JPH0456843B2 - - Google Patents

Description

[Detailed description of the invention]

[Field of Technology] The present invention relates to a preactivated catalyst for α-olefin polymerization and a method for producing the same. More specifically, the present invention relates to a catalyst comprising a titanium trichloride composition and an organoaluminum compound, and a method for producing the catalyst, which is prepared by reacting an α-olefin and an electron donor simultaneously or in a mixed manner. [Prior Art] It is well known that a so-called Ziegler-Natsuta catalyst, which is a combination of a transition metal compound of group ~ and an organometallic compound of group ~ of the periodic table, can be used as a catalyst for α-olefin polymerization. Among these, the titanium trichloride composition as the transition metal compound can be used for highly crystalline homopolymers such as propylene or butene-1, or highly crystalline copolymers of ethylene/propylene or butene-1. Widely used. This titanium trichloride composition is a composition obtained by reducing titanium tetrachloride with various reducing agents or by post-reduction treatment, and consisting of a substantially trivalent titanium chloride and an oxidizable material obtained by oxidizing the reducing agent. It is a thing. The present inventors have previously used a titanium trichloride composition-based α-olefin polymerization catalyst that has high storage stability and thermal stability and high catalytic activity. provided a method for producing olefin polymers (JP-A-56-110707, JP-A-56-110707;
-120712, etc., hereinafter referred to as the earlier invention). The catalysts used in these methods have been preactivated with α-olefin, have high catalytic activity, and have the advantage of having a low rate of by-product of amorphous polymers such as atactic polypropylene. However, the method of the present inventors' previous invention had practical problems (or limitations in catalyst performance) as shown in the following items. These problems are that in order to increase the amount of α-olefin polymerized per unit capacity of the polymerization vessel, the concentration of the α-olefin polymer slurry in the vessel must be increased to 30% or more, or the residence time of the slurry must be increased. It becomes obvious when the length of the In other words, (a) the by-product rate of amorphous polymer increases, (b) the shape of the α-olefin polymer particles deteriorates, and (c) the α-olefin polymer powder is dried or transported in the equipment after the polymerization process is completed. Occlusion caused by the powder or
It sometimes became difficult to discharge the amorphous polymer. In addition, when producing a binary or ternary copolymer consisting of ethylene, propylene, butene-1, etc. using a catalyst combined with a titanium trichloride composition having a particularly small average particle size, E is used as a by-product. The soluble content of solvents such as hexane increases, and α
- It was not possible to increase the slurry concentration of the olefin polymer, and as a result, it was sometimes necessary to reduce the amount of α-olefin polymerized per unit time. It is also known to increase the amount of electron donor in combination with titanium trichloride compositions and organoaluminum compounds to control the formation of by-products such as atactic polypropylene. However, when this method is applied to the high slurry concentration slurry polymerization method according to the present invention, the catalyst activity decreases or abnormal polymerization occurs due to the presence of a large amount of electron donors. As a result of the increase in the number of parts, the molecular weight distribution of the polymer becomes wider, and the flowability of the product polymer during molding or film formation may deteriorate, resulting in poor moldability or poor haze transparency of the film. It was hot. In addition to the above-mentioned "earlier invention," there are also known methods of adding an electron donor to a catalyst that is to be preactivated or has been preactivated (Note: For example, Japanese Patent Application Laid-Open No. 104907/1983). . However, in any case, the electron donor is added to the catalyst without the coexistence of α-olefin, and in this respect, the above-mentioned limitations of known techniques related to addition of electron donors (Note: High concentration slurry polymerization (difficulty in execution) could not be exceeded. [Summary of the Invention] In view of the above-mentioned problems with the known techniques, the present inventors have developed the following method when producing a copolymer using a high concentration slurry polymerization method using a titanium trichloride composition having a particularly small average particle size. Even if the residence time of the slurry in the polymerization vessel is increased or its concentration is increased, the solvent soluble content in the produced polymer can be greatly reduced without causing a significant decrease in catalyst activity or deterioration of polymer quality. We have conducted intensive research to find a preactivation method that can improve the polymerization volume per unit volume of the polymerization vessel and the amount of polymerization per unit time without increasing the amount of polymerization. As a result, when preactivating a titanium trichloride composition-organoaluminum compound catalyst with an α-olefin, it was found that the above-mentioned problems could be solved by reacting an electron donor with the catalyst at the same time as the α-olefin. With this knowledge, the present invention was completed. As is clear from the above description, an object of the present invention is to provide a preactivated catalyst for α-olefin polymerization that is capable of high-concentration slurry polymerization, and a method for producing the same. Another object is to provide an alpha-olefin polymerization method using the catalyst. [Operation] The present invention has the following main configuration (1) and embodiment configurations (2) and (3). (1) A solid product obtained by reacting an organic ether and titanium tetrachloride with a solid obtained by reacting titanium tetrachloride with an organoaluminum compound or a reaction product of an organoaluminum compound and an organic ether. α-olefin and one or more electron donors selected from organic ethers, hydrogen sulfide, or aromatic carboxylic acid esters are simultaneously reacted with a catalyst formed by combining a titanium trichloride composition and an organoaluminum compound. Alternatively, a preactivated catalyst for α-olefin polymerization obtained by mixing and reacting (high concentration slurry method). (2) The organoaluminum compound is a compound represented by the general formula AlRnR′n′X ₃ −(n+n′) (wherein R and R′ are alkyl, aryl, alkaryl, or cycloalkyl groups having 1 to 20 carbon atoms, or an alkoxy group, X is fluorine, chlorine, bromine or iodine, n and n' are 0<n+n'3
The preactivated catalyst for α-olefin polymerization according to item 1 above, which represents an arbitrary number of . (3) The α-olefin is a linear monoolefin having 2 to 10 carbon atoms, a branched monoolefin or diolefin having 4 to 10 carbon atoms, or 1 selected from styrenes having 8 to 10 carbon atoms in place of the α-olefin. The preactivated catalyst for α-olefin polymerization according to item 1 above. The configuration and effects of the present invention will be explained in detail below. The titanium trichloride composition used in the present invention has an average particle size of 2 to 50 microns, preferably 5 to 30 microns, and although its shape is not limited, it is preferably spherical and has a narrow particle size distribution. The method for producing the titanium trichloride composition is also not particularly limited, and specific examples include the following method. That is, first, an organoaluminum compound and an electron donor mainly composed of organic ethers are reacted to form a reaction product ().
Examples include a method of obtaining a titanium trichloride composition by reacting this () with titanium tetrachloride under stirring, and then reacting the reactant with an electron donor and an electron acceptor. can. The reaction between the organoaluminum compound (A ₁ ) and the electron donor (B ₁ ) is carried out in the solvent (D) at -10°C to 50°C for 30
The reaction is carried out in seconds to 5 hours, and the appropriate ratio of amounts used is 1 to 4 mol of electron donor and 0.5 to 2 mol of solvent per 1 mol of organic aluminum. The reaction between the thus obtained reaction product () and titanium tetrachloride (C) was 0.
The reaction is carried out under stirring at ~200°C, preferably 10-90°C, for 5 minutes to 8 hours. in the reaction product ()
The reaction is carried out at a ratio of the number of Al atoms to the number of Ti atoms in titanium tetrachloride (Al/Ti) of 0.05 to 1.0, preferably 0.06 to 0.2. After the reaction is completed, the liquid portion is separated and removed by filtration or decantation at a temperature of 50°C or higher, and then washing with a solvent is repeated at a temperature of 30°C or higher to donate electrons to the obtained solid product (). The body (B ₂ ) and the electron acceptor (E) are reacted. During this reaction, preferably a solvent such as an aliphatic hydrocarbon is allowed to coexist. The amount used is 50 to 200 (B ₂ ) per 100 g of solid product ().
g, (E) 20~500g, solvent 100~1000ml, and 50~
It is desirable to react at 100°C for 5 minutes to 5 hours.
After the reaction is completed, the liquid portion is separated and removed by filtration or decantation, and then washing is repeated with a solvent to obtain a titanium trichloride composition. The obtained titanium trichloride composition is either dried and taken out as a solid, or left suspended in a solvent for the next use. Another example of the titanium trichloride composition used in the present invention is obtained by reacting an electron donor with a reduced solid obtained by reducing titanium tetrachloride with organoaluminium, and then reacting it with titanium tetrachloride. There are also titanium trichloride compositions. The preactivated catalyst for α-olefin polymerization of the present invention combines the titanium trichloride composition and an organoaluminum compound in the presence or absence of an electron donor, and then combines the α-olefin and the electron donor simultaneously or It is obtained by performing preactivation which includes mixing, adding and reacting. As a specific example, a catalyst preactivated by combining the titanium trichloride composition and an organoaluminum compound (A ₂ ) and then reacting an α-olefin (F ₁ ) and an electron donor (B ₃ ); After combining the titanium trichloride composition, the organoaluminum compound (A ₂ ), and the electron donor (B ₄ ), preactivation is performed by reacting the α-olefin (F ₁ ) and the electron donor (B ₃ ). or a preactivated catalyst to which an electron donor (B ₅ ) is added, or a reaction product (G) of an electron donor (B ₆ ) and an organoaluminum compound (A ₃ ) after The catalyst preactivated by adding (F ₁ )
and (B ₃ ), and after the reaction, a preactivated catalyst obtained by reacting α-olefin (F ₂ ), ~
After that, there are preactivated catalysts obtained by reacting α-olefin (F ₂ ). A specific example of the above is shown in a flow sheet as follows. Titanium trichloride composition + organic Al (A ₂ ) α-olefin (F ₁ ) ――――――――――――→ Electron donor (B ₃ ) Preactivated catalyst 1 Titanium trichloride composition Physical organic Al (A ₂ ) + electron donor (B ₄ ) α-olefin (F ₁ ) ――――――――――――→ Electron donor (B ₃ ) Preactivated catalyst 2 Preliminary Activated catalyst 1 or 2− ――――――――――→ Electron donor (B ₅ ) Preactivated catalyst 3 Same as above − ――――――――――――→ Reaction product (G ) Preactivated catalyst 4 Preactivated catalyst 1 or 2 α-olefin (F ₂ ) ――――――――――――――→ − Preactivated catalyst 5 ′ Preactivated catalyst 3, 4―― ――――――――――――――――――→ Electron donor B ₄ or reaction product (G) Preactivated catalyst 5' Preactivated catalyst 3 or 4α-olefin (F ₂ ) - ――――――――――――――→ ― Preactivation catalyst 6 Preactivation is performed by adding 0.1 to 10 g of organoaluminum (A ₂ ), 0 to 5 g of solvent, and 1 g of titanium trichloride composition. An operation including a step of reacting a combination of 0 to 1.0 g of electron donor (B ₄ ) and 0.01 to 50 g of α-olefin (F ₁ ) and 0.001 g to 2.0 g of electron donor (B ₃ ) simultaneously or in a mixed manner. conduct. The α-olefin (F ₁ ) and the electron donor (B ₃ ) may be added separately and at the same time during the preactivation reaction.
After mixing (F ₁ ) and (B ₃ ), the mixture may be added and reacted. At that time, one or both of (F ₁ ) and (B ₃ ) dissolved in solvents 0 to 5 may be added to the above combination and reacted. During preactivation, the concentration ratio of (F ₁ ) and (B ₃ ) used in the reaction is sometimes not limited, but both (F ₁ ) and (B ₃ ) react with the catalyst according to the combination. It is necessary to perform an operation such as adding A○ (F ₁ ) and then adding (B ₃ ) in the presence of unreacted (F ₁ ), or adding B○ (F ₁ ) and (B ₃ ). There are methods such as adding the mixture after mixing. (F ₁ ) and (B ₃ )
After reacting simultaneously, the electron donor (B ₅ ) is
It is also possible to add 0.001g to 2.0g of electron donor (B ₆ ) and 0.01 to 10g of organic aluminum (A ₃ ) as reaction products (G) in 10 to 10000g of solvent.
The (G)0.02-15 reacted at ~100℃ for 1 minute to 20 hours
g can also be used. α-olefin (F ₁ )
The conditions for adding and reacting the electron donor (B ₃ ) are preferably carried out in an aliphatic hydrocarbon solvent at 10 to 50°C for 10 minutes to 20 hours. After reaction by adding α-olefin (F ₁ ) and electron donor (B ₃ ), the solvent used in the reaction can be removed to obtain a solid catalyst component. The reaction of α-olefin (F ₂ ) with preactivated catalyst 1 or 2 can be carried out in an aliphatic hydrocarbon solvent or in a liquefied α-olefin such as liquefied propylene without using a solvent. etc. can also be reacted in the gas phase. This reaction can also be carried out in the presence of a previously obtained α-olefin polymer or hydrogen. The reaction of α-olefin (F ₂ ) is from 0 to 100
C., preferably 10 to 80.degree. C. for 1 minute to 20 hours. The α-olefins (F ₁ ) and (F ₂ ) used to preactivate the catalyst are linear or branched α-olefins.
Olefins, such as ethylene, propylene, butene-1, 2-methylpropene, pentene-1, 2-methyl-butene-1, 3-methyl-butene-1, hexene-1, 4-methyl-pentene, 3 -methyl-pentene-1, heptene-1,
Examples include octene-1. α-olefin (F ₁ )
and (F ₂ ) may be the same or different, and may be the same or different from the α-olefin to be polymerized. After preactivation, the solvent, part of the organoaluminium, and unreacted α-olefin can be removed by filtration or distillation under reduced pressure, and the dried granules can be used for polymerization, or they can be used for polymerization by adding a solvent. It can be diluted or organoaluminum can be added. In addition, in preactivated catalysts 3 and 4, the electron donor (B ₅ ) or the reaction product (G) and the slurry containing the titanium trichloride composition are stored in separate tanks and placed in the polymerization vessel. They can be added separately or mixed just before the polymerization vessel to form a preactivated catalyst. The thus obtained preactivated catalyst can be subjected to slurry polymerization, bulk polymerization, gas phase polymerization of α-olefin without phase change, bulk polymerization followed by gas phase polymerization, or slurry polymerization followed by gas phase polymerization. Any method can exhibit the effects of the present invention. The method of producing α-olefin using the catalyst of the present invention, i.e., the polymerization method, includes slurry polymerization in a hydrocarbon catalyst such as n-pentane, n-hexane, n-heptane, n-octane, benzene, toluene, etc. There are bulk polymerizations carried out in liquefied α-olefin monomers such as liquefied propylene and liquefied butene-1, gas phase polymerizations carried out in gas phase monomers such as ethylene and propylene, and combinations thereof. In all cases, the polymerization temperature was room temperature (20
℃)~200℃, polymerization pressure is normal pressure (0Kg/ ^cm2G )~
It is usually carried out at 50Kg/cm ² G for about 5 minutes to 20 hours. During polymerization, steps such as adding an appropriate amount of hydrogen to control the molecular weight are the same as in conventional polymerization methods. It is also used in the multi-stage polymerization of α-olefins, including gas phase polymerization, slurry polymerization, and bulk polymerization, in which 2 to 10 reactors are connected in series, the polymerization phase is changed in each reactor, the catalyst is fed, - It is also possible to change olefin and hydrogen. The α-olefins subjected to polymerization in the method of the present invention are linear monoolefins of ethylene, propylene, butene-1, hexene-1, octene-1, 4-methyl-pentene-1, 2-methyl- These include branched monoolefins such as pentene-1 and 3-methyl-butene-1, diolefins such as butadiene, isoprene, and chloroprene, and styrene, and the method of the present invention not only homopolymerizes each of these, but also They can be copolymerized by combining each other with other olefins, such as propylene and ethylene, butene-1 and ethylene, propylene and butene-1, or by combining three components such as propylene, ethylene, and butene-1. It is also possible to do
In addition, block copolymerization can also be carried out by changing the type of α-olefin to be fed in multi-stage polymerization. The organoaluminum compound used in the present invention has the general _formula AlRnR'n' Indicates the group,
X represents a halogen such as fluorine, chlorine, bromine, or iodine, and n and n' represent any number in the range 0<n+n'3, and specific examples include trimethylaluminum, triethylaluminum, tri-n-propyl aluminum, tri-n-
Trialkylaluminums such as butylaluminum, tri-i-butylaluminum, tri-n-hexylaluminum, tri-i-hexylaluminum, tri-2-methylpentylaluminum, tri-n-octylaluminum, tri-n-decylaluminum, diethylaluminum monochloride , di-n-propyl aluminum monochloride, di-i-butyl aluminum monochloride,
Diethylaluminum monohalides such as diethylaluminium monofluoride, diethylaluminium monobromide, diethylaluminum monoiodide, alkylaluminum hydrides such as diethylaluminium hydride, methylaluminum sesquichloride, ethylaluminum sesquichloride, ethylaluminum dichloride, i- Examples include alkyl aluminum halides such as butylaluminum dichloride, and alkoxyalkylaluminums such as monoethoxy diethyl aluminum and diethoxy monoethyl aluminum can also be used. These organoaluminum compounds are 2
It is also possible to use a mixture of more than one species. The organoaluminum compound (A ₁ ) is combined with the titanium trichloride composition to obtain the reaction product (A ₂ ), the organoaluminum compound (A ₃ ) is combined with the electron donor (B ₆ ) may be the same or different. Electron donors used in the present invention (B ₁ ), (B ₂ ),
Each component constituting (B ₃ ), (B ₄ ), (B ₅ ), and (B ₆ ) is an organic compound or inorganic compound having any one of oxygen, nitrogen, sulfur, or phosphorus atoms, and ethers. , alcohols, esters, aldehydes,
These include fatty acids, ketones, nitriles, amines, amides, urea or thioureas, isocyanates, azo compounds, phosphines, phosphites, phosphinites, hydrogen sulfide or thioethers, thioalcohols, and the like. Specific examples include diethyl ether, di-n-propyl ether, diisopropyl ether, methyl n-butyl ether, methyl tert-butyl ether, ethyl n-propyl ether, di-n-butyl ether,
Di-n-pentyl ether, di(2-methylbutyl) ether, di(3-methylbutyl) ether, methyl n-amyl ether, methyl isoamyl ether, ethyl n-amyl ether, ethyl neopentyl ether, di-n-hexyl ether, di i-hexyl ether, ethyl n-hexyl ether, ethyl α-methylhexyl ether, di-n-octyl ether, di-i-octyl ether, di-n-dodecyl ether, diphenyl ether, ethylene glycol dimethyl ether,
Ethers such as diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, tetrahydrofuran, methanol, ethanol, propanol, butanol, n-amyl alcohol, isoamyl alcohol, 2-methylbutanol, hexanol, octanol, phenol, cresol, xylenol, Alcohols such as ethylphenol and naphthol, methyl methacrylate, ethyl acetate, butyl formate, amyl acetate,
Vinyl butyrate, vinyl acetate, ethyl benzoate, propyl benzoate, butyl benzoate, octyl benzoate, 2-ethylhexyl benzoate, methyl toluate, ethyl toluate, 2-ethylhexyl toluate, methyl anisate, ethyl anisate, anisic acid Esters such as propyl, ethyl cinnamate, methyl naphthoate, ethyl naphthoate, propyl naphthoate, butyl naphthoate, 2-ethylhexyl naphthoate, ethyl phenylacetate, aldehydes such as acetaldehyde and benzaldehyde, formic acid, acetic acid, propion acid, butyric acid, oxalic acid,
Fatty acids such as succinic acid, acrylic acid, and maleic acid, aromatic acids such as benzoic acid, ketones such as methyl ethyl ketone, methyl isobutyl ketone, and benzophenone, nitrile acids such as acetonitrile,
Methylamine, diethylamine, tributylamine, triethanolamine, β(N,N-dimethylamino)ethanol, pyridine, quinoline, α
-picoline, 2,4,6-trimethylpyridine,
Amines such as N,N,N',N'-tetramethylhexaethylenediamine, aniline, dimethylaniline, formamide, hexamethylphosphoric acid triamide, N,N,N',N',N''-pentamethyl-
Amides such as N'-β-dimethylaminomethylphosphoric acid triamide and octamethylpyrophosphoramide, ureas such as N,N,N',N'-tetramethylurea, and isocyanates such as phenyl isocyanate and tolyl isocyanate. azo compounds such as azobenzene, phosphines such as ethylphosphine, triethylphosphine, tri-n-butylphosphine, tri-n-octylphosphine, triphenylphosphine, triphenylphosphine oxide, dimethylphosphine, dimethylphosphine, Phosphites such as n-octylphosphite, triethylphosphite, tri-n-butylphosphite, and triphenylphosphite; phosphinites such as ethyldiethylphosphinite, ethylbutylphosphinite, and phenyldiphenylphosphinite; Examples include thioethers such as diethyl thioether, diphenyl thioether, methyl phenyl thioether, ethylene sulfide and propylene sulfide, and thio alcohols such as ethyl thio alcohol, n-propyl thio alcohol and thiophenol. These electron donors can also be used in combination. The first effect of the present invention is to provide a catalyst that can suppress the formation of polymers soluble in solvents such as n-hexane even if the concentration of polymer slurry is increased by increasing the residence time of the catalyst in the polymerization vessel. It is. As a result, for example, in the production of polypropylene,
The isotactic index (n
- Hexane (20° C.) The ratio of isotactic polypropylene as insoluble matter to the total amount of polymer produced (100%) reaches 98.0-99.8%. As a result,
Even if the atactic polymer is not removed, the physical properties of the polymer, especially the rigidity, will not be reduced, so the amount of polymerization per polymerization vessel can be increased while the removal of the atactic polymer can be omitted. It has become possible to significantly improve productivity. The second effect of the present invention is that when producing a copolymer using a titanium trichloride composition with a small average particle size, the formation of a solvent-soluble polymer can be suppressed even without using an excess electron donor. The goal is to provide a catalyst that can help. This makes it possible to increase the slurry concentration in the production of copolymers, making it possible to produce copolymers without reducing the production volume per polymerization vessel, and making it possible to produce solvent-soluble polymers. Production costs have been lowered by improving the unit consumption of monomers and comonomers due to a reduction in the amount of polymers used, and handling such as discharge and recovery of solvent-soluble polymers has also become easier. The third effect of the present invention is that it is no longer necessary to use an excess of electron donors, so there is no significant decrease in catalyst activity, and the broadening of the molecular weight distribution due to abnormal polymerization is less likely. This means that flowability and formability during molding and film formation are no longer reduced, and quality deterioration such as deterioration of film haze is no longer caused. Examples are shown below. Example 1 (1) Production of titanium trichloride composition A stirring blade was attached to a reactor with an inner diameter of 180 m/m, a height of 220 m/m, and a semi-elliptical bottom and an internal volume of 5.
A solution of 0.83 mol of diethylaluminium monochloride (DEAC) dissolved in 1.17 mol of n-hexane and 1.99 mol of diisoamyl ether were mixed for 5 minutes,
Reaction product liquid () kept at 35℃ for 1 hour
(Molar ratio of diisoamyl ether/DEAC 2.40)
I got it. The reactor was replaced with nitrogen and titanium tetrachloride 7.47
mol, heated to 45°C, and stirred at 220 rpm, the above reaction product solution () was heated to 45°C over 1 hour.
It was added dropwise while keeping the temperature at °C. After dropping, heat at 45℃ for 1
The mixture was maintained at 78° C. for an additional 1 hour, and then allowed to settle at the same temperature, and the supernatant liquid was removed. n-
After repeating the operation of adding 3 hexane and removing the supernatant liquid by decantation twice, 284 g of the obtained solid product () was suspended in 300 ml of n-hexane, and 493 g of titanium tetrachloride and diisoamyl ether were added.
274g was added and reacted at 65°C for 1 hour. After the reaction, the supernatant liquid was removed at 35°C, and the operation of adding n-hexane and washing in step 3 was repeated five times, and then dried under reduced pressure to obtain a titanium trichloride composition (average particle size).
25μ) 301g was obtained. (2) Preparation of preactivated catalyst After purging a stainless steel reactor with internal volume 1 with inclined blades with nitrogen gas, 500 ml of n-hexane,
6.6 g of diethylaluminium monochloride, 0.022 g of diethylene glycol dimethyl ether, the above titanium trichloride composition (average particle size 25 microns)
Add 3.0g of propylene at 30℃ for 7 hours.
A mixture of 15 g and 1.89 g of methyl p-toluate was fed, and after the feeding was completed, the reaction was continued with stirring for an additional 3 hours, and unreacted monomers were purged to obtain a preactivated catalyst. Reference example 1 After replacing a stainless steel reactor with internal volume 50 with inclined blades with nitrogen gas, n-hexane 12.7,
69 ml of the above preactivated catalyst slurry (containing 0.40 g of the titanium trichloride composition and 3.53 g of the preactivated catalyst) was added, the reactor was closed, hydrogen 7 was added, and propylene was heated at 75°C to 6 kg/cm ² Polymerization was carried out at G for 10 hours. After polymerization, by drying, 5.6
Kg of polypropylene was obtained. The polymer yield per gram of titanium trichloride composition was 14,000 g, and even though the polymer slurry concentration ([polymer/(n-hexane + polymer)] x 100%) was 40%, the isotactic index was 98.7%. Ta. Example 2 15g of propylene and 1.89g of methyl p-toluate
A preactivated catalyst was obtained in the same manner as in Example 1, except that instead of using a mixture of 9 g of propylene and 0.01 g of hydrogen sulfide, a mixed gas of 9 g of propylene and 0.01 g of hydrogen sulfide was fed. Reference Example 2 Instead of using 69 ml of the pre-activated catalyst slurry obtained in Example 1, 69 ml of the pre-activated catalyst slurry obtained in Example 2 (containing 0.40 g of the titanium trichloride composition and 2.48 g of the pre-activated catalyst) was used. ) was used in the same manner as in Example 1 to obtain 5.2 kg of polypropylene. The polymer yield per gram of titanium trichloride composition is
Even if the polymer slurry concentration is 38.3% at 13000g,
The isotactic index was 98.5%. Example 3 15 g of propylene and 1.89 g of methyl p-toluate
100 ml of n-hexane, instead of using a mixture of
A preactivated catalyst was obtained in the same manner as in Example 1, except that a solution consisting of 5 g of propylene and 0.01 g of triethylene glycol dimethyl ether was fed. Reference Example 3 Propylene polymerization was carried out in the same manner as in Example 1, except that 80 ml of the preactivated catalyst slurry obtained in Example 3 was used. The polymer yield per 1 g of titanium trichloride composition was 11,800 g, and the slurry concentration was
Even at 39%, the isotactic index is 99.2
It was %. Example 4 A mixed gas of 9 g of propylene and 0.01 g of hydrogen sulfide was fed, and after the feeding was finished, the mixture was stirred at 30°C for 3 hours to react, and then 0.01 g of diethylene glycol dimethyl ether was added. A preactivated catalyst was obtained. Reference Example 4 Propylene polymerization was carried out in the same manner as in Example 1, except that 80 ml of the preactivated catalyst slurry obtained in Example 4 was used. Even though the polymer yield per gram of titanium trichloride composition was 11,200g and the polymer slurry concentration was 36.9%, the isotactic index was
It was 99.4%. Example 5 A mixed gas of 9 g of propylene and 0.01 g of hydrogen sulfide was fed, and after the feeding was finished, the reaction was stirred at 30°C for 3 hours, and then 0.6 g of triethylaluminum was added.
g and 1.20 g of ethyl p-anisate in n-hexane.
A preactivated catalyst was obtained in the same manner as in Example 2, except that the reaction solution obtained by reacting for 2 hours at 25° C. in 50 ml was added. Reference Example 5 Propylene polymerization was carried out in the same manner as in Reference Example 1, except that 88 ml of the preactivated catalyst slurry obtained in Example 5 was used. The polymer yield per 1 g of the titanium trichloride composition was 14,800 g, and the isotactic index was 99.0% even though the polymer slurry concentration was 41%. Example 6 n-hexane 300ml, diethyl aluminum 4.8
g, titanium trichloride composition obtained in Example 1 (1) 3.0
After adding g, add propylene to 100ml of n-hexane.
6.0g, hydrogen sulfide 0.01g and diethylene glycol dimethyl ether were dissolved at 20℃ for 3 hours.
The reaction was carried out over a period of time, and after the reaction was completed, the mixture was further stirred for 4 hours to obtain a preactivated catalyst. Reference Example 6 Polymerization of propylene was carried out in the same manner as in Reference Example 1 except that 53 ml of the preactivated catalyst slurry obtained in Example 6 was used. The polymer yield per 1 g of the titanium trichloride composition was 12,300 g, and the isotactic index was 98.8% even though the polymer slurry concentration was 38%. Example 7 A preactivated catalyst was obtained in the same manner as in Example 6, except that 6.0 g of propylene, 0.01 g of hydrogen sulfide, and diethylene glycol dimethyl ether were reacted at 20°C for 3 hours, and then 0.5 g of methyl p-toluate was added. . Reference Example 7 Polymerization of propylene was carried out in the same manner as in Reference Example 1 except that 54 ml of the preactivated catalyst slurry obtained in Example 7 was used. The polymer yield per 1 g of the titanium trichloride composition was 11,400 g, and the isotactic index was 99.0% even when the polymer slurry concentration was 36%. Example 8 A solution of 0.60 mol of triethylaluminum in 2.0 mol of n-hexane and di-n-butyl ether
1.44 mol was mixed for 10 minutes and held at 40°C for 3 hours to obtain a reaction product liquid (2). 7.2 mol of titanium tetrachloride was placed in a reactor, kept at 18°C, and the above reaction product solution was added dropwise over 3 hours while stirring. After the dropwise addition was completed, it was kept at 18°C for 2 hours, and then kept at 65°C for another 2 hours. After that, the supernatant liquid was removed, and the solid product () was decantated three times with n-hexane 5.
I got g. Further, 500 ml of n-hexane, 342 g of diisoamyl ether, and 512 g of titanium tetrachloride were added to this, and the mixture was reacted at 75°C for 2 hours. After the reaction was completed, the mixture was filtered, and n-hexane (3) was added thereto, stirred, and filtered five times, followed by drying to obtain 326 g of a titanium trichloride composition (average particle size: 8.0 μm). A preactivated catalyst was obtained in the same manner as in Example 1 using 3.0 g of the above titanium trichloride composition. Reference Example 8 Polymerization of propylene was carried out in the same manner as in Reference Example 1, except that 68 ml of the preactivated catalyst slurry obtained in Example 8 was used. The polymer yield per gram of titanium trichloride composition was 13,800 g, the slurry concentration was 39%, and the isotactic index was 98.4%. The relationship between preactivation conditions and polymerization results for the above Examples and Reference Examples is shown in the table.

[Table] Example 9 (1) Production of titanium trichloride composition A stirring blade was attached to a reactor with an inner diameter of 180 m/m, a height of 220 m/m, and a semi-elliptical bottom and an internal volume of 5.
A solution of 0.83 mol of diethylaluminium monochloride (DEAC) dissolved in 1.17 mol of n-hexane and 1.99 mol of diisoamyl ether were mixed for 5 minutes,
Keep it at 35℃ for 1 hour to react and collect the reaction product liquid ()
(Molar ratio of diisoamyl ether/DEAC 2.40)
I got it. The reactor was replaced with nitrogen and titanium tetrachloride 7.47
mol, heated to 18℃, and stirred at 220rpm, the above reaction product solution () was heated to 18℃ for 1 hour.
It was added dropwise while keeping the temperature at °C. After dropping, heat at 18°C.
The mixture was maintained at 68° C. for an additional 1 hour, and then allowed to settle at the same temperature, and the supernatant liquid was removed. n-
After repeating the operation of adding 3 hexane and removing the supernatant liquid by decantation twice, 284 g of the obtained solid product () was suspended in 300 ml of n-hexane, and 493 g of titanium tetrachloride and diisoamyl ether were added.
274g was added and reacted at 65°C for 1 hour. After the reaction, the supernatant liquid was removed at 35°C, and the operation of adding n-hexane and washing in step 3 was repeated five times, and then dried under reduced pressure to obtain a titanium trichloride composition (average particle size).
7μ) 301g was obtained. (2) Preparation of preactivated catalyst After purging a stainless steel reactor with an internal volume of 100 mm with inclined blades with nitrogen gas, 50 mm of n-hexane,
660 g of diethylaluminium monochloride, 2.2 g of diethylene glycol dimethyl ether, 300 g of the titanium trichloride composition (average particle size 7 microns)
300g of propylene over 2 hours at 30°C.
g and 3 g of methyl p-toluate and 500 g of hexane
ml was reacted with stirring at 30° C. for 4 hours, and unreacted monomers were purged to obtain a preactivated catalyst. Reference Example 9 After purging a stainless steel reactor with internal volume 100 with inclined blades with nitrogen gas, 47 ml of n-hexane was charged, and 133 ml of the above preactivated catalyst was produced per hour.
(Titanium trichloride composition 0.8g, preactivated catalyst 4.2
), hexane 15, hydrogen 15, ethylene
A propylene-ethylene copolymer was produced at 60° C. and 13 kg/cm ² G by continuously feeding 0.28 kg of propylene and 11 kg of propylene. 11.2 kg of copolymer was continuously obtained per hour from the slurry discharged from the reactor. The polymer yield per gram of titanium trichloride composition is
Isotactic index is 98.5 at 14000g
It was %. Comparative Example 1 and Comparative Reference Example 1 A preactivated catalyst was obtained in the same manner as in Example 1 (2) except that 1.89 g of methyl p-toluate was not used, and propylene polymerization was carried out in the same manner as in Reference Example 1. Ivy. At a slurry concentration of 40%, the isotactic index was 96.2% and the polymer yield per gram of titanium trichloride composition was 9400 grams. Comparative Example 2 and Comparative Reference Example 2 15 g of propylene and 1.89 g of methyl p-toluate
Instead of using a mixture of 15 g of propylene and 30
After reacting at ℃ for 7 hours, 1.89 g of methyl p-toluate was added and reacted for 3 hours to obtain a preactivated catalyst. Polymerization of propylene was carried out in the same manner. At a slurry concentration of 40%, the isotactic index was 97.0% and the polymer yield per gram of titanium trichloride composition was 9800 g. Comparative Example 3 and Comparative Reference Example 3 Diethylene glycol dimethyl ether 0.022
Instead of using g, diethylene glycol dimethyl ether 0.022 g and methyl p-toluate
A preactivated catalyst was obtained in the same manner as in Example 1 (2) except that 1.89 g of propylene was used and only 15 g of propylene was fed, and propylene polymerization was carried out in the same manner as in Reference Example 1. At a slurry concentration of 40%, the isotactic index was 97.5% and the polymer yield per gram of titanium trichloride composition was 8900 g.

[Brief explanation of the drawing]

FIG. 1 is a flow sheet showing the manufacturing process of a preactivated catalyst according to the present invention.

Claims (1)

[Scope of Claims] 1 Titanium tetrachloride is reacted with (a) an organoaluminum compound or (b) a reaction product of an organoaluminum compound and an organic ether, and the solid obtained is reacted with an organic ether and titanium tetrachloride. α-olefin and one or more electron donors selected from organic ethers, hydrogen sulfide, or aromatic carboxylic acid esters are added to a catalyst formed by combining a titanium trichloride composition, which is a solid product, and an organoaluminum compound. A preactivated catalyst for α-olefin polymerization, which is obtained by simultaneously reacting or mixing the following. 2 The organoaluminum compound is a compound represented by the general formula AlRnR'n'X ₃ -(n+n') (wherein R and R' are alkyl, aryl, alkaryl, cycloalkyl, or alkoxy groups having 1 to 20 carbon atoms). , X represents fluorine, chlorine, bromine, or iodine, and n and n' represent arbitrary numbers of 0<n+n'3). catalyst. 3 α-olefin is a linear monoolefin having 2 to 10 carbon atoms, a branched monoolefin or diolefin having 4 to 10 carbon atoms, or one or more styrenes having 8 to 10 carbon atoms instead of α-olefin. α- according to claim 1, which is
Preactivated catalyst for olefin polymerization.