JPH0536444B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a method for advantageously producing an olefin-based polymer having a wide molecular weight distribution on an industrial scale by polymerizing olefin using a novel vanadium-based catalyst. In addition, in the following invention, the word "polymerization" may be used to include not only homopolymerization but also copolymerization, and the word "polymer" may be used to include not only homopolymer but also copolymer. be. There are many proposals regarding methods for carrying out olefin polymerization using a catalyst formed from a typical vanadium compound catalyst component such as vanadyl trihalide or vanadium tetrahalide and an organoaluminum compound catalyst component. The major drawbacks of this catalyst system are that the polymer yield per unit vanadium is not at a fully satisfactory level and the resulting olefinic polymer has a narrow molecular weight distribution. As a method for improving this drawback, several methods have been proposed in which organic halogen compounds are used in combination, and although some results have been achieved, they are still not satisfactory. In the specific examples of these proposals, vanadyl trichloride or vanadium tetrachloride is exclusively used as the vanadium compound, and lower alkyl aluminum halide is exclusively used as the organoaluminum compound. Furthermore, although several methods have been disclosed for supplying these catalyst components to the polymerization system, no particularly effective method has been found. Even if these conventionally known vanadium catalysts are used, it has not been possible to produce olefinic polymers, particularly olefinic polymers with a wide molecular weight distribution, in high yields. BACKGROUND OF THE INVENTION Conventionally, titanium-based catalysts have generally been used industrially to produce olefin-based polymers such as polyethylene. However, although this catalyst system has the advantage of high polymer yield per unit amount of catalyst and high activity, it has the disadvantage that the resulting polymer has a narrow molecular weight distribution, making it unsuitable for blow molding, film, and sheet molding. have. In view of the above-mentioned situation regarding catalysts for producing olefin-based polymers, the present inventors have developed a highly active vanadium-based catalyst that can industrially advantageously produce olefin-based polymers with a wide molecular weight distribution. As a result of intensive studies, it was discovered that the above object could be achieved by using an improved vanadium catalyst formed from a specific vanadium catalyst component, an organoaluminum compound catalyst component, and a halogen compound component, and the present invention was achieved. According to the present invention, when olefin polymerization is carried out using this improved vanadium-based catalyst, the yield of olefin-based polymer per unit amount of vanadium atoms is not only higher than that of conventional vanadium-based catalysts, but also the molecular weight distribution is It has the characteristic that a wide range of olefin-based polymers can be obtained, and furthermore, it has the characteristic that the molecular weight distribution is wider than that of conventional titanium-based catalysts. To summarize the present invention, the present invention comprises: (A) a vanadium catalyst component formed by contacting a magnesium compound, an electron donor, an organoaluminium compound, and a vanadium compound; (B) an organoaluminum compound catalyst component; The gist of the invention is a method of polymerizing or copolymerizing an olefin in the presence of a catalyst formed from: and (C) a halogen compound component. The catalyst component vanadium catalyst component (A) used in the process of the invention is a solid vanadium catalyst component formed by contacting a magnesium compound, an electron donor, an organoaluminum compound and a vanadium compound. The method of contacting each component when preparing the vanadium catalyst component (A) is not particularly limited, but the following method can be exemplified. (1) Bringing a vanadium compound into contact with a solid component obtained by further contacting an organoaluminum compound with an electron donor adduct of a magnesium compound produced by contacting a magnesium compound with an electron donor. Method. (2) A method of contacting a vanadium compound with an electron donor adduct of a magnesium compound produced by contacting a magnesium compound with an electron donor, and further contacting an organoaluminium compound. (3) A method of contacting a vanadium compound with a solid component produced by contacting a magnesium compound, an electron donor, and an organoaluminum compound. (4) A method of bringing an organic aluminum compound into contact with a component produced by contacting a magnesium compound, an electron donor, and a vanadium compound. (5) A method of contacting a mixture consisting of a magnesium compound, an electron donor, an organoaluminium compound, and a vanadium compound. Although it is possible to prepare the vanadium catalyst component that can be used in the method of the present invention by any of the methods described above, among these methods, adopting method (1) or (3) produces a highly active catalyst. It is preferable to use the method (1) because it can be obtained. The composition of each component supplied when preparing the vanadium catalyst component (A) is that the magnesium compound is usually in the range of 5 to 20 mol%, preferably 10 to 15 mol%, and the electron donor is usually in the range of 20 to 50 mol%. The organic aluminum compound is usually in the range of 40 to 70 mole%, preferably 50 to 60 mole%, and the vanadium compound is usually in the range of 0.5 to 5 mole%, preferably 1 to 40 mole%. It is in the range of 3 mol%. Further, the ratio of electron donor to magnesium compound when preparing the vanadium catalyst component (A) is usually 1 to 10 moles/1 gram atom, preferably 2 to 5 moles of electron donor per 1 gram atom of magnesium. The ratio of organoaluminum compound to magnesium compound is usually in the range of 2 to 20, preferably 3 to 6 as the ratio of aluminum atoms to magnesium atoms (Al/Mg), and the ratio of organoaluminum compound to magnesium compound is in the range of 2 to 20, preferably 3 to 6. The ratio of vanadium compounds is the ratio of vanadium atoms to magnesium atoms (V/
Mg) usually 0.025 to 1, preferably 0.05
to 0.3, and the ratio of vanadium compounds to organoaluminum compounds is the ratio of vanadium atoms to aluminum atoms (V/Al).
The ratio of the organoaluminum compound to the electron donor is usually 0.5 to 4.0 g atoms/mol, preferably 1 to 2 aluminum atoms per mole of the electron donor. It is in the range of gram atom/1 mole. When preparing the vanadium catalyst component, the above (1)
When forming an electron donor adduct of a magnesium compound by contacting the magnesium compound with an electron donor in method (2), the contact may be carried out in the absence of a solvent, or the adduct may be formed by contacting the magnesium compound with an electron donor. It can also be carried out in the presence of a solvent inert to the formation. The temperature during the formation of the adduct is usually 0 to 200°C, preferably 20 to 150°C. Furthermore, in the method (1) above, the temperature at which the organoaluminum compound is brought into contact with the electron donor adduct of the magnesium compound is usually in the range of -20°C to 150°C, preferably 0 to 100°C, and then The temperature during contact with the vanadium compound is usually -20 to 150°C, preferably 0 to 100°C.
is within the range of Preparation of the vanadium catalyst component (A) is preferably carried out in a hydrocarbon medium such as an aliphatic hydrocarbon, an alicyclic hydrocarbon, or an aromatic hydrocarbon. At that time, the electron donor adduct of the magnesium compound may be dissolved in the hydrocarbon medium or suspended as a solid component, but it does not matter whether it is in either state. . In either state, when an organoaluminum compound is brought into contact, a solid component is produced and becomes a suspension. By bringing a vanadium compound into contact with this suspension-like solid component, the vanadium catalyst component is
(A) is formed. Furthermore, in the method (2) above,
The temperature at which the vanadium compound is brought into contact with the electron donor adduct of the magnesium compound is usually in the range of 0 to 80°C, preferably 20 to 50°C,
Next, the temperature during contact with the organoaluminum compound is usually -20 to 150°C, preferably 0 to 100°C.
℃ range. In this case as well, the vanadium catalyst component is preferably prepared in a hydrocarbon medium as described above. At that time, when the electron donor adduct of the magnesium compound is in a solution, the component produced by contacting the vanadium compound is in a solution state, and when the electron donor adduct is in a suspension, The component produced by contacting with a vanadium compound is a solid component. In each case, the vanadium catalyst component which is then obtained by contacting the organoaluminum compound is a solid component. In the method (3) above, a magnesium compound,
The contacting of the electron donor and the organoaluminum compound is carried out as before in an inert medium, preferably in a hydrocarbon medium as before. The temperature during the contact is usually in the range -20 to 150°C, preferably 0 to 100°C, and the contact produces solid components in suspension. Furthermore, the contact of the vanadium compound to this suspension is usually at -20 to 150°C, preferably at 0.
It is carried out at temperatures between 100°C and 100°C. As a result, a solid vanadium catalyst component in suspension is obtained. In the method (4) above as well, the contact treatment is carried out in an inert catalyst as above, preferably in a hydrocarbon medium as above. The temperature during contacting of the magnesium compound, electron donor and vanadium compound is usually in the range of 0 to 80°C, preferably 20 to 50°C, and then the temperature during contacting of the organoaluminum compound is usually -20 to 150°C. , preferably 0
The temperature ranges from 100℃ to 100℃. This contact treatment yields a solid vanadium catalyst component in suspension. In the method (5) above as well, the contact treatment is carried out in an inert catalyst as above, preferably in a hydrocarbon medium as above. The temperature during contact of the magnesium compound, electron donor, organoaluminum compound and vanadium compound is usually -20 to 150°C;
Preferably it is in the range of 0 to 100°C. This contact treatment yields a solid vanadium catalyst component in suspension. To prepare the vanadium catalyst component, the magnesium compound, electron donor, organoaluminum compound and vanadium compound are used in each case in the proportions indicated above. When preparing the vanadium catalyst component, the electron donor and the organoaluminum compound react with each other and partially disappear, so that the electron donor component and the organoaluminum compound contained in the vanadium catalyst component after preparation are The content of is smaller than the content of each component supplied during preparation. The content of magnesium compound in the prepared vanadium catalyst component is usually in the range of 10 to 30% by weight, preferably 15 to 25% by weight, and the content of electron donor is usually in the range of 0 to 5% by weight, preferably 0 to 3%. weight%
The content of organoaluminum compounds is usually 0 to 10% by weight, preferably 0.5 to 5% by weight, and the content of vanadium compounds is usually 0.5 to 10% by weight, preferably 1 to 5% by weight. % range. In particular, it is preferable to use a vanadium catalyst component in which the electron donor content in the vanadium catalyst component is 3% by weight or less, particularly 2% by weight or less, since an olefinic polymer with a wide molecular weight distribution can be obtained. be. Although the structure of the vanadium catalyst is not clear,
It is a substance with a complex structure made up of components that interact with each other. The catalyst used in the method of the present invention is a catalyst formed by contacting the vanadium catalyst component (A), the organoaluminum compound catalyst component component (B), and the halogen compound component (C). It is. The feed ratio of each component forming the catalyst of the present invention is usually 1 gram atom of vanadium in the vanadium catalyst component (A) as aluminum atom in the organoaluminum compound catalyst component.
from 1000 to 1000 gram atoms, preferably from 10 to 200
gram atom range, also the vanadium catalyst component
The halogen atom in the halogen compound component (C) per 1 gram atom of vanadium in (A) is usually in the range of 1 to 5000 gram atom, preferably 10 to 500 gram atom. The catalyst of the present invention can be prepared by sequentially adding and contacting the halogen compound component (C) and the vanadium catalyst component (A) to the organoaluminum compound catalyst component (B); )
A method in which the organoaluminum compound catalyst component (B) and the halogen compound component (C) are sequentially added to and brought into contact with the vanadium catalyst component (A), the organoaluminum compound catalyst component (B) and the halogen compound component
Examples include a method of adding and contacting (C) at the same time, and a method of sequentially adding and contacting the halogen compound component (C) and the organoaluminum compound catalyst component (B) to the vanadium catalyst component (A). can. Among these preparation methods, it is preferable to employ the first method. Preparation is usually in an inert medium,
It is preferably carried out in a hydrocarbon medium such as an aliphatic hydrocarbon, an alicyclic hydrocarbon or an aromatic hydrocarbon. The temperature during preparation is usually 0 to 100℃,
Preferably it is in the range of 10 to 90°C. The catalyst of the invention prepared in a hydrocarbon medium is usually a solid component in suspension. Next, the constituent components of the catalyst used in the method of the present invention will be explained. The magnesium compound constituting the vanadium catalyst component (A) may be either a soluble or insoluble magnesium compound in the inert medium, and may also be an organic magnesium compound or an inorganic magnesium compound. good. Specific examples include magnesium halide, magnesium sulfate, magnesium nitrate, magnesium phosphate, magnesium carboxylate, dialkylmagnesium, diarylmagnesium, alkylmagnesium halide, alkylmagnesium alkoxide, dialkoxymagnesium, alkoxymagnesium halide, etc. can. More specifically, magnesium halides such as magnesium chloride, magnesium bromide, magnesium iodide, magnesium stearate,
Magnesium carboxylates such as magnesium oleate, diisobutylmagnesium, di-n-
Dialkylmagnesiums such as octylmagnesium, diarylmagnesiums such as diphenylmagnesium, ethylmagnesium chloride, n-butylmagnesium chloride, alkylmagnesium halides such as isodecylmagnesium, arylmagnesium halides such as phenylmagnesium chloride, n- Alkylmagnesium alkoxides such as butylmagnesium isopropoxide, isobutylmagnesium-2-ethyl-hexoxide, dialkoxymagnesiums such as di-n-octoxymagnesium, di-n-dodecyloxymagnesium, 2-ethylhexoxymagnesium chloride, oleyl Examples include alkoxymagnesium halides such as oxymagnesium chloride. When a magnesium compound formed from a magnesium compound and an electron donor component described below is used as the magnesium compound, the electron donor component may or may not be used again. The electron donor constituting the vanadium catalyst component (A) is usually a compound containing an oxygen atom or a nitrogen atom, such as alcohol, phenol, carboxylic acid, ester, aldehyde, ether, amine, amide, ketone, or phosphorus. Examples include acid esters, phosphorous esters, and carboxylic esters. More specifically, methanol, ethanol, n-propanol, isopropanol,
Aliphatic alcohols such as n-butanol, n-hexanol, n-octanol, 2-ethylhexanol, n-decanol, n-tetradecyl alcohol, oleyl alcohol, alicyclic alcohols such as cyclohexanol, methylcyclohexanol, benzyl Alcohol, aromatic alcohols such as methylbenzyl alcohol and isopropylbenzyl alcohol, aliphatic alcohols containing alkoxyl groups such as n-butyl cellosolve and 1-butoxy-2-propanol, caprylic acid, 2-ethylhexanoic acid, nonylic acid, and capric acid. acids, carboxylic acids such as undecylenic acid and oleic acid, aldehydes such as capryaldehyde, 2-ethylhexylaldehyde, decylaldehyde, and undecylaldehyde, di-n-hexyl ether, di-n-hexyl ether, di-n-octyl ether , di-n-decyl ether, di-n-
Ethers such as tridecyl ether, hexyl octyl ether, bis(1-octenyl) ether, bis(benzyl) ether, amines such as heptylamine, octylamine, nonylamine, decylamine, laurylamine, undecylamine, 2-ethylhexylamine, Examples include phosphite esters such as triethyl phosphite, tripropyl phosphite, and tributyl phosphite, and phosphoric esters such as triethyl phosphate, tripropyl phosphate, and tributyl phosphate. As the vanadium compound constituting the vanadium catalyst component, a vanadium compound having a valence of three or more is usually used. The vanadium compound has the general formula VO(OR)aXb or V(OR)cXd (wherein R is a hydrocarbon group, 0≦a≦3, 0≦b
≦3, 2≦a+b≦3, 0≦c≦4, 0≦d≦
4, 3≦c+d≦4) can be cited as a typical example. More specifically, _VOCl3 , VO( _OC2H5 ) _Cl2 , _VO
(OC ₂ H ₅ ) ₂ Cl, VO (Oiso C ₃ H ₇ ) Cl ₂ , VO (On−
_C4H9 ) _Cl2 , VO _{( OC2H5} ) _{3 , VOBr2} , _VCl4 ,
Examples include _VOCl2 and _VO (On- _C4H9 ) ₃ . In the method of the present invention, a compound having at least one Al-carbon bond in the molecule can be used as the organoaluminum compound or organoaluminum compound catalyst component (B) that is a component of the vanadium catalyst component (A). , for example, the following types of compounds can be mentioned: ( ⁱ ) General formula (R ¹ ) _{n Al} ( ^{OR 2} ) _o H _p
15 hydrocarbon groups, preferably 1 to 4 hydrocarbon groups, which may be the same or different from each other. X is halogen, m is 0≦m<3, n is 0≦n<3, p is 0
≦p<3, q is a number of 0≦q<3, and m+n+p+q=3), (ii) a general formula M ¹ Al(R ¹ ) ₄ (where, M ¹ is Li, Na or K, and R ¹ is the same as above), and complex alkylated products of Group 1 metal and aluminum can be mentioned. Examples of the organoaluminum compounds belonging to (i) above include the following. An organoaluminum compound represented by the general formula (R ¹ ) _n Al(OR ² ) _3-n (where R ¹ and R ² are the same as above. m is preferably a number of 1.5≦m<3) , an organoaluminum compound represented by the general formula (R ¹ ) _n AlX _3-n (where R ¹ is the same as above, X represents a halogen, and m is preferably 0<m<3), general An organoaluminum compound represented by the formula (R ¹ ) _n AlH _3-n (where R ¹ is the same as above. m is preferably 2≦m<3), a general formula (R ¹ ) _n Al( OR ² ) _o X _q (Here, R ¹ and R ² are the same as above.
3 and m+n+q=3). In the aluminum compound belonging to (i) above,
More specifically, trialkylaluminum such as triethylaluminum and tributylaluminium, trialkenylaluminum such as triisoprenylaluminum, alkylaluminum alkoxide such as diethylaluminum ethoxide, dibutylaluminum butoxide, ethylaluminum sesquiethoxide, butylaluminum Besides alkyl aluminum sesquialkoxides such as sesquibutoxide, partially alkoxylated alkylaluminums, diethylaluminum chloride, dibutyl aluminum with an average composition represented by the general formula (R ¹ ) _2.5 Al(OR ² ) _0.5 , etc. chloride, dialkyl aluminum halogenides such as diethyl aluminum bromide, ethyl aluminum sesquichloride, butyl aluminum sesquichloride, alkyl aluminum sesquihalogenides such as ethyl aluminum sesquibromide, ethyl aluminum dichloride, propyl aluminum dichloride, butyl aluminum dibromide, etc. partially halogenated alkyl aluminum, such as alkyl aluminum dihalogenide, diethylaluminum hydride,
Dialkyl aluminum hydrides such as dibutyl aluminum hydride, partially hydrogenated alkylaluminums such as alkyl aluminum dihydrides such as ethyl aluminum dihydride, propyl aluminum dihydride, ethyl aluminum ethoxy chloride, butyl aluminum butoxy chloride, ethyl aluminum ethoxy bromide partially alkoxylated and halogenated alkyl aluminums such as Also (i)
As a compound similar to , an organoaluminum compound in which two or more aluminum atoms are bonded via an oxygen atom or a nitrogen atom may be used. Examples of such compounds include (C ₂ H ₅ ) ₂ AlOAl(C ₂ H ₅ ) ₂ ,
( _C4H9 ) _{2AlOAl ( C4H9} ) _{2 ,}

[Formula] (C ₂ H ₅ ) ₂ can be exemplified. Further, these exemplified compounds may be mixed and used. Examples of compounds belonging to (ii) above include LiAl(C ₂ H ₅ ) ₄ and LiAl(C ₇ H ₁₅ ) ₄ . Among these, it is particularly preferable to use trialkyl aluminum and alkyl aluminum halide. Halogen compound (C) which is a catalyst component of the present invention
is an organic halogen compound or an inorganic halogen compound that can be converted into an organic halogen compound in a reaction system, such as halogenated hydrocarbons, halogen-containing carboxylic acid derivatives (esters, acid halides, etc.),
Examples include organic halogen compounds such as halogenated ketones and halogenated ethers, and inorganic halogen compounds that can be converted into organic halogen compounds in the reaction system, such as halogen molecules such as chlorine, bromine, and iodine. Furthermore, more specifically dichloromethane, trichloromethane, tetrachloromethane, dichloroethane, trichloroethane,
Tetrachloroethane, dichloropropane, trichloropropane, 1,4-dichlorobutane, tert-
Halogenated hydrocarbons such as butyl chloride, 2,3-dichlorobutane, chlorobenzene, benzotrichloride, hexachlorocyclopentadiene,
Methyl trichloroacetate, ethoxyethyl trichloroacetate, ethyl 2,3,4,4-tetrachloro-3-butenoate, 2,3,4,4-tetrachloro-
Examples include halogen-containing carboxylic acid derivatives such as methyl 2-butenoate, perchlorocrotonic acid chloride, and butyl perchlorocrotonate, and halogenated ketones such as hexachloroacetone. Among these halogen compounds, trichloromethane, dichloromethane, tetrachloroethane, tetrachloromethane and the like are particularly preferred. In the method of the present invention, the olefins used for polymerization include ethylene, propylene, 1-butene, 1-hexene, 1-octene, 4-methyl-
Examples include 1-pentene. These are used not only for homopolymerization, but also for random copolymerization and block copolymerization, and are utilized in the production of crystalline polymers and amorphous polymers. During copolymerization,
Conjugated dienes such as butadiene, dicyclopentadiene and 5-ethylidene-2-norbornene,
Polyunsaturated olefins such as non-conjugated dienes such as 1,7-octadiene may also be selected as copolymerization components. Polymerization can be carried out in the liquid phase. In liquid phase polymerization, an inert hydrocarbon such as hexane, heptane, or cyclohexane or the olefin itself to be polymerized can be used as a reaction medium, and polymerization can be carried out under conditions where the polymer is dissolved in the reaction medium. . The amount of each catalyst component to be used is usually 0.001 to 10 milligram atoms, especially 0.005 milligram atoms in terms of vanadium catalyst component (A) per reaction volume.
1 to 1 milligram atom of organoaluminium compound catalyst component (B), usually 1 to 1 milligram atom of aluminum per 1 gram atom of vanadium in component (A).
Preference is given to 1000 milligram atoms, especially 10 to 200 milligram atoms. The preferred amount of the halogen compound component (C) to be used varies depending on its type, but it is usually 1 to 5000 gram atoms, particularly 10 to 500 gram atoms, as a halogen atom per 1 gram atom of vanadium in component (A). It is desirable that the range be within the range of . In the method of the present invention, by polymerizing olefin in the presence of the vanadium catalyst,
In order to produce an olefin polymer, the polymerization reaction is usually carried out in the presence of hydrogen, and the ratio of hydrogen partial pressure in the gas phase/olefin partial pressure in the polymerization system is usually 0.05 to 3, preferably 0.15. It is in the range of 2 to 2. The temperature during the polymerization reaction is usually between 20 and
300°C, preferably in the range of 50 to 180°C.
In addition, the pressure during the polymerization reaction is normal pressure to 100Kg/
cm ² , preferably in the range of 2 to 50 kg/cm ² ,
Preferably, the polymerization reaction is carried out under pressurized conditions. Furthermore, the polymerization reaction can be carried out in any of the batch, semi-continuous and continuous methods. moreover,
It is also possible to carry out the polymerization reaction in multiple stages with different reaction conditions. Next, the present invention will be specifically explained using examples. Example 1 After slurrying 30 mmol of magnesium chloride with 30 ml of decane, 2-ethylhexyl alcohol was added.
90 mmol was added and the temperature was raised to 130°C to solubilize magnesium chloride. Add 300ml of decane to this and
Cool to ℃ and add triethylaluminum into it.
45 mmol was added dropwise. After the dropwise addition was completed, the temperature was raised to 90°C and maintained at this temperature for 2 hours. As a result of this operation, precipitation of solid was observed. Cool this slurry to room temperature and add 45% of ethylaluminum dichloride into it.
mmol was added dropwise, and the temperature was again raised to 90°C and kept at this temperature for 1 hour. Thereafter, the supernatant liquid was removed and the slurry was made into a slurry again using decane. After performing this operation twice, 200 ml of decane was added. Again, 45 mmol of ethylaluminum dichloride was added dropwise thereto, and the same operation as above was repeated. 3 mmol of vanadyl trichloride was added dropwise to the slurry thus obtained. After dropping, raise the temperature to 80℃, and at this temperature
It kept time. Thereafter, the solid product was collected by filtration and washed with decane until no free vanadium was detected in the washing solution, to obtain catalyst component (A). The remaining amount of 2-ethylhexyl alcohol in this catalyst component (A) was 0.24 wt%. (Polymerization) 1 part purified hexane in an autoclave with an internal volume of 2 parts.
, triisobutylaluminum 2.0 mmol,
1.0 mmol of trichloromethane, the above catalyst component (A)
After charging 0.02 mmol in terms of vanadium atoms, hydrogen gas was introduced and the pressure was increased to 1.5 Kg/cm ² gauge.
Thereafter, the temperature was raised to 80°C, ethylene gas was introduced, and the total pressure was set to 8 kg/cm ² gauge to initiate polymerization. Thereafter, only ethylene gas was supplied to maintain the total pressure at 8 kg/cm ² gauge, and polymerization was carried out for 2 hours. After polymerization,
The polymer slurry was filtered and dried under reduced pressure at 80° C. for a day and night. The yield of polymer was 150 g. The MFR of this polymer was 0.20, w/n=21.6. Examples 2 to 5, Comparative Example 1 Polymerization was carried out in exactly the same manner as in Example 1, except that the catalyst component produced in Example 1 was used and ethylene was polymerized under the stated polymerization conditions. Example 6 A catalyst was produced in the same manner as in Example 1 except that VCl ₄ was used instead of VOCl ₃ . Furthermore, ethylene polymerization was carried out in exactly the same manner as in Example 1. Example 7 After an autoclave with an internal volume of 3 was sufficiently purged with nitrogen, 1.5 ml of purified decane, 75 g of commercially available MgCl ₂ , 109 g of ethanol, and 10 g of Emazol 320 (manufactured by Kao Atlas Co., Ltd., sorbitan distearate) were added, and the system was stirred. The temperature was raised to 12°C and the mixture was stirred at 600 rpm for 20 minutes. The internal pressure of the system was set to 10 kg/cm ² gauge with nitrogen, and the tube of the SUS tube with an inner diameter of 3 mm, which was directly connected to the autoclave and kept at 125°C, was opened.
5 glass flask (with stirrer) filled with purified decane 3 pre-cooled to -15℃
The liquid was transferred to The amount of liquid transferred is 1, and the required time is 20
It was hot in seconds. The produced solid was collected by filtration and thoroughly washed with hexane. 50 mmol of the above solid (converted to magnesium atoms)
- A slurry was made with 200 ml of decane, cooled to 0°C, and 150 mmol was added dropwise over 30 minutes while maintaining this temperature. After the dropwise addition was completed, the mixture was kept at room temperature for 1 hour, then the temperature was raised to 90°C and kept at this temperature for 3 hours. Thereafter, this slurry was allowed to stand still, the supernatant liquid was removed, and the slurry was made into a slurry again using decane. After performing this operation twice, Deccan 200
Added ml. To this was added dropwise 75 mmol of ethylaluminum dichloride, and the temperature was again raised to 80°C and kept at this temperature for 1 hour. Thereafter, the same operation as above was repeated. 5 mmol of vanadyl trichloride was added dropwise to the slurry thus obtained. After the dropwise addition was completed, the temperature was raised to 80°C and maintained at this temperature for 1 hour. Thereafter, the solid product was collected by filtration and washed with decane until no free vanadium was detected in the washing solution, to obtain catalyst component (A). The remaining amount of ethanol in this catalyst component (A) was 1.9 wt%. (Polymerization) Polymerization was carried out in exactly the same manner as in Example 1, except that the hydrogen pressure was changed to 2 Kg/cm ² . Example 8 A catalyst was produced in exactly the same manner as in Example 7, except that the organic Al compounds listed in Table 1 were used. Furthermore, ethylene polymerization was carried out in exactly the same manner as in Example 7. Example 9 50 mmol of magnesium chloride was made into a slurry with 200 ml of decane, and 150 mmol of butyl cellosolve (C ₄ H ₉ O CH ₂ CH ₂ OH) was added dropwise into the slurry. The temperature was raised to 80°C, kept for 1 hour, then cooled to 0°C, and diethylaluminum chloride was poured into it.
150 mmol was added dropwise. After the dropwise addition was completed, the temperature was raised to 90°C and maintained at this temperature for 2 hours. Cool this to room temperature and add ethylaluminum dichloride into it.
100 mmol was added dropwise and the temperature was again raised to 90°C and kept at this temperature for 1 hour. Thereafter, the supernatant liquid was removed and the slurry was made into a slurry again using decane. After performing this operation twice, 200 ml of decane was added. 5 mmol of vanadyl trichloride was added dropwise to the slurry thus obtained. After the dropwise addition was completed, the temperature was raised to 80°C and maintained at this temperature for 1 hour. Thereafter, a solid product was collected by filtration and washed with decane until no free vanadium was detected in the washing solution, to obtain catalyst component (A).
The remaining amount of butyl cellosolve in this catalyst component (A) is
It was 0.52wt%. (Polymerization) Polymerization was carried out in exactly the same manner as in Example 1, except that the hydrogen pressure was 2 Kg/cm ² . Example 10 A catalyst was produced in exactly the same manner as in Example 9, except that tri-n-butyl phosphate was used instead of n-butyl cellosolve. Ethylene polymerization was also carried out in exactly the same manner as in Example 9. Example 11 To a solution prepared by diluting 50 mmol of ethylmagnesium chloride with 50 ml of tetrahydrofuran, 50 mmol of the obtained solution was added dropwise. At this time, the temperature was kept at 0°C. After the dropwise addition was completed, the temperature was raised to 50°C and the mixture was reacted for 1 hour. 300 ml of hexane was added to this solution to precipitate a solid. Take the solid product and add 200ml of decane to it.
was added to make a slurry. This was cooled to 0°C, and 75 mmol of ethylaluminum dichloride was added dropwise thereto. After the addition was completed, the temperature was raised to 90°C and maintained at this temperature for 1 hour. The above operation was repeated once again. The subsequent operations were carried out in the same manner as in Example 9. (Polymerization) The polymerization was carried out in exactly the same manner as in Example 9. These results are shown in Table 1. Comparative Example 2 In Example 1, catalyst component (A) was synthesized without using 2-ethylhexyl alcohol, and polymerization was carried out in the same manner as in Example 1 using this catalyst component. Polymer yield was 4.3g.

【table】

【table】 [Brief explanation of drawings]

FIG. 1 is a flowchart showing the manufacturing process of a catalyst according to the present invention.

Claims (1)

[Scope of Claims] 1 (A) A vanadium catalyst component formed by contacting a magnesium compound, an electron donor containing an oxygen atom, an organoaluminium compound, and a vanadium compound having a valence of 3 or more; (B) A method of polymerizing or copolymerizing an olefin in the presence of a catalyst formed from an organoaluminum compound catalyst component and (C) a halogenated hydrocarbon component.