JPH02103209A - Method for producing polypropylene - Google Patents

Abstract

PURPOSE:To obtain the title polymer having high crystallinity and excellent transparency by using a preliminarily activated catalyst obtained by polymerizing a small amount of specific monomer with a combination of Ti-containing solid catalyst component and organic Al compound. CONSTITUTION:(D) Allyltoluene and/or allylstyrene is subjected to polymerization reaction with a combination of (A) Ti-containing solid catalyst component and (B) organic Al compound (e.g., trimethylaluminum) and as necessary (electron donor (e.g., dimethyl ether) at an amount of 0.001-100g based on 1g Al to afford a preliminarily activated catalyst. Then polymerization of propylene or copolymerization of propylene and other alpha-olefin is carried out using the above-mentioned catalyst. Furthermore, as the component A, a compound obtained by carrying TiCl4 on a Mg compound and consisting of essentially of Ti, Mg, halogen and electron donor is preferably used.

Description

[Detailed description of the invention]

[Industrial Application Field] The present invention relates to a method for producing polypropylene, and more particularly to a method for producing polypropylene with high crystallinity and good transparency using a specific preactivated catalyst. [Conventional technology and its performance 1] Compared to other plastics, polypropylene has excellent lightness, moldability, mechanical strength, chemical stability, etc., and is also economically advantageous, so it has been widely used in films and sheets. It is widely used in the production of various molded products. However, polypropylene is translucent, which may impair its commercial value in the field of use, and there has been a desire for improved transparency. For this reason, attempts have been made to improve the transparency of polypropylene, such as aluminum salts of aromatic carboxylic acids (Japanese Patent Publication No. 1,652/1980, etc.) and benzylidene sorbitol derivatives (Japanese Patent Publication No. 51-22/1989). There is a method of adding a nucleating agent to polypropylene (such as Japanese Patent Publication No. 740), but when an aluminum salt of an aromatic carboxylic acid is used, the dispersibility is poor and the effect of improving transparency is insufficient. In addition, when benzylidene sorbitol derivatives are used, although a certain improvement is seen in transparency, there are problems such as strong odor during processing and additive bleed phenomenon (embossment). Was. As a result of intensive research into a method for producing polypropylene with improved transparency, the present inventors discovered that a specific The polypropylene obtained by polymerizing propylene, or propylene and an α-olefin other than propylene using a preactivated catalyst obtained by polymerizing a small amount of monomers, has significantly improved not only transparency but also crystallinity. We have discovered that this is the case, and have arrived at the present invention. An object of the present invention is to provide a method for producing polypropylene with extremely high transparency. [Means for Solving the Problems] The present invention has the following configuration. (1) [1] Combine the titanium-containing solid catalyst component, (1) an organoaluminum compound (A+), and, if necessary, (2) an electron donor (81), and add allyltoluene and/or
or allyl styrene for 1 g of the titanium-containing solid catalyst component
A method for producing polypropylene, characterized in that propylene, or propylene and an α-olefin other than propylene are polymerized using a preactivated catalyst obtained by polymerization reaction of 0.0013 to 100 g. (2) The method according to item 1 above, in which a titanium trichloride composition is used as the titanium-containing solid catalyst component. (3) The method according to item 1 above, in which the titanium-containing solid catalyst component is a titanium-containing solid catalyst component containing titanium, magnesium, halogen, and an electron donor (B1) as essential components. (4) As an organoaluminum compound (A+), the general formula is ^IR'-"a4s-+a*11 (in the formula 11, R
2 represents a hydrocarbon group or alkoxy group represented by an alkyl group, cycloalkyl group, or aryl group; X represents a halogen; 1) The method according to item 1 above, using the organoaluminum compound represented by 1). (S) 1 selected from O-furyltoluene, p-allyltoluene, 2-allyl-p-xylene, 4-allyl-O-xylene, and 5-allyl-■-xylene as allyltoluene and/or allylstyrene; 2. The method according to item 1 above, wherein more than one type of monomer is used. As the titanium-containing solid catalyst component used in the present invention, any known titanium-containing solid catalyst component for producing stereoregular polypropylene can be used. A titanium-containing solid catalyst component containing titanium trichloride as a main component obtained by the method described in JP-A No. 28,573, JP-A-58-17,1 (14), and JP-A-62-104.810. Publication No., JP-A-62-
A titanium-containing solid catalyst component containing titanium, magnesium, halogen, and an electron donor as essential components, in which titanium tetrachloride is supported on a magnesium compound described in JP-A No. 104,811, JP-A-82-104,812, etc. is used. In addition, the general formula of the organoaluminum compound (AL+) is AIR'! 'lX5-1m4m+'+ (wherein, R
1, R2Gf A hydrocarbon group or alkoxy group represented by a furkyl group, cycloalkyl group, or aryl group, represented by 1), where X represents a halogen, and m and 1 represent any number of O<men'≦3. Organoaluminum compounds are used. Specific examples include trimethylaluminum, triethylaluminum, tri-n-propylaluminum, tri-n
-butylaluminum, tri-l-butylaluminum,
Trialkylaluminums such as tri-n-hexylaluminum, tri-hexylaluminum, tri-2-methylpentylaluminum, tri-n-octylaluminum, tri-n-decylaluminum, diethylaluminum monochloride, moro-propylaluminum monochloride, di-I - Dialkyl aluminum monohalides such as butyl aluminum monochloride, diethylaluminium monofluoride, diethylaluminium monobromide, diethylaluminum monoiodide, dialkyl aluminum hydrides such as diethyl aluminum hydride, methyl aluminum sesquichloride, ethyl aluminum sesquichloride, etc. Alkylaluminum sesquihalides, ethylaluminum dichloride, 1-butylaluminum dichloride, and other monoalkylaluminum cybalides, and monoethoxydiethylaluminum, monoethylaluminum dichloride, etc.
Alkoxyalkylaluminums such as jetoxymonoethylaluminum can also be used. These organic aluminums can also be used in combination with Z fl or more. Furthermore, the electron donor (B+) used as necessary is as follows:
During normal propylene polymerization, a known electron donor is used for the purpose of improving stereoregularity. Those used as electron donors are organic compounds containing any one of oxygen, nitrogen, sulfur, and phosphorus atoms, that is,
Ethers, alcohols, esters, aldehydes, fatty acids, ketones, nitriles, amines, amides, urea or thioureas, isocyanates, azo compounds, phosphines, phosphites, phosphinites, These include hydrogen sulfide, thioethers, thioalcohols, silanols, and organosilicon compounds having a 5i-0-C bond. Specific examples include dimethyl ether, diethyl ether, di-n-propyl ether, di-n-butyl ether, sheet amyl ether, di-n-pentyl ether,
di-n-hexyl ether, sheet hexyl ether,
Ethers such as di-n-octyl ether, di-mi-octyl ether, di-n-dodecyl ether, diphenyl ether, ethylene glycol monoethyl ether, diethylene glycol dimethyl ether, tetrahydrofuran, methanol, ethanol, propatool, butanol, pentanol, hexanol , octatool,
Alcohols such as 2-ethylhexanol, allyl alcohol, benzyl alcohol, ethylene glycol, glycerin, phenols such as phenol, cresol, xylenol, ethylphenol, naphthol, methyl methacrylate, methyl formate, methyl acetate, methyl butyrate,
Ethyl acetate, vinyl acetate, n-propyl acetate, l-acetate
Propyl, butyl formate, amyl acetate, octyl acetate, octyl acetate, phenyl acetate, ethyl propionate, methyl benzoate, ethyl benzoate, propyl benzoate, butyl benzoate, octyl benzoate, 2-ethylhexyl benzoate, methyl toluate , ethyl toluate, methyl anisate, ethyl anisate, propyl anisate, phenyl anisate, ethyl cinnamate, methyl naphthoate, ethyl naphthoate, propyl naphthoate, butyl naphthoate, toethylhexyl naphthoate, ethyl phenylacetate aliphatic polyhydric carboxylic acid esters such as diethyl succinate, diethyl methylmalonate, diethyl butylmalonate, dibutyl maleate, diethyl butyl maleate, monomethyl phthalate, dimethyl phthalate, phthalate, etc. Diethyl acid, di-n-propyl phthalate, n-butyl phthalate, di-n-butyl phthalate, di-l-butyl phthalate, di-n-butyl phthalate, di-2-ethylhexyl phthalate, Phthalic acid di-
Aromatic polyvalent carboxylic acid esters such as n-octyl, diethyl isophthalate, dipropyl isophthalate, dibutyl isophthalate, sheet ethylhexyl isophthalate, diethyl terephthalate, dipropyl terephthalate, dibutyl terephthalate, di-l-butyl naphthalene dicarboxylate, etc. aldehydes such as acetaldehyde, propionaldehyde, benzaldehyde, carboxylic acids such as formic acid, acetic acid, propionic acid, butyric acid, oxalic acid, succinic acid, acrylic acid, maleic acid, valeric acid, benzoic acid, benzoic anhydride,
Acid anhydrides such as phthalic anhydride and tetrahydrophthalic anhydride, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and benzophenone, acetonitrile,
Nitriles such as benzonitrile, methylamine, diethylamine, tributyl atom, triethanolamine,
β(N,N-dimethylamino)ethanol, pyridine,
Quinoline, a-picoline, 2,4.8-trimethylpyridine,! , 2.11.8-tetramethylpiperidine, 2
．． 2.5゜5-tetramethylpyrrolidine, N, N, N'
, N'-tetramethylethylenediamine, aniline, dimethylaniline and other amines, formamide, hexamethylphosphoric triamide, N, N, N', N', N-pentamethyl-N'-β-dimethylaminomethylphosphoric triamide , amides such as octamethylpyrophosphoramide, ureas such as N,N,N',N'-tetramethylurea, isocyanates such as phenyl isocyanate and tolylisocyanate, azo compounds such as azobenzene, ethylphosphine, triethyl Phosphines such as phosphine, tri-n-octylphosphine, triphenylphosphine, triphenylphosphine oxyto, dimethylphosphite, mono-cutylphosphine, triethylphosphite, tri-n-butylphosphite, triphenylphosphite, etc. Phosphites, phosphinites such as ethyldiethylphosphinite, ethylbutylphosphinite, phenyldiphenylphosphinite, thioethers such as diethylthioether, diphenylthioether, methylphenylthioether, ethylthioalcohol, n-propylthioalcohol , thioalcohols and thiophenols such as thiophenol, silanols such as trimethylsilanol, triethylsilanol, triphenylsilanol, trimethylmethoxysilane, dimethyldimethoxysilane, methylphenyldimethoxysilane, diphenyldimethoxysilane, methyltrimethoxysilane, Vinyltrimethoxysilane, phenyltrimethoxysilane, trimethylethoxysilane, dimethyljethoxysilane, diphenyljethoxysilane, methyltriethoxysilane, ethyltriethoxysilane,
5l-0 such as vinyltriethoxysilane, butyltriethoxysilane, phenyltriethoxysilane, ethyltril-propoxysilane, vinyltriacetoxysilane, etc.
Examples include organosilicon compounds having a -C bond. The above-mentioned (1) titanium-containing solid catalyst component, (2) an organoaluminum compound (^1), and, if necessary, (2) an electron donor (B1) are combined, and this is combined with allyltoluene and/or allylxylene (hereinafter 0.001 g to 100 g of the titanium-containing solid catalyst component (sometimes referred to as a specific allyl monomer) is polymerized and preactivated to obtain a preactivated catalyst used in the present invention. Pre-activated, per 1g of titanium-containing solid catalyst component, organic aluminum compound (B+) O, 05g~50
0g, electron donor (Il*) 0.01g to 500g,
Solvent o~5G, L, hydrogen 1) N1N10O0, and 0.0011-5.000 g of a specific allyl monomer are used. Pre-activation is performed at a temperature of 0°C to 10°C and atmospheric pressure to 50 kg.
0.Olg -100g of the specific allyl monomer is polymerized per 1g of titanium-containing solid catalyst component over a period of 1 minute to 20 hours under a pressure of /cm''a.Polymerization reaction per 1g of titanium-containing solid catalyst component If the amount is less than 0,001 g, the effect of improving the transparency and crystallinity of the obtained polypropylene will be insufficient, and if it exceeds 100 g, the improvement in the effect will not be significant and it will be economically disadvantageous. The reaction can also be carried out in a hydrocarbon solvent such as propane, butane, n-pentane, n-hexane, n-hebutane, benzene, toluene, etc., and hydrogen may also be present in the preactivation. After the completion of the reaction, the preactivated catalyst slurry can be used as it is for propylene polymerization.In addition, the coexisting solvent, unreacted specific allyl monomer,
Organic aluminium, ram compound (81), and electron donor (B+) are removed by filtration to form powder, and this is further added with organic aluminum compound (^2) and electron donor (
A preactivated catalyst obtained by combining B2) and subjecting it to the polymerization of propylene or by evaporating the coexisting solvent and unreacted specific allyl monomer to form a granular material, or the granular material. Furthermore, organoaluminum compounds (^
It is also possible to use a combination of 1) and the electron donor (B3) in the polymerization of propylene. Allyltoluene and/or allylstyrene used for preactivation of the present invention is 1 selected from 0-allyltoluene, 2-allyl-p-xylene, 4-allyl-0-xylene, and 5-allyl-xylene. It is a specific allyl monomer of more than one species. In addition, during the polymerization or copolymerization of propylene, the organoaluminum compounds (^2) and (^1) and electron donors (B2) and (8,), which are used as necessary, undergo a preactivation reaction, respectively. Examples include those similar to the organoaluminum compound (^1) and electron donor (B1) used in the above, and 1 fl or more of the same or different types may be used. The amount used is also within the same range as in the preactivation reaction. The preactivated catalyst thus obtained is used for homopolymerization of propylene or copolymerization of propylene and an α-olefin other than propylene, but it is also possible to add a solvent and use it in a slurry state for polymerization. In the method of the present invention, the polymerization method for polymerizing propylene, or propylene and an α-olefin other than propylene, includes: ■ Hydrocarbon solvents such as n-pentane, n-hexane, n-hebutane, n-octane, benzene, or toluene. 1. Bulk polymerization carried out in liquefied propylene, 2. Gas phase polymerization in which propylene is polymerized in the gas phase, or a method in which two or more of 0 or more of 1 to 2 are combined stepwise. In either case, the polymerization temperature was room temperature (
20℃) to 200℃, polymerization pressure is normal pressure (Okg/c
rd G)~50kg/crn"G, usually 5 minutes~20
It will be carried out for about an hour. During polymerization, steps such as adding an appropriate amount of hydrogen to control the molecular weight are the same as in conventional polymerization methods. In the method of the present invention, the α-olefins subjected to polymerization together with propylene include linear monoolefins such as ethylene, butene-1, hexene-11 octene-1,
-Methylpentene-1,2-methyl-pentene-! ,3
- Branched monoolefins such as methyl-butene-1, diolefins such as butadiene, isoprene, and chlorobrene, etc. The method of the present invention involves not only the homopolymerization of propylene but also the combination of propylene with other olefins. For example, copolymerization can be carried out by combining propylene and ethylene, propylene and butene-1, or by combining three components such as propylene, ethylene, butene-1, or in the first stage of propylene polymerization in multistage polymerization. Block copolymerization in which other α-olefins are polymerized in the latter stage can also be carried out.

[For use]

Since the polypropylene obtained by the method of the present invention contains a highly stereoregular allyltoluene polymer and/or allylxylene polymer dispersed therein, the allyltoluene polymer and/or allylxylene polymer is The polymer exhibits a nucleating effect, which reduces the spherulite size of polypropylene and promotes crystallization.
It increases the transparency and crystallinity of the entire polypropylene. Further, as described above, the allyltoluene polymer and/or allylxylene polymer introduced by the method of the present invention is a stereoregular high molecular weight polymer, so that it does not bleed onto the surface. [Example] The present invention will be described below with reference to Examples. Definitions of terms used in Examples and Comparative Examples and measurement methods are as follows. MFR Nimelt Flow Index ^ Based on STM D-1238 (L). (Unit: g/lo min) Internal haze: This is the haze inside the film excluding surface effects, and is produced using a press at a temperature of 200°C and a pressure of 200K.
The thickness of polypropylene is 15 g/crn”G.
After applying liquid paraffin to both sides of the film, the haze was measured in accordance with JIS 7105. (Unit: %) Crystallization temperature: Measured using a differential scanning calorimeter at a cooling rate of 10° C./min. (Unit: 2℃) Flexural modulus: Polypropylene 10G! For i quantity part,
Tetrakis[methylene-3-(3°-15°-di-1-
20.1 parts by weight of butyl-4°-hydroxyphenyl)propionate cometa, and 0.1 parts by weight of calcium starate.
1 part by weight, and the mixture was made into a scriero diameter of 40 m5.
It was granulated using an extrusion granulator. Then, the granules were subjected to JI using an injection molding machine at a molten resin temperature of 230°C and a mold temperature of 50°C.
After creating an S-shaped test piece and leaving the test piece in a room with a temperature of 50% and a room temperature of 23°C for 72 hours,
The flexural modulus was measured in accordance with JfS K "1203. (Unit = f/cn?) Example 1 (1) Preparation of titanium-containing solid catalyst component n-hexane 6J!, diethyl aluminum monochloride (DEAC) ) 5.0 mol and 12.0 mol of diisoamyl ether were mixed at 25°C for 1 minute, and reacted at the same temperature for 5 minutes to form reaction product liquid (I) (molar ratio of diisoamyl ether/DEAC 2.4). 40 mol of titanium tetrachloride was placed in a reactor purged with nitrogen and heated to 35°C.
After adding the entire amount of the reaction product liquid (1) dropwise to this over 30 minutes, the temperature was kept at the same temperature for 30 minutes, the temperature was raised to 75°C, and the temperature was further increased for 1 hour.
The reaction mixture was allowed to react for an hour, cooled to room temperature, the supernatant liquid was removed, n-hexane 201 was added, and the supernatant liquid was removed by decantation, and this operation was repeated four times to obtain a solid product (II). The entire amount of this (1) was suspended in 30 IL of n-hexane, 200 g of diethylaluminum monochloride was added, and 1.01 °C of propylene was added at 30 °C and reacted for 1 hour to obtain a polymerized solid compound ( After the reaction, the supernatant was removed, and 300 ml of n-hexane was added and removed by decantation, which was repeated twice to carry out the above polymerization treatment. 2.5Kg of solid product (II-A) was converted into n-
Hexane 6j! After adding 3.5 g of titanium tetrachloride to 3.5 g of titanium tetrachloride at room temperature for about 10 minutes and reacting at 80°C for 30 minutes, 1.6 kg of diisoamyl ether was further added and the mixture was heated to 80°C. After the reaction was completed for 1 hour, the supernatant was removed by decantation, 40 Jil of n-hexane was added, stirred for 10 minutes, allowed to stand, and the supernatant was removed, which was repeated 5 times. Thereafter, it was dried under reduced pressure to obtain a titanium-containing solid catalyst component. (2) Adjustment of preactivated catalyst After purging a stainless steel reactor with inclined blades with internal volume aOX with nitrogen gas, 40 g of n-hexane, 200 g of diethylaluminium monochloride, and the titanium-containing solid catalyst component obtained in (1) were added. After adding 450 g at room temperature, the temperature inside the reactor was raised to 40 °C, and 4-allyl-0-xylene 4
．． 9 and reacted at 40°C for 2 hours (per 1 g of titanium-containing solid catalyst component, 4-allyl-〇-xylene O
, Bg reaction). After the reaction was completed, unreacted 4-allyl-0-xylene and the solvent were removed by filtration, washed with rhohexane, and dried to obtain a preactivated catalyst in the form of powder. (3) Propylene polymerization After purging a stainless steel reactor with a stirrer and an internal volume of 5ooIL with nitrogen gas, the mixture was heated with 200μ of n-hexane at room temperature.
, 36g of diethylaluminum monochloride, (2)
15 g of the preactivated catalyst obtained in 1 as a titanium-containing solid catalyst component and 100 NJZ of hydrogen were added. Subsequently, the polymerization temperature was 70°C, and the propylene partial pressure was 10Kg/c+.
After the completion of the 0 reaction in which propylene was polymerized for 2 hours and 30 minutes at e''G, 100 g of methanol was added, and the catalyst was deactivated at 70°C for 30 minutes, then cooled to room temperature and the resulting polymer was dried. Since the dried polymer contained lumps, the entire amount of the polymer was pulverized by crushing it into a powder, and polypropylene with an MFR of 1.6 [i 1Kg
I got it. Comparative Example 1 Propylene was produced in the same manner as in Example 1, except that 10 g of the titanium-containing solid catalyst component obtained in (1) was used for the propylene polymerization in (3) without performing the preactivation reaction in (2). Polymerization was performed. Comparative Example 2 and Example 2.3 By changing the amount of 4-allyl-O-xylene used in (2) of Example 1, the amount of polymerization reaction per 1 g of the titanium-containing solid catalyst component was 0.0001 g. 0.05g, O,.10g of preactivated catalyst was obtained. After that, propylene polymerization was carried out in the same manner as in Example 1 (3). Example 4 (1) Preparation of titanium-containing solid catalyst component In a stainless steel reactor equipped with a stirrer, decane 31
, anhydrous magnesium chloride 480g, orthotitanic acid n-
1.7 kg of butyl and 1.95 kg of 2-ethyl-1-hexanol were mixed and heated to 130° C. for 1 hour while stirring to dissolve and form a uniform solution. The homogeneous solution was
Diisobutyl phthalate IBOg at 0°C and while stirring.
After stirring for 1 hour, 5.2 kg of silicon tetrachloride was added dropwise over 2.5 hours to precipitate a solid, and the mixture was further heated to 70° C. for 1 hour. The solid was separated from the solution and washed with hexane to give a solid product (Ill). The entire amount of the solid product (lil) is mixed with titanium tetrachloride 15J2 dissolved in 1,2-dichloroethane 15J2,
Subsequently, 360 g of diisobutyl phthalate was added and the mixture was reacted at 100°C for 2 hours with stirring.The liquid phase was removed by decantation at the same temperature, and 1.2-
Dichloroethane 15j2 and titanium tetrachloride 15λ were added, stirred at 100°C for 2 hours, washed with hexane and dried to obtain a titanium-containing solid catalyst component. (2) Preparation of preactivated catalyst After purging a stainless steel reactor with inclined blades with a volume of 301 cm with nitrogen gas, prepare the following mixture using 20J2 n-hexane, 1.5 kg of triethylaluminum, 480 g of diphenyldimethoxysilane, and (1). After adding 200 g of titanium-containing solid catalyst component at room temperature, the temperature inside the reactor was lowered to 40 g.
℃, add 2.0 g of 2-allyl-p-xylene,
Reacted at 40°C for 2 hours (titanium-containing solid catalyst component 1
0.3 g of 2-allyl-p-xylene per g reaction). After the reaction was completed, unreacted 2-allyl-p-xylene and the solvent were removed by filtration, washed with n-hexane, and dried to obtain a preactivated catalyst. (3) Polymerization of propylene In the reactor used in Example 1 (3), add 20 g of n-hexane.
0J! , 60 g of triethylaluminum, 20 g of diphenyldimethoxysilane, 4.0 g of the preactivated catalyst obtained in (2) as a titanium-containing solid catalyst component, and 5 ONJl of hydrogen were added. Subsequently, propylene was polymerized for 2 hours at a polymerization temperature of 70°C and a propylene partial pressure of 7kg/cm''G.After the reaction was completed, 100g of methanol was added, and a catalyst deactivation reaction was performed at 70°C for 30 minutes. It was cooled to room temperature and the obtained polymer was dried.The dried polymer contained lumps, so the entire amount of the polymer was pulverized by a pulverizer, and MFRIJ's Polypropylene 4
6Kg was obtained. Comparative Example 3 In Example 4, 3.5 g of the titanium-containing solid catalyst component obtained in (1) was used instead of the preactivated catalyst during propylene polymerization in (3) without conducting the preactivation reaction in (2). Polymerization of propylene was carried out in the same manner except for the above. Example 5 n-hexane 12j! 27.0,000 liters of titanium tetrachloride was added to the solution, and after cooling to 1°C, 12.51 liters of n-hexane containing 27.0 mol of diethylaluminum monochloride was added.
was added dropwise over 4 hours at 1°C. After the completion of the 0 drop, the temperature was kept at the same temperature for 15 minutes to react, and then the temperature was raised to 65°C over 1 hour, and the reaction was further continued at the same temperature for 1 hour. The supernatant was removed, n-hexane lOλ was added, and the operation of removing with a decantation process was repeated 5 times to obtain the solid product (II
) Of the 5.7 kg, 1.8 kg is n-hexane 11
A and diisoamyl ether 1.611
was added. After stirring this suspension at 35°C for 1 hour, rhohexane 3j! A treated solid was obtained by washing with water 5 times. The resulting treated solid was suspended in 6It of a 40% by volume titanium tetrachloride solution in n-hexane. This suspension was heated to 65°C,
After the 0 reaction was completed at the same temperature for 2 hours, 20J of n-hexane was added at a time! The obtained solid was washed three times using the following methods, and then dried under reduced pressure to obtain a titanium-containing solid catalyst component. (2) In (2) of Example 1, 450 g of the titanium-containing solid catalyst component obtained in (1) was used as the titanium-containing solid catalyst component, and 450 g of the titanium-containing solid catalyst component obtained in (1) was also used in place of 4-allyl-0-xylene.
A preactivated catalyst was prepared in the same manner except that 2.3 g of -allyltoluene was used. (3) Polymerization of propylene was carried out in the same manner as in (3) of Example 1 except that the preactivated catalyst obtained in (2) above was used as the preactivated catalyst. Comparative Example 4 In Comparative Example 1, propylene was polymerized in the same manner as in Comparative Example 1 except that the titanium-containing solid catalyst component 108 obtained in Example 5 (1) was used as the titanium-containing solid catalyst component. Example 6 (1) Preparation of titanium-containing solid catalyst component 4.0Kg of aluminum trichloride (anhydrous) and 1.2Kg of magnesium hydroxide! When the mixture was pulverized in a vibrating mill at 250°C for 3 hours, the reaction occurred with the generation of hydrogen chloride gas. After heating, the mixture was cooled in a nitrogen stream to obtain a solid product (III). In a stainless steel reactor with a stirrer, purified Deca:
/6JL solid product (III) 1.0Kg, #J
/) n-butyl titanate 3.4Kg,! -ethyl 1
- Mix 3.9 kg of hexanol and while stirring 1
The mixture was heated to 30° C. for 2 hours to dissolve and form a uniform solution. The solution was heated to 70°C, and 2.0 g of ethyl p-toluate was added.
was added and reacted for 1 hour, then 0.0% diisobutyl phthalate was added.
After adding 8 to 4 and reacting for another 1 hour, 10.4 kg of silicon tetrachloride was added dropwise over 2 hours without stirring to precipitate a solid, and the mixture was further stirred at 70°C for 1 hour. The solid was separated from the solution and washed with purified hexane to yield a solid product ([V). To the total amount of the solid product (IV) was added 0.4 g of diisobutyl phthalate along with 10 It of 1,2-dichloroethane and 10 I of titanium tetrachloride, and with stirring 10
After reacting at 0℃ for 2 hours, decantate at the same temperature.
The liquid phase was removed by a tank, and 1,2-dichloroethane ton and titanium tetrachloride 10j! were added again. After adding 0.4 kg of diisobutyl phthalate and reacting at 100°C for 2 hours with stirring, the solid part was collected by hot filtration, washed with purified hexane, and dried under reduced pressure at 25°C for 1 hour to obtain titanium. A containing solid catalyst component was obtained. (2) Preparation of preactivated catalyst In (2) of Example 4, the titanium-containing solid catalyst component 2 obtained in the above (1) was used as the titanium-containing solid catalyst component.
00g, and 5-allyl-p-xylene instead of 2-allyl-p-xylene.
A preactivated catalyst was prepared in the same manner except that 880 g of allyl-■-xylene was used. (3) Polymerization of propylene Propylene was polymerized in the same manner as in Example 4 (3) except that the preactivated catalyst obtained in (2) above was used as the preactivated catalyst. Comparative Example 5 In Comparative Example 3, propylene was polymerized in the same manner as in Comparative Example 3, except that 3.5 g of the titanium-containing solid catalyst component obtained in Example 6 (1) was used as the titanium-containing solid catalyst component. Example 7 (Preparation of +1 titanium-containing solid catalyst component 41 mols of n-hebutane, 5.0 mols of diethylaluminum monochloride, 9.0 mols of diisoamyl ether, and 5.0 mols of moro-butyl ether were reacted at 18°C for 30 minutes. The reaction solution obtained by
After dropping at 0°C for 300 minutes, the temperature was increased to 1.
After reacting for 5 hours, the temperature was raised to 65°C, reacted for 1 hour, the supernatant liquid was removed, n-hexane was added at 20°C, and the operation was removed by decantation, which was repeated 6 times to obtain a solid product ( I+) 1.8 g of titanium tetrachloride was suspended in n-hexane 7J2, titanium tetrachloride 1.8 Kg% n-butyl ether 1
．． After the completion of the reaction, the supernatant liquid was removed by decantation, and the n of 201 was added to 8 and reacted for 3 hours at 60°C.
- Hexane was added, stirred for 5 minutes, left to stand, and the supernatant liquid removed. After repeating this operation three times, the mixture was dried under reduced pressure to obtain a titanium-containing solid catalyst component. (2) Preparation of preactivated catalyst In (2) of Example 1, the titanium-containing solid catalyst component 4 obtained in (1) above was used as the titanium-containing solid catalyst component.
50 g, and instead of 4-allyl-0-xylene,
A preactivated catalyst was prepared in the same manner except that 720 g of p-allyltoluene was used. (3) In (3) of the propylene polymerization example, the preactivated catalyst obtained in (2) above is used as the preactivated catalyst, and
Propylene-ethylene copolymerization was carried out in the same manner except that ethylene was further supplied so that the concentration in the gas phase of the polymerization vessel was maintained at 0.2% by volume during propylene polymerization. Comparative Example 6 In Example 7, (2) without preactivation reaction (
During the propylene-ethylene copolymerization in step 3), propylene-ethylene copolymerization was carried out in the same manner except that 10 g of the titanium-containing solid catalyst component obtained in step (1) was used. The preactivation conditions and results of the above Examples and Comparative Examples are shown in the table. [Effects of the Invention] The polypropylene obtained by the method of the present invention has excellent transparency and crystallinity. As is clear from the above-mentioned examples, the internal haze of the pressed film using polypropylene obtained by the method of the present invention is 4.5% to 6.8%, and It has significantly higher transparency than a press film using conventional polypropylene obtained using an unconverted catalyst. In addition, the crystallinity as well as the transparency were improved, and an increase in the crystallization temperature of the polypropylene powder and an improvement in the flexural modulus of the injection molded test piece were observed.

[Brief explanation of drawings]

FIG. 1 is a detailed process diagram illustrating the present invention.

Claims (5)

[Claims] (1) [1] A titanium-containing solid catalyst component, [2] an organoaluminum compound (A_1), and optionally [3] an electron donor (B_1) are combined, and this is combined with allyltoluene and/or
or allyl styrene for 1 g of the titanium-containing solid catalyst component
A method for producing polypropylene, characterized in that propylene, or propylene and an α-olefin other than propylene are polymerized using a preactivated catalyst obtained by polymerizing 0.001 g to 100 g per polymer. (2) The method according to claim 1, in which a titanium trichloride composition is used as the titanium-containing solid catalyst component. (3) The method according to claim 1, in which the titanium-containing solid catalyst component is a titanium-containing solid catalyst component containing titanium, magnesium, halogen, and an electron donor (B_2) as essential components. (4) As the organoaluminum compound (A_1), the general formula is AlR^1_mR^2_m'・X_3_-_(_m
___+_m') (wherein R^1 and R^2 represent a hydrocarbon group or alkoxy group represented by an alkyl group, cycloalkyl group, or aryl group, X represents a halogen, and m, m'
represents an arbitrary number satisfying 0<m+m'≦3. ) Claim 1 using an organoaluminum compound represented by
The method described in section. (5) As allyltoluene and/or allylstyrene, o-allyltoluene, p-allyltoluene, 2-
2. The method of claim 1, using one or more monomers selected from allyl-p-xylene, 4-allyl-o-xylene, and 5-allyl-m-xylene.