JPH0155283B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a method for producing polyolefin.
More particularly, the present invention relates to a method for polymerizing α-olefins using a catalyst system consisting of solid titanium trichloride, an organoaluminium compound, and a specific combination of electron-donating compounds. Conventionally, when polymerizing olefins, especially stereospecific polymerization of α-olefins, using a catalyst system consisting of a solid titanium trichloride catalyst and an organoaluminum compound, it has not been possible to use an electron-donating compound as a third component. well known. In this case, the purpose of using an electron-donating compound as the third component of the catalyst system is to improve the stereoregularity of the resulting polymer even a little, thereby reducing the amount of amorphous polymer by-produced. The aim is to reduce the bulk density of the produced polymer powder, improve the yield of the crystalline polymer, or improve the rigidity of the produced polymer.
The purpose of improving powder properties such as particle size distribution is to facilitate the handling and transport of polymerized powders or slurries, and to reduce the reactor capacity. It is common knowledge that a large number of studies have been carried out, and considerable results have been obtained. For example, the special public official court in 1977-
21337 and Special Publication No. 49-4832, TiCl ₄
When propylene is polymerized using a catalyst system consisting of titanium trichloride obtained by reducing with Al, then pulverizing and activating it, and an organoaluminum compound such as diethylaluminum monochloride, methacrylic acid ester or acrylic acid is used as the third component. A method has been proposed for improving the stereoregularity of polypropylene by using carboxylic acid derivatives such as acid esters and vinyl ethers such as ethyl vinyl ether. Furthermore, Tokko Akira
No. 46-12140 proposes a method for similarly improving the stereoregularity of polypropylene by using a benzoic acid derivative such as ethyl benzoate as the third component. When the oxygen-containing compounds listed here are used as the third component, they improve the stereoregularity of the resulting polymer, but at the same time the polymerization rate decreases little, and in these respects they are industrially useful third components. It can be said that it is one of the In addition, the special public
-19546, in polymerizing propylene in an aliphatic or alicyclic saturated hydrocarbon solvent substantially free of oxygen compounds using a catalyst system consisting of titanium trichloride and an organoaluminum compound. Methods have been proposed to improve the stereoregularity and bulk density of polymerized powders by using aromatic hydrocarbons such as toluene as a component or part of the polymerization solvent, and some of the present inventors have also previously Special public service in 1977-
9001, propylene is polymerized using a catalyst system consisting of a highly active titanium trichloride-based catalyst complex produced by a specific method, an organoaluminium compound, and an aromatic hydrocarbon, and the polymer powder has high stereoregularity and bulk density. We proposed a method to obtain polypropylene with high catalytic efficiency. On the other hand, in the case of packaging films, which are one of the major uses of polypropylene, transparency and impact resistance are important properties that determine commercial value, and higher transparency and impact resistance are preferred. However, according to studies conducted by the present inventors, when propylene is polymerized using a conventionally known electron-donating compound as the third component of the catalyst system, polypropylene with high stereoregularity and bulk density of the polymer powder is produced. However, it has been found that when it is extruded into a water-cooled blown film or a T-die film, its transparency and impact resistance are reduced. Moreover, as the stereoregularity of the resulting polymer is improved, such as by increasing the amount of the third component, the so-called "stiffness" of the film will be improved, but on the other hand, the transparency and impact resistance mentioned above will be improved. The decline became remarkable. The reason for this is of course not clear, but according to the studies of the present inventors, one of the factors that has a close correlation with the transparency and impact resistance of the film is the molecular weight distribution of the polymer, and this molecular weight distribution Furthermore, it was found that there is a close correlation with the type and amount of the third component during polymerization. That is, when conventionally known electron-donating compounds are used, the stereoregularity of the polymer is of course improved, but at the same time, the molecular weight distribution also increases, and the transparency and impact resistance of the film tend to decrease. It was done. Although it is currently unclear why there is a correlation between these two properties of the film and the molecular weight distribution, the present inventors have conducted extensive studies to solve this drawback by preventing an increase in the molecular weight distribution. As a result, when certain combinations of electron-donating compounds are used as the third component, the stereoregularity is improved, but the molecular weight distribution remains small, resulting in improved film transparency and impact strength. This is a totally surprising result that could not have been predicted from the prior art. According to the method of the present invention, a polymer having sufficiently large stereoregularity and bulk density together with the combined catalyst and cocatalyst can be obtained with high activity, that is, with high catalytic efficiency. This method is also advantageous from the viewpoint of the manufacturing process, as it makes it possible to omit the step of removing residual catalyst and to streamline the step of removing residual catalyst. Therefore, the gist of the present invention is to use a catalyst system consisting of solid titanium trichloride, an organoaluminium compound, an aromatic hydrocarbon, and vinyl ethers.
- A method for producing a polyolefin, characterized by polymerizing an olefin. To explain the present invention in detail, the solid titanium trichloride used as a catalyst includes pure titanium trichloride obtained by hydrogen reduction of titanium tetrachloride, and titanium trichloride-trichloride obtained by aluminum reduction of titanium tetrachloride. Aluminum chloride eutectic ( _TiCl3
-1/3AlCl ₃ ) and mechanically crushed titanium trichloride, etc. can also be used, but the amount of amorphous polymer to be removed is small, and the catalyst removal process can be simplified or omitted. It is preferable to use the following solid titanium trichloride-based catalyst complex, which is a highly active catalyst, because the powder properties of the polymer are also good. Such solid titanium trichloride catalyst complexes are disclosed in Japanese Patent Application Laid-open No. 47-34478, No. 48-64170, No. 50-
112289, 50-143790, 51-16297, 51-
16298, 51-76196, 51-123796, etc., but to explain, the aluminum content is 0.15 or less in terms of the atomic ratio of aluminum to titanium, preferably 0.1 or less, more preferably 0.02 or less, and complexed. It contains an agent. The content of the complexing agent is 0.001 as the molar ratio of the complexing agent to titanium trichloride in the solid titanium trichloride catalyst complex.
It is preferably 0.01 or more. in particular,
Titanium trichloride, the formula AlR ¹ _p X _3-p in which ^the atomic ratio of aluminum to titanium in titanium trichloride is 0.15 or less containing a complexing agent in a molar ratio of 0.001 or more to aluminum halide and titanium trichloride, represented by the number 0≦p≦2);
For example, the formula TiCl ₃ (AlR ¹ _p X _3-p ) _s (C) _t (where R ¹
is a hydrocarbon group having 1 to 20 carbon atoms, X is a halogen atom, p is a number of 0≦p≦2, C is a complexing agent, s is a number of 0.15 or less, t teeth
Of course, in addition to the TiCl ₃ component, the _AlR ¹ _p Partially or fully substituted with iodine or bromine, or MgCl ₂ ,
It may contain an inorganic solid for a carrier such as MgO, an olefin polymer powder such as polyethylene or polypropylene, and the like. Examples of the complexing agent C include ethers, thioethers, ketones, carboxylic acid esters, amines, carboxylic acid amides, and polysiloxanes, among which ethers and thioethers are particularly preferred. As the ether or thioether, the general formula R ² -O-R ³ or R ² -S-
Examples include those represented by R ³ (wherein R ² and R ³ represent a hydrocarbon group having 15 or less carbon atoms). Examples of AlR ¹ _p X _3-p include AlCl ₃ and AlR ¹ Cl ₂ . Further, it is particularly preferable that the solid titanium trichloride-based catalyst complex has a halo of maximum intensity at a position corresponding to the strongest peak position of α-type titanium trichloride in its X-ray diffraction pattern (around 2θ = 32.9°). . Furthermore, during the production of solid titanium trichloride-based catalyst complexes,
Those that have not been subjected to thermal history at temperatures exceeding 150°C are preferred. Furthermore, the cumulative pore volume with a pore radius between 20 Å and 500 Å measured using the mercury porosimeter method is
Those characterized by a pore volume with an extremely fine pore diameter of 0.02 cm ³ /g or more, especially 0.03 cm ³ /g to ^{0.15 cm 3} /g, are advantageous in that there is no need to remove amorphous polymers. , particularly preferred. However, such a solid titanium trichloride-based catalyst complex can be prepared from a liquid containing titanium trichloride liquefied in the presence of (a) ether or thioether at 150°C;
(b) Solid titanium trichloride obtained by reducing titanium tetrachloride with an organoaluminum compound or metal aluminum can be produced by a method of precipitating it at the following temperature: or (b) treating it with a complexing agent and a halogen compound. can. A method for obtaining a liquid containing liquefied titanium trichloride in method (a) is to use titanium tetrachloride as a starting material, and to process it in the presence of an ether or thioether and, if necessary, a suitable hydrocarbon solvent. A method of reduction with an aluminum compound is used. There are no particular restrictions on the method for precipitating the fine particulate solid titanium trichloride catalyst complex, and the liquid may be deposited as it is or after adding a hydrocarbon diluent if necessary, at a temperature of 150°C or lower, preferably 40 to 120°C. , Particularly preferably, the temperature is raised to 60 to 100°C to precipitate. Note that when the total number of moles of titanium and aluminum in the titanium trichloride liquid is smaller than the number of moles of ether or thioether, a liberating agent may be added to promote precipitation. As liberating agents, titanium tetrachloride, aluminum halide,
For example, aluminum trihalide, alkyl aluminum dihalide, and the like are preferred. The amount of the liberating agent used is preferably 5 moles or less of titanium in the liquid. As the complexing agent in the method (b), those exemplified above as complexing agent C can be similarly mentioned.
Examples of the halogen compound include titanium tetrachloride and carbon tetrachloride. The complexing agent treatment and the halogen compound treatment may be performed simultaneously, or the complexing agent treatment may be performed first and then the halogen compound treatment may be performed. The complexing agent treatment is usually carried out by adding a complexing agent to solid titanium trichloride in a diluent in an amount of 0.2 to 3 moles relative to TiCl ₃ at a temperature of -20 to 80°C. After the complexing agent treatment, it is preferable to separate and wash the obtained solid. Halogen compound treatment is usually carried out in a diluent at a temperature of -10 to 50°C. The amount of halogen compound used is usually 0.1 per TiCl ₃
~10 times by mole, preferably 1 to 5 times by mole. After the halogen compound treatment, it is preferable to separate and wash the obtained solid. On the other hand, the organoaluminum compound of the cocatalyst has the general formula AlR ⁴ _o Cl _3-o (wherein R ⁴ has a carbon number of 1 to 20
is a hydrocarbon group, n is a number from 1.95 to 2.10). Among them, diethylaluminum monochloride in which R ⁴ is an ethyl group and n is 2 can be used satisfactorily;
Particularly preferred are the cocatalysts described in No. 55-38833, in which R ⁴ is a normal propyl group or a normal hexyl group. When R ⁴ is normal propyl group or normal hexyl group, n is 1.95≦n≦
It is important that the ratio is 2.10, and within this range, high results can be obtained in both polymerization activity and stereoregularity by polymerizing in combination with the solid titanium trichloride catalyst complex described above. Among the two kinds of third components used, the aromatic hydrocarbon is a hydrocarbon having a benzene ring, and may have a hydrocarbon group such as an alkyl group or an alkenyl group, or a substituent such as a halogen. . Specifically, monocyclic aromatic hydrocarbons such as benzene, toluene, ethylbenzene, xylene, styrene, n-propylbenzene, ethyltoluene, trimethylbenzene, tetramethylbenzene, and chlorobenzene;
Examples include polycyclic aromatic hydrocarbons such as diphenyl, diphenylmethane, triphenylmethane, naphthalene, methylnaphthalene, dimethylnaphthalene, vinylnaphthalene, phenanthrene, anthracene, and vinylanthracene, but when using a solid titanium trichloride catalyst complex There are several reasons why using the same type of solvent as the one used in its production or prepolymerization is advantageous in terms of solvent recovery, it is inexpensive and easy to handle, and it evaporates easily during polymer drying. Accordingly, monocyclic aromatic hydrocarbons that are liquid at room temperature and have a relatively low boiling point, such as benzene, toluene, and xylene, which can also be used as the solvent, are preferred. On the other hand, vinyl ethers include vinyl methyl ether, vinyl ethyl ether, vinyl n-
propyl ether, vinyl n-butyl ether,
Alkyl vinyl ethers such as vinyl i-butyl ether, vinyl n-hexyl ether, vinyl n-octyl ether, vinyl i-octyl ether, vinyl stearyl ether, cycloalkyl vinyl ethers such as cyclohexyl vinyl ether, aryl vinyl ethers such as phenyl vinyl ether, benzyl vinyl ether, etc. carbon number 25
The following vinyl ethers are mentioned, but vinyl methyl ether,
Vinyl ethyl ether, vinyl n-butyl ether and vinyl i-butyl ether are preferred. The ratio of each catalyst component used is usually a molar ratio of titanium trichloride: organoaluminum compound: aromatic hydrocarbon: vinyl ether in solid titanium trichloride, preferably 1:1 to 100:20 to 10000:0.01 to 10. is selected to be 1:2~40:50~5000:0.05~2. When the complexing agent and C component contained in the solid titanium trichloride catalyst complex are vinyl ethers,
The amount added should be adjusted so that the sum of the content of and the amount newly added as a catalyst component becomes the above-mentioned molar ratio. When polymerization is carried out in a hydrocarbon solvent, the aromatic hydrocarbon is used in an amount of 0.1 to 20% by volume, preferably 0.5 to 5% by volume, based on the solvent. If this amount is too small, the effect of improving the transparency and impact resistance of the film will not be sufficient, and if it is too large, the burden of recovering aromatic hydrocarbons from the polymer or polymerization solvent will increase, which is undesirable. The impact appears. In the method of the present invention, a catalyst system is prepared from the above-mentioned solid titanium trichloride, an organoaluminum compound, and a third component consisting of an aromatic hydrocarbon and a vinyl ether. Any known method can be used to prepare this catalyst system. I can do it. For example, a method in which the above four components are simply mixed in advance in a hydrocarbon solvent such as hexane, heptane, benzene, or toluene (if aromatic hydrocarbons such as benzene or toluene are used as the solvent, the total number of moles of (selected so as to have a usage ratio of ), and a method in which the above two components, for example, an organoaluminum compound and a vinyl ether, are mixed in advance. There are no particular restrictions on the mixing temperature, time, etc., but the usual temperature is preferably room temperature to the polymerization temperature, and the time is preferably not too long, usually within several days. Alternatively, a method may be adopted in which each of the catalyst components is separately supplied to the polymerization vessel without being mixed in advance. Further, the solid titanium trichloride used as a catalyst is pretreated with a small amount of the α-olefin described below in the presence of an organoaluminum compound before use. This pretreatment is effective in improving the physical properties of the polymer slurry, such as bulk density. The pretreatment is performed at a temperature lower than the polymerization temperature, generally from 20°C to 60°C, and the polymer produced by the pretreatment/titanium trichloride in solid titanium trichloride = 0.1 to 50/1 (weight ratio), usually 1 to 60°C. It is done so that the ratio is 20/1. As the solvent for this pretreatment, aliphatic hydrocarbons such as hexane and heptane, and alicyclic hydrocarbons such as cyclohexane can be used, but aromatic hydrocarbons themselves, which are added as the third component such as benzene and toluene, can be used as solvents. It is preferable to use it because it improves not only the stereoregularity but also the bulk density of the final polymer. Therefore, in the present invention, the α-olefin is polymerized in the presence of a catalyst system consisting of solid titanium trichloride, an organoaluminum compound, and a third catalyst component. As the α-olefin, propylene, butene-1, 3-methylbutene-1, 4
- α-olefins such as methylpentene-1, pentene-1, hexene-1, etc.
- Homopolymerization of olefins, random copolymerization of mixtures of these with ethylene, or mixtures of these with each other, or block copolymerization of these α-olefins or of these α-olefins and ethylene. In particular, propylene homopolymer, propylene 90% by weight
It is suitable for stereoregular polymerization to produce a random copolymer containing the above or a block copolymer containing 80% by weight or more of propylene. The polymerization reaction may be carried out by gas phase polymerization or by slurry polymerization in the presence of a solvent.
Examples of the solvent include aliphatic hydrocarbons such as pentane, heptane, hexane, and decane; alicyclic hydrocarbons such as cyclohexane and methylcyclohexane; however, the above-mentioned olefins themselves such as propylene are also preferably used. In addition, the polymerization reaction can be carried out either batchwise or continuously, and there are no particular limitations on the polymerization temperature and pressure, but it is usually
~100℃, preferably 60-90℃, pressure is atmospheric pressure ~
The pressure is about 100 atm. In addition, during polymerization, the molecular weight of the produced polymer can be controlled using a known molecular weight controlling agent such as hydrogen or halogenated hydrocarbon. As described above, α-olefin is polymerized, and the effects of high polymerization activity and high stereoregularity brought about by the method of the present invention can be achieved by polymerization with high catalytic efficiency, such as titanium trichloride (TiCl) in solid titanium trichloride. ₃ ) This is particularly noticeable in polymerizations in which 5,000 grams or more, preferably 10,000 grams or more of polymer is produced per gram, and the amount of catalyst remaining in the polymer is further reduced, resulting in improved stereoregularity of the resulting polymer. Such highly catalytic efficiency polymerization is particularly preferred because of its improved properties. According to the α-olefin polymerization method of the present invention described in detail above, not only high results are obtained in both polymerization activity and stereoregularity of the polymer, but also transparency and impact resistance are improved when formed into a film. High results can be obtained in both cases, and excellent effects not seen with conventional methods can be achieved. Therefore, the present invention has great industrial value. Next, the present invention will be explained in more detail with reference to Examples and Comparative Examples. In addition, in the examples and comparative examples, the catalyst efficiency CE is the total amount of propylene polymer produced per 1 g of titanium trichloride in solid titanium trichloride,
Polymerization activity K per hour, propylene pressure 1Kg/cm ²
This is the total amount of propylene polymer produced per gram of titanium trichloride. The total amount of propylene polymer produced herein refers to the amount including the amorphous polymer. The bulk density ρ _B of the polymer powder was measured according to JIS-K-6721. II-XLN is the total amount of polymer remaining after completely dissolving the polymer together with a stabilizer in boiling xylene, allowing it to slowly cool to room temperature, filtering out the precipitated polymer, and washing with xylene. It represents the stereoregularity of the total polymer. Polymer melt flow index, MFI is
Measured according to ASTM-D1238. FR is the extrusion rate of molten polymer at 230℃ with a load of 5.528Kg, and 0.553
Expressed as the ratio of the same extrusion amount at Kg load and 230℃,
This is a simple method to show the spread of molecular weight distribution. Film haze (transparency) is ASTM-
It was measured using a Nippon Denshoku haze meter according to D1003. This indicates the transparency of the film. In addition, the dirt, drop, impact, and DDI of the film are manufactured by Toyo Seiki in accordance with ASTM-D1709.
Measurements were made using a DDI measuring machine with a hemisphere of 1.5 inches and a height of 20 inches. This indicates the impact resistance of the film. FIG. 1 is a flowchart to help understand the technical content included in the present invention, and the present invention is not limited in any way by the flowchart unless it deviates from the gist thereof. Catalyst production example 1 (A) Production of solid titanium trichloride catalyst complex A purified n-hexane (5.0 g) was charged into an autoclave with a capacity of 10 that was sufficiently purged with nitrogen, and while stirring,
2.7 moles of di-n-octyl ether and 3.0 moles of titanium tetrachloride were charged. Adjust the internal temperature to 30℃ and add diethylaluminum monochloride.
0.5 of n-hexane solution containing 1.0 mol was added to obtain a brown homogeneous solution. When the temperature was then raised, purple fine particles of solid were observed to precipitate from around 50°C. After holding at 95°C for about 1 hour, granular purple solids were separated and washed repeatedly with n-hexane to obtain 345 g of titanium trichloride solid catalyst complex. As a result of elemental analysis and gas-chromatography analysis, the composition of this substance is TiCl ₃・(AlCl ₃ ) _0.004・[(n-
C ₈ H ₁₇ ) ₂ O] _0.11 . (B) Pretreatment with propylene 12.5 ml of purified n-hexane was charged into an autoclave with a capacity of 20 that was sufficiently purged with nitrogen, and 1.6 ml of diethylaluminum monochloride was charged with stirring.
The solid titanium trichloride-based catalyst complex obtained in (A) above was charged so that the amount of TiCl ₃ was 250 g.
Then, the internal temperature was adjusted to 30°C, and while stirring, blowing of propylene gas was started and continued at the same temperature until the amount of polymerized propylene reached 1250 g. The solid was then separated and n-
Washing with hexane was repeated to obtain polypropylene-containing titanium trichloride. Examples 1 to 11 and Comparative Examples 1 to 5 The polypropylene-containing solid titanium trichloride obtained in Catalyst Production Example 1 (B) was added to a reactor with a capacity of 400 that was sufficiently purged with nitrogen, and the TiCl ₃ feed rate was as shown in Table 1. At the same time, the organoaluminum compound was fed at a molar ratio of 8 to TiCl ₃ (organic Al compound/TiCl ₃ ), and the aromatic hydrocarbon was fed in the type and amount shown in Table 1 ( (Displayed as volume % with respect to the solvent n-hexane and molar ratio with respect to TiCl ₃ ), vinyl ethers were used in the types and amounts listed in Table 1 (molar ratio with respect to TiCl ₃ , vinyl ethers/
TiCl ₃ ), n-hexane, propylene and hydrogen were each continuously supplied, and the propylene partial pressure was 13.0.
Kg/cm ² and the molar ratio of hydrogen to propylene in the gas phase was 0.045, and polymerization was carried out continuously at 70° C. for an average residence time of 5.0 hours. In Examples 1 to 4 and Comparative Examples 1 to 5, di-n-propyl aluminum monochloride was used, and in Examples 5 to 11, di-n-hexane aluminum monochloride was used. Table 1 shows the polymerization activity determined from the catalyst supply rate and polymer production rate. The polymer slurry was purged of unreacted propylene in a degassing tank, then isopropanol was added so that the isopropanol concentration in the inert solvent solution was 5% by weight, and after continuous treatment at 70°C, the polymer slurry was degassed in a centrifuge. It was separated into a combined cake and liquid. The product propylene polymer was taken out as a powder from the cake through a drying process, and the amorphous polymer dissolved in the solvent was concentrated and separated from the liquid. The ratio of the amorphous polymer thus obtained to the total polymer is shown in Table 1 as the amorphous polymer production rate. To the product powder obtained as above, 0.2% by weight of BHT and 0.3% by weight of silica were added as antioxidants and pelletized at 250℃ using a pelletizer with an inner diameter of 40mm, and then formed into a water-cooled inflation film with a thickness of 30μ. Molded. The haze (transparency) and DDI (impact resistance) of this film were measured. FR was measured for these results. These results are summarized in Table 1. In Examples 1 to 4, polymerization was carried out using toluene as the aromatic hydrocarbon and various vinyl ethers. Comparative Examples 1 to 3 are conventionally known methods that do not use aromatic hydrocarbons. ,
The haze of the film increases, i.e. the transparency deteriorates,
In addition, impact strength and DDI decreased, but Examples 1 to 4
When used in combination with toluene, the haze of the film is reduced, which improves transparency and impact strength.
It is clear that DDI also improves. Furthermore, it can be seen that FR, which is an index of molecular weight distribution, also decreased. On the other hand, in Comparative Examples 4 and 5, when the third component was not used or when only the aromatic hydrocarbon was used, the transparency and impact resistance of the film were satisfactory, but the production rate of amorphous polymer was low. is large,
and shows that the stereoregularity II-XLN is low. As a result, the yield of propylene polymer deteriorated and the rigidity of the film decreased. Another effect obtained by the method of the present invention is that when attempting to increase II-XLN using only vinyl ethers, the polymerization activity K decreases relatively greatly.
It is clear from a comparison between Examples 1 to 4 and Comparative Examples 1 to 3 that when toluene is used in combination, the decrease in K is small. In Examples 5 to 7, the amount of toluene was changed, but it is shown that the effect is already visible at 0.5% by volume of toluene. Examples 8 to 11 are examples in which various aromatic hydrocarbons were used, and while the amorphous polymer production rate was reduced and the stereoregularity II-XLN was improved, the transparency and impact resistance of the film were also improved. This shows that both have been improved.

【table】

[Table] Catalyst production example 2 (A) Production of solid titanium trichloride-based catalyst complex 5.0 mol of purified toluene was charged into an autoclave with a capacity of 10 that was sufficiently purged with nitrogen, and while stirring, 5.0 mol of di-n-butyl ether and 5.0 mol of di-n-butyl ether and tetrachloride were charged. Titanium
5.0 mol was charged. After adjusting the internal temperature to 30° C., 0.7 mol of a toluene solution containing 2.5 mol of diethylaluminum monochloride was added to obtain a brown homogeneous solution. Then, when the temperature was increased to 40
From around the time the temperature exceeded ℃, a purple fine particulate solid was observed to precipitate. After holding at 95℃ for about 1 hour, the granular purple solid was separated and washed repeatedly with toluene.
778 g of titanium trichloride solid catalyst complex was obtained. As a result of elemental analysis and gas-chromatography analysis, the composition of this substance is TiCl ₃・(AlCl ₃ ) _0.003・[(n-
C ₄ H ₉ ) ₂ O] was _0.07 . (B) Pretreatment with propylene 12.5 mol of purified toluene was charged into an autoclave with a capacity of 20 that was sufficiently purged with nitrogen, and while stirring, 1.6 mol of diethyl aluminum monochloride,
The solid titanium trichloride catalyst complex obtained in (A) above is
250g of TiCl ₃ was charged. Then check the internal temperature
The temperature was adjusted to 20°C, and while stirring, blowing of propylene gas was started and continued at the same temperature until the amount of polymerized propylene reached 1250 g. The solid was then separated and washed repeatedly with toluene to obtain polypropylene-containing titanium trichloride. In Comparative Examples 6 to 9, which will be described later, after washing with toluene, toluene was replaced with n-hexane. Examples 12 to 16 and Comparative Examples 6 to 10 In Example 1, the polypropylene-containing solid titanium trichloride obtained in Catalyst Production Example 2 (B) was used as the solid catalyst component, and the types of aromatic hydrocarbons and vinyl ethers were Polymerization was carried out in the same manner as in Example 1, except that the amounts used were as shown in Table 2 and the supply rate of TiCl ₃ was as shown in Table 2. Propylene polymer was obtained by isopropanol treatment, separation, and drying. Ta. Then, it was formed into a water-cooled inflation film and various measurements were performed. These results are summarized in Table 2. In Examples 12 to 16, various vinyl ethers were polymerized using toluene, which is a solvent for a solid titanium trichloride slurry containing polypropylene.
Comparing with Comparative Examples 6 to 8, by using aromatic hydrocarbons in combination with vinyl ethers, the amorphous polymer production rate also decreased, and the stereoregularity II-
It is clear that as the XLN increases, the transparency and impact resistance of the film are improved. Also, similar to the previous example, the decrease in polymerization activity was small. Such an effect cannot be achieved by using vinyl ethers or aromatic hydrocarbons alone, but can only be achieved by the combination of the two.

【table】

[Table] Catalyst production example 3 (A) Production of solid titanium trichloride-based catalyst complex In an autoclave with a capacity of 10 that was sufficiently purged with nitrogen, purified n-hexane 1.0 and titanium tetrachloride were added.
2.0 mol was charged. Adjust the internal temperature to 5℃ and add 4.0% of ethylaluminum sesquichloride while stirring.
2.0 mol of n-hexane solution was added and stirring was continued at 5° C. for an additional 2 hours. Then, washing was performed with n-hexane to obtain a reddish-purple solid substance. The amount of n-hexane is 3.0, and the internal temperature is 30.
After adjusting the temperature to 30°C, 0.42% of di-iso-amyl ether was added under stirring, and stirring was continued for an additional 1.5 hours at 30°C. Washing with n-hexane and drying under reduced pressure gave a brown solid substance. Next, 8 mol of titanium tetrachloride was added and stirring was continued for 2 hours at 35°C, followed by washing with n-hexane to obtain about 400 g of a purple titanium trichloride solid catalyst complex. As a result of elemental analysis and gas-chromatography analysis, the composition of this substance is TiCl ₃・(AlCl ₃ ) ₀₀₂・[(i-
_C5H11 ) _2O ] was _{0.11 .} (B) Pretreatment with propylene 12.5 ml of purified n-hexane was charged into an autoclave with a capacity of 20 that was sufficiently purged with nitrogen, and 1.6 ml of diethylaluminum monochloride was charged with stirring.
250 g of the solid titanium trichloride catalyst complex obtained in (A) above was charged as TiCl ₃ . Then, the internal temperature was adjusted to 20℃, and while stirring, blowing propylene gas was started, and 1250g of polymerized propylene was produced.
Blowing of propylene gas was continued at the same temperature until the temperature reached . The solid was then separated and washed repeatedly with n-hexane to obtain polypropylene-containing titanium trichloride. Examples 17 to 19 and Comparative Examples 11 to 13 In Example 1, the polypropylene-containing solid titanium trichloride obtained in Catalyst Production Example 3 (B) was used as the solid catalyst component, and the types of aromatic hydrocarbons and vinyl ethers were Polymerization was carried out in the same manner as in Example 1, except that the amounts used were as shown in Table 3 and the supply rate of TiCl ₃ was as shown in Table 3, followed by isopropanol treatment, separation, and drying to obtain a propylene polymer. Ta. Then, it was formed into a water-cooled inflation film and various measurements were performed. These results are summarized in Table 3. As mentioned above, it is clear that the combined use of aromatic hydrocarbons improves the transparency and impact resistance of the film.

【table】 [Brief explanation of drawings]

1 and 2 are flowcharts showing one embodiment of the present invention.

Claims (1)

[Scope of Claims] 1. A solid catalyst component obtained by pretreating a solid titanium trichloride catalyst complex with α-olefin in the presence of an organoaluminum compound, an organoaluminum compound,
A method for producing a polyolefin by polymerizing α-olefin using a catalyst system consisting of aromatic hydrocarbons and vinyl ethers, the method comprising: (a) titanium tetrachloride in the presence of an ether or thioether as a solid titanium trichloride catalyst complex; (b) A method in which liquefied titanium trichloride obtained by reducing titanium tetrachloride is precipitated at a temperature of 150°C or lower, or (b) solid titanium trichloride obtained by reducing titanium tetrachloride with an organoaluminum compound or metal aluminum is complexed A method for producing a polyolefin using a solid titanium trichloride catalyst complex having an aluminum content in an atomic ratio of aluminum to titanium of 0.15 or less obtained by a method of treating with a curing agent and a halogen compound.