precipitated. If necessary, a liquid titanium compound, preferably titanium tetrachloride, or a liquid titanium compound, preferably titanium tetrachloride, is reacted with an electron donor. In particular, in the present invention, when a magnesium compound or an electron donor complex is precipitated as a spherical solid from a liquid in the method (1), or when a solid component is precipitated in the form of a spherical solid in the method (2), Good results can be obtained if the test is carried out under conditions such that solids precipitate. Magnesium compounds used in the preparation of the titanium catalyst component include magnesium oxide, magnesium hydroxide, hydrotalcite, magnesium carboxylate, alkoxymagnesium, allyloxymagnesium, alkoxymagnesium halide, allyloxymagnesium halide, magnesium dihalide, organomagnesium compounds,
Examples include reactants of organomagnesium compounds and electron donors, halosilanes, alkoxysilanes, silanols, aluminum compounds, and the like. The organoaluminum compound that may be used in the preparation of the titanium catalyst component can be selected from organoaluminum compounds that can be used in the olefin polymerization described below. moreover,
Examples of halogen-containing silicon compounds that may be used in preparing the titanium catalyst component include silicon tetrahalides, silicon alkoxy halides, silicon alkyl halides, and halopolysiloxanes. Examples of titanium compounds used in the preparation of the titanium catalyst component include titanium tetrahalide, alkoxytitanium halide, allyloxytitanium halide, alkoxytitanium, allyloxytitanium, and titanium tetrahalide, especially titanium tetrachloride. preferable. Electron donors that can be used to prepare the titanium catalyst component include alcohols, phenols,
Oxygen-containing electron donors such as ketones, aldehydes, carboxylic acids, esters of organic or inorganic acids, ethers, acid amides, alkoxysilanes of acid anhydrides, nitrogen-containing electron donors such as ammonia, amines, nitriles, isocyanates, etc. Can be used. More specifically, alcohols having 1 to 18 carbon atoms such as methanol, ethanol, propanol, pentanol, hexanol, octanol, dodecanol, octadecyl alcohol, benzyl alcohol, phenylethyl alcohol, cumyl alcohol, isopropylbenzyl alcohol; Phenols having 6 to 20 carbon atoms which may have a lower alkyl group such as phenol, cresol, xylenol, ethylphenol, propylphenol, nonylphenol, cumylphenol naphthol; acetone, methyl ethyl ketone, methyl isobutyl ketone, acetophenone, benzophenone, etc. Ketones with 3 to 15 carbon atoms; aldehydes with 2 to 15 carbon atoms such as acetaldehyde, propionaldehyde, octylaldehyde, benzaldehyde, tolualdehyde, naphthaldehyde; methyl formate, methyl acetate, ethyl acetate, vinyl acetate, propyl acetate , octyl acetate, cyclohexyl acetate, ethyl propionate,
Methyl butyrate, ethyl valerate, methyl chloroacetate,
Ethyl dichloroacetate, methyl methacrylate, ethyl crotonate, ethyl cyclohexanecarboxylate, methyl benzoate, ethyl benzoate, propyl benzoate, butyl benzoate, octyl benzoate,
Cyclohexyl benzoate, phenyl benzoate, benzyl benzoate, methyl toluate, ethyl toluate, amyl toluate, ethyl ethylbenzoate, methyl anisate, ethyl anisate, ethyl ethoxybenzoate, dibutyl malonate, isopropyl malonate Diethyl, n-butyl diethyl malonate, phenyl diethyl malonate, 2-allyl diethyl malonate, diisobutyl diethyl malonate,
Di-n-butyl diethyl malonate, di-n-butyl succinate, diethyl methyl succinate, dibutyl ethyl succinate, dimethyl maleate, dibutyl maleate, monooctyl maleate, dioctyl maleate, dibutyl butyl maleate, diethyl butyl maleate, fumaric acid Diisooctyl, diethyl itaconate, di-n-butyl itaconate, dimethyl citraconate, diethyl 1,2-cyclohexanedicarboxylate, di2-ethylhexyl 1,2-cyclohexanedicarboxylate, dimethyl phthalate,
Monoisobutyl phthalate, diethyl phthalate, ethyl n-butyl phthalate, di-n propyl phthalate,
n-butyl phthalate, isobutyl phthalate, di-n-heptyl phthalate, di-2-ethylhexyl phthalate, di-n-octyl phthalate, dineopentyl phthalate, benzylbutyl phthalate, diphenyl phthalate, diiso-butyl naphthalene dicarboxylate ,
Organic acid esters having 2 to 30 carbon atoms, such as di-2-ethylhexyl sebacate, γ-butyrolactone, δ-valerolactone, coumarin, phthalide, and ethylene carbonate; Acid halides having 2 to 15 carbon atoms; ethers having 2 to 20 carbon atoms such as methyl ether, ethyl ether, isopropyl ether, butyl ether, isoamyl ether, tetrahydrofuran, anisole, and diphenyl ether; acetic acid amide, benzoic acid amide, toluyl Acid amides such as acid amide; amines such as methylamine, ethylamine, diethylamine, tributylamine, piperidine, tribenzylamine, aniline, pyridine, picoline, tetramethylmethylenediamine, tetramethylethylenediamine; acetonitrile, benzonitrile, trinitrile, etc. Nitriles; organic phosphorus compounds having a P-O-C bond such as trimethyl phosphite and triethyl phosphite; alkoxysilanes such as ethyl silicate and diphenyldimethoxysilane; and the like. Two or more types of these electron donors can be used. Electron donors preferably contained in the titanium catalyst component (A) include esters of organic or inorganic acids, alkoxy(aryloxy)silane compounds, ethers, ketones, tertiary amines, acid halides, and acid anhydrides. Organic acid esters and alkoxy (aryloxy) silane compounds are particularly preferred, and among them, esters of aromatic monocarboxylic acids and alcohols having 1 to 8 carbon atoms, malonic acid, substituted malonic acids, and substituted succinic acids are preferred. Particularly preferred are acids, esters of dicarboxylic acids such as maleic acid, substituted maleic acid, 1,2-cyclohexanedicarboxylic acid, and phthalic acid, and alcohols having 2 or more carbon atoms. Of course, these electron donors do not necessarily need to be used as raw materials during the preparation of the titanium catalyst, but may be used as other compounds that can be converted into these electron donors and converted into these electron donors during the catalyst preparation process. The titanium catalyst component obtained by the methods exemplified above can be purified by thoroughly washing with a liquid inert hydrocarbon after the reaction is completed. Inert liquid hydrocarbons used for this purpose include n-pentane, isopentane, n-hexane, isohexane, n-heptane, n-octane, isooctane, n-decane, n-dodecane, kerosene, liquid paraffin, etc. Aliphatic hydrocarbons such as cyclopentane, methylcyclopentane, cyclohexane, methylcyclohexane; Aromatic hydrocarbons such as benzene, toluene, xylene, cymene; Halogenated hydrocarbons such as chlorobenzene, dichloroethane Examples include hydrocarbons and mixtures thereof. As the organoaluminum compound catalyst component (B) used in the present invention, a compound having at least one Al-carbon bond in the molecule can be used, for example, (i) a compound having the general formula R ¹ _n Al (OR ² ) _o H _{p _} ^{_ _} , n≦n<
3, p is a number of 0≦p<3, q is a number of 0≦q<3, and m+n+p+q=3), (ii) general formula M ¹ AlR ¹ ₄
(Here, M ¹ is Li, Na, K, and R ¹ is the same as above.) A complex alkylated product of a Group 1 metal and aluminum can be mentioned. Examples of the organoaluminum compounds that belong to (i) above include the following. General formula R ¹ _n Al
(OR ² ) _3-n (where R ¹ and R ² are the same as above. m
is preferably a number of 1.5≦n≦3). general formula
R ¹ _n lX _3-n (Here, R ¹ is the same as above. X is halogen,
m is preferably 0<m≦3), general formula R ¹ _n
AlH _3-n (where R ¹ is the same as above, m is preferably 2≦m<3), general formula R ¹ _n Al(OR ² ) _o X _q (where R ¹ and R ² are Same as .X is halogen, 0
<m≦3, 0≦n<3, 0≦q<3, m+n+
Examples include those represented by q=3). Among the aluminum compounds belonging to (i), more specifically, trialkylaluminum such as triethylaluminum and tributylaluminium, trialkenylaluminum such as triisoprenylaluminum, dialkylaluminum alkoxide such as diethylaluminum ethoxide and dibutylaluminum butoxide, In addition to alkylaluminum sesquialkoxides such as _{ethylaluminum} sesquiethoxide and butylaluminum sesquibutoxy, R ¹ _2.5 Al (OR ² ) _0.5
Partially alkoxylated alkyl aluminum halides, such as diethylaluminum chloride, dibutyl aluminum chloride, diethylaluminium bromide, ethyl aluminum sesquichloride, butyl aluminum sesquichloride, ethyl aluminum sesquibromide, etc., with an average composition of alkyl aluminum sesquihalides, such as
Partially halogenated alkylaluminiums such as alkylaluminum dihalides such as ethylaluminum dichloride, propylaluminum dichloride, butylaluminum dibromide etc., dialkylaluminum hydrides such as diethylaluminum hydride, dibutylaluminum hydride, ethylaluminum dihydride, Partially hydrogenated alkyl aluminums such as alkyl aluminum dihydrides such as propyl aluminum dihydride, partially alkoxylated and halogenated alkyl aluminums such as ethyl aluminum ethoxy chloride, butyl aluminum butoxy chloride, ethyl aluminum ethoxy bromide It is. Further, as a compound similar to (i), it may be an organoaluminum compound in which two or more aluminum atoms are bonded via an oxygen atom or a nitrogen atom. Examples of such compounds include (C ₂ H ₅ ) ₂ AlOAl(C ₂ H ₅ ) ₂ , (C ₄ H ₉ ) ₂ AlOAl(C ₄ H ₉ ) ₂ ,

[Preparation of highly active, highly stereoregular solid titanium catalyst component (A)]

Anhydrous magnesium chloride 7.14 g (75 mmol), decane 37 ml and 2-ethylhexyl alcohol 35.1 g
ml (225 mmol) was heated at 130℃ for 2 hours to form a homogeneous solution, and phthalic anhydride was added to this solution.
Add 1.67g (11.3mmol) and further add 1.67g (11.3mmol) at 130℃.
Stir and mix for a period of time to dissolve the phthalic anhydride into the homogeneous solution. After the homogeneous solution thus obtained was cooled to room temperature, the entire amount was dropped over 1 hour into 200 ml (1.8 mmol) of titanium tetrachloride maintained at -20°C. After charging, the temperature of this mixture was raised to 110℃ over 4 hours, and when it reached 110℃, 4.0ml (18.8mmol) of diisobutyl phthalate was added.
was added and kept at the same temperature for 2 hours with stirring. After the completion of the 2-hour reaction, the solid portion was collected by heating, and after resuspending this solid portion in 275 ml of TiCl ₄ , the heating reaction was performed again at 110° C. for 2 hours.
After the reaction is complete, collect the solid part by heating again.
Wash thoroughly with decane and hexane at 110°C until no free titanium compound is detected in the washing solution. The titanium catalyst component (A) synthesized by the above production method is stored as a hexane slurry, and a portion of this is dried for the purpose of investigating the catalyst composition. The composition of the titanium catalyst component (A) obtained in this way was 2.5% by weight of titanium, 58.0% by weight of chlorine, and magnesium.
18.0 wt% and diisobutyl phthalate 13.5 wt%. The titanium catalyst component (A) was a granular catalyst with an average particle size of 13μ and a geometric standard deviation (σg) of particle size distribution of 1.2. [Polymerization] Purified hexane in an autoclave with an internal volume of 2
750 ml was charged, and 0.75 mmol of triethylaluminum and 0.075 mmol of diphenyldimethoxysilane were charged under a propylene atmosphere at 40°C, and further, 0.015 mmol of the titanium catalyst component (A) was charged in terms of titanium atom. Next, after introducing 100ml of hydrogen, propylene,
After introducing ethylene and butene-1 mixed gas, 60
The temperature was raised to 0.degree. C., and polymerization was carried out for 2 hours. The pressure during polymerization was maintained at 2.5 Kg/cm ² G. After the polymerization was completed, the slurry containing the produced copolymer was filtered and separated into a white powdery copolymer and a liquid phase.
After drying the white powdery copolymer, the yield, apparent bulk density (AD), and melt flow ratio (MFR) were measured, and the composition of the copolymer was determined using ^C13 -NMR.
The melting point was measured by DSC. Furthermore, by concentrating the liquid phase, the yield of the solvent-soluble copolymer was measured, and the yield of the white powdery copolymer relative to the total copolymer produced was calculated. The composition of the mixed gas used in the polymerization and the polymerization results are shown in Table 1. Examples 3 and 4 [Highly active, highly stereoregular solid titanium catalyst component]
Preparation of (A)] Internal volume 2 is also a high-speed stirring device (manufactured by Tokushu Kika Kogyo)
After sufficiently replacing with N ₂ , 700ml of refined kerosene, commercially available.
10 g of MgCl ₂ , 24.2 g of ethanol, and 3 g of Emazol 320 (manufactured by Kao Atlas Co., Ltd., sorbitan distearate) were added, and the temperature of the system was raised while stirring.
The mixture was stirred at 120° C. and 800 rpm for 30 minutes. Under high speed stirring,
Using a Teflon tube with an inner diameter of 5 mm, the liquid was transferred to a 2-glass flask (equipped with a stirrer) filled with refined kerosene 1 previously cooled to -10°C. The produced solid was collected by filtration and thoroughly washed with hexane to obtain a carrier. After 7.5 g of the carrier was suspended in 150 ml of titanium tetrachloride at room temperature, 1.3 ml of diisobutyl phthalate was added and the system was heated to 120°C. After stirring and mixing at 120°C for 2 hours, the solid part was collected by filtration and heated again at 150°C.
The suspension was suspended in ml of titanium tetrachloride and stirred and mixed again at 130°C for 2 hours. Furthermore, a reaction solid was collected from the reaction product by filtration and washed with a sufficient amount of purified hexane to obtain a titanium catalyst component (A). The components were 2.3% by weight of titanium, 64.0% by weight of chlorine, and 21.0% by weight of magnesium in terms of atoms. The titanium catalyst component (A) was a spherical catalyst with an average particle size of 31μ and a geometric standard deviation (σg) of particle size distribution of 1.6. [Polymerization] Polymerization was carried out in the same manner as in Example 1. The results are shown in Table-1. Examples 5 and 6 [Highly active, highly stereoregular solid titanium catalyst component]
Preparation of (A)] 4.76 g of anhydrous magnesium chloride, 23.2 ml of 2-ethylhexyl alcohol, and 25 ml of decane at 120°C.
A heating reaction was carried out for 2 hours to obtain a homogeneous solution, and 1.4 ml of ethyl benzoate was further added. This homogeneous solution was stirred and dropped into 200 ml of titanium tetrachloride cooled to -20°C over 1 hour. After completion of the dropwise addition, the mixture was heated to 90°C over 1.5 hours, at which time 1.8 ml of ethyl benzoate was added, and the mixture was further kept under stirring at 90°C for 2 hours, after which the solid portion was collected by filtration. This was then resuspended in 200ml of titanium tetrachloride and heated to 90°C.
After carrying out a heating reaction for 2 hours, the solid material was collected by filtration, thoroughly washed and dried with purified hexane until no free titanium compound was detected in the washing solution, and catalyst component (A) was obtained. The components include 3.5% by weight of titanium, 56% by weight of chlorine, 18% by weight of magnesium and 14.5% by weight of ethyl benzoate. The catalyst component (A) was a granular catalyst with an average particle size of 11μ and a geometric standard deviation (σg) of particle size distribution of 1.2. [Polymerization] Purified hexane in an autoclave with an internal volume of 2
0.50 mmol of triethylaluminum, 0.25 mmol of ethylaluminum sesquichloride, and 0.15 mmol of methyl p-toluate were charged under a propylene atmosphere at 40°C, and the titanium catalyst component (A) was added to 0.015 mmol in terms of titanium atoms. mmol was charged.
Next, after introducing 200ml of hydrogen, propylene, ethylene,
After introducing butene-1 mixed gas, the temperature was raised to 60°C and polymerization was carried out for 2 hours. The pressure during polymerization is 2.5
Kg/cm ² G was maintained. After the polymerization was completed, the slurry containing the produced copolymer was filtered and separated into a white powdery copolymer and a liquid phase.
After drying the white powdery copolymer, the yield, apparent bulk density (AD), and melt flow ratio (MFR) were measured, and the composition of the copolymer was determined using ^C13 -NMR.
The melting point was measured by DSC. Furthermore, by concentrating the liquid phase, the yield of the solvent-soluble copolymer was measured, and the yield of the white powdery copolymer relative to the total produced copolymer was calculated. The composition of the mixed gas used in the polymerization and the polymerization results are shown in Table 1. Examples 7 and 8 High-speed stirring device with internal volume 2 (manufactured by Tokushu Kika Kogyo)
After sufficiently replacing the water with _N2 , 700ml of refined kerosene and commercially available
10 g of MgCl ₂ , 24.2 g of ethanol, and 3 g of Emazol 320 (manufactured by Kao Atlas Co., Ltd., sorbitan distearate) were added, and the temperature of the system was raised while stirring.
The mixture was stirred at 120° C. and 8000 rpm for 30 minutes. Under high speed stirring,
Using a Teflon tube with an inner diameter of 5 mm, the liquid was transferred to a 2-glass flask (equipped with a stirrer) filled with refined kerosene 1 previously cooled to -10°C. The produced solid was collected by filtration and thoroughly washed with hexane to obtain a carrier. Microscopic observation revealed that the solid was perfectly spherical. 10g of solid obtained in this way
(containing 30.7 mmol of MgCl ₂ ) and 100 ml of refined kerosene
was placed in a 300 ml glass flask, and 21.1 ml of triethylaluminum was added dropwise at 5°C while stirring.
The mixture was stirred at 25°C for 1 hour, and further stirred at 80°C for 3 hours. The solid portion was collected by filtration, thoroughly washed with hexane, and then dried. The resulting solid was suspended in 100 ml of purified kerosene and dry air was blown in with stirring at room temperature for 2 hours. The solid portion was collected by filtration and thoroughly washed with hexane. After suspending the produced solid in 100 ml of refined kerosene, 1.9 ml of ethyl benzoate was added, and the
After stirring at 80°C for 1 hour, the mixture was further stirred at 80°C for 2 hours.
The solid portion was collected by filtration, thoroughly washed with hexane, and then dried. 100 ml of TiCL ₄ was added to the solid transferred to a 200 ml glass flask, and the mixture was stirred at 90°C for 2 hours, the supernatant was removed by decantation, and 100 ml of TiCl ₄ was added, followed by stirring at 9°C for 2 hours. The solid portion was thoroughly washed with hot kerosene and hexane by hot filtration to obtain a Ti-containing catalyst. The components are Ti3.8wt%, Cl61.0wt%, Mg18.0wt in terms of atoms.
%, and ethyl benzoate was 10.1 wt%. The catalyst component (A) was a spherical catalyst with an average particle size of 33μ and a geometric standard deviation (σg) of particle size distribution of 1.6. [Polymerization] Polymerization was carried out in the same manner as in Example 5. The results are shown in Table-1. Examples 9 and 10 A copolymer was produced by continuous polymerization using a polymerization system consisting of two 100 polymerization pots. Pretreatment of catalyst 50% of purified hexane and triethylaluminum were added to a 100% reactor with sufficient nitrogen purging under stirring.
5 mol, 1 mol of diphenyldimethoxysilane, and 0.5 mol in terms of titanium atoms of the titanium catalyst component (A) synthesized on a scale 300 times as described in Example 1, and then propylene was added at a flow rate of 800/Hr. A constant feed was applied for 2 hours to carry out small weight polymerization of propylene. The polymerization temperature during this period is 25~
It was 30 degrees Celsius. After the polymerization was completed, the liquid layer was removed and 50% of purified hexane was added instead. Production of copolymer Triethylaluminum, diphenyldimethoxysilane, and the pretreated product of the titanium catalyst component (A) were added to the first stage reaction vessel.
The titanium atomic ratio in the titanium catalyst component (A) was 80 (molar ratio), and the titanium atomic ratio in the diphenyldimethoxysilane/titanium catalyst component (A) was 5 (molar ratio). The polymerization temperature was 55℃ for both reaction vessels, and the polymerization pressure was 5Kg/cm ² G (first stage) 3
Kg/cm ² G (second stage) residence time was 2.5 hours in both reaction vessels. Propylene, ethylene, butene-1
Table 1 shows the feed amount ratio and polymerization results.
I wrote it down. Example 11 [Highly active, highly stereoregular solid titanium catalyst component]
Preparation of (A)] 83.6 ml of decane solution containing 50 mmol of ethylbutylmagnesium and 2-ethylhexyl alcohol
Both 23.1 ml (150 mmol) were heated at 80°C for 2 hours to form a homogeneous solution, and 1.4 ml of ethyl benzoate was added to this solution to make a sufficiently homogeneous solution. Add dropwise to titanium chloride with stirring over 1 hour. After the dropwise addition was completed, the mixture was heated to 90°C over 1.5 hours, at which time 1.8 ml of ethyl benzoate was added, and the mixture was further kept under stirring at 90°C for 2 hours, after which the solid portion was collected by filtration. , this was resuspended in 200 ml of titanium tetrachloride and heated to 90°C.
After carrying out a heating reaction for 2 hours, the solid material was collected by filtration, thoroughly washed and dried with purified hexane until no free titanium compound was detected in the washing solution,
Obtain titanium catalyst component (A). The ingredients are 2.8% by weight of titanium, 61% by weight of chlorine, and 20% by weight of magnesium.
% by weight and 13.8% by weight of ethyl benzoate,
The catalyst component (A) was a granular catalyst with an average particle size of 13μ and a geometric standard deviation (σg) of particle size distribution of 1.4. [Polymerization] Polymerization was carried out in the same manner as in Example 5. The results are shown in Table-1. Comparative Example 1 [Preparation of solid catalyst component (A)] 20 g of anhydrous magnesium chloride, ethyl benzoate
5.0 ml and 3.0 ml of silicone oil (TSS-451, 20cs, manufactured by Shin-Etsu Chemical Co., Ltd.) as a grinding aid were added to a stainless steel (SUS-32) ball 2.8 mm in diameter in a nitrogen atmosphere.
Pour into a stainless steel (SUS-32) ball mill container with an internal volume of 800 ml and an internal diameter of 100 mm, containing 1 kg.
Contact with impact acceleration of 7G for 24 hours. 15 g of the obtained co-pulverized material was suspended in 150 ml of titanium tetrachloride,
After contacting with stirring at 80°C for 2 hours, the solid part was collected by filtration, thoroughly washed with purified hexane until no free titanium compound was detected in the washing liquid, and then dried to remove the catalyst component (A). obtain. The components were 1.8% by weight of titanium, 64.0% by weight of chlorine, 23.0% by weight of magnesium, and 7.6% by weight of ethyl benzoate. The average particle size of the catalyst component (A) was 28μ, and the geometric standard deviation of the particle size distribution was 2.9. [Polymerization] Polymerization was carried out in the same manner as in Example 5. The results are shown in Table-1. Comparative Example 2 [Preparation of solid catalyst component (A)] 20 g of anhydrous magnesium chloride, 8.0 ml of diisobutyl phthalate, and 3.0 ml of silicone oil (TSS-451, 20cs, manufactured by Shin-Etsu Chemical Co., Ltd.) as a grinding aid were prepared in a nitrogen atmosphere with a diameter of 15 mm. Ball made of stainless steel (SUS-32)
The product was placed in a stainless steel (SUS-32) ball mill container with an internal volume of 800 ml and an internal diameter of 100 mm containing 2.8 kg, and was left in contact for 24 hours with an impact acceleration of 7 G. 15 g of the obtained co-pulverized material was suspended in 150 ml of titanium tetrachloride, and after contacting at 110°C for 2 hours with stirring, the solid portion was collected by filtration, and free titanium compounds were detected in the washing liquid. The catalyst component (A) is obtained by thoroughly washing with purified hexane until no more residue is present and then drying. The components are 3.7% by weight of titanium, 59.0% by weight of chlorine,
Magnesium 16.0% by weight, diisobutyl phthalate
It was 11.3% by weight. Also, the average particle size of the catalyst component (A) is
At 27μ, the geometric standard deviation of the particle size distribution was 3.1. [Polymerization] Polymerization was carried out in the same manner as in Example 1. The results are shown in Table-1.

【table】

[Table] * Total feed amount ratio of first stage + second stage ** The polymer was porridge-like and it was not possible to separate the solid polymer from the solvent.

[Brief explanation of drawings]

FIG. 1 is a flowchart schematically showing the steps for preparing a catalyst used in the method of the present invention.

Claims (1)

[Claims] 1. In the presence of a Ziegler-type olefin polymerization catalyst, propylene, ethylene and α having 4 or more carbon atoms
- Random copolymerization of olefins with a propylene content of 85 to 98 mol% and an ethylene content of 1 to 98 mol%
10 mol%, α-olefin content of carbon number 4 or more is 1 to 10 mol%, and crystallinity is 40% by weight.
(A) contains magnesium, titanium, halogen and an electron donor as essential components, and has an average particle size of 1 to 200μ and a geometric standard deviation of particle size distribution of 2.1
(B) an organoaluminum compound catalyst component; and (C) an electron donor catalyst component.