KR820001966B1 - Method for producing -olefin polymers - Google Patents

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Description

How to prepare α-olefin polymer

The present invention relates to a method for producing a highly crystalline α-olefin polymer by a catalyst having a high activity. Various inventions using an electron donor as one component of a catalyst for α-olefin polymerization have been proposed. For example, MgCl ₂ (anhydrous), solids having Mg-Cl bonds, magnesium carbonate, oxides or hydroxides of elements of the II or Group VIII group of the periodic table are used as main components, and electron donors are used as one component. There is.

On the other hand, the present inventors support the transition metal compound by various methods on the solid product (I) obtained by reaction of a halide which is a trivalent metal and a compound of a divalent metal as a catalyst for ethylene or α-olefin polymerization. Have been developing a catalyst for use.

For example, 1) a method of using a solid product obtained by reacting a polysiloxane or an electron donor with the solid product (I) described above and then reacting a transition metal compound (Ko 52-13827 (Ko 49-994) 75/919), Atomic Components 52-127750) (2) A polysiloxane or an electron donor and a transition metal compound are simultaneously added to the solid product (1), or a complex of polysiloxane and transition metal compound prepared in advance. Or by adding a complex of an electron donor and a transition metal compound (Special Elements 53-21246, 53-21247, etc. 53-32031, etc.) ② React the transition metal compound to the solid product (I) described above. After the reaction of the trivalent metal alcoholate, the method of reacting the transition metal compound again (Japanese Patent Application Laid-Open No. 52-19790 (Japanese Patent Application No. 50-96247)) and the like have already been filed.

As a result of various studies on the improvement of these source inventions, the inventors found that the method of reacting the electron donor and the electron acceptor to the solid product (I) has a great difference in terms of effect. As a result of various studies, the present invention has been reached.

In other words, the present invention relates to a solid product (I) obtained by reacting a halide of a trivalent metal with a hydroxide, oxide, carbonate of a divalent metal, a double salt containing these, or a hydrate of a divalent metal compound. Either one or both of the electron acceptors of the phase and one or more electron acceptors are reacted in a plurality of times, and at least one of the electron acceptors is thydan tetrachloride, and thus the solid product (II) and the organoaluminum compound The present invention relates to a method for producing an α-olefin polymer, wherein the α-olefin is polymerized in the presence of a combined catalyst.

Below, the adjustment method of the catalyst used for the polymerization method of this invention is demonstrated in detail. First, the solid product (I) is obtained by reacting a halide of a trivalent metal with a divalent metal compound. As the halide of the trivalent metal, aluminum trichloride (anhydrous), aluminum trihydride (anhydrous), iron trichloride (anhydrous) and the like are used. As the divalent metal compound, for example, hydroxides such as Mg (OH) ₂ , Ca (OH) ₂ , Zn (OH) ₂ , Mn (OH) ₂ , oxides such as MgO, CaO, ZnO, MnO, MgAlO ₄ , Mg Complex oxide containing a divalent metal such as ₂ SiO ₄ Mg ₆ AlnO ₈ , MgCO ₃ , MnCO ₃ , MgCO ₃ . Carbonates such as CaCO ₃ , SnCl ₂ · 2H ₂ O, MgCl ₂ · nH ₂ O (n = 1 to 6), NiCI ₂ · 6H ₂ O, MnCl ₂ · 4H ₂ O, KMgCl ₃ · 6H ₂ O Halides such as halide hydrates, MgCl ₂ nMg (OH) ₂ mH ₂ O (n = 1 to 3, m = 1 to 6) and hydrates containing hydroxides, 3 MgO ₂ SiO ₂ 2H ₂ O and Hydrates are double salts of the same oxide, carbonates such as 3MgCO ₃ .Mg (OH) ₂ 3H ₂ O and hydrates are double salts of hydroxide, and divalent metals such as Ng ₆ Al ₂ (OH) ₁₆ CO ₃ 4H ₂ O And hydrates of carbonate hydroxide contained.

Solid product (I) is manufactured as follows. It is preferable that the trivalent metal halide and the divalent metal compound are pulverized for 5 to 50 hours as a bowl mill and for 1 to 10 hours as a vibration mill, and the mixture is sufficiently mixed. The mixing ratio of the divalent metal compound is usually 0.1 to 20 mol, with respect to 1 mol of the trivalent metal halide, and is preferably in the range of 1 to 10 mol. The reaction temperature is usually room temperature (20 ° C) to 500 ° C, preferably 50 ° C to 300 ° C. 30 minutes-50 hours are suitable, and when reaction temperature is low, it is made to react for a long time, and reaction is made to fully perform so that unreacted trivalent metal may not remain. The solid product thus obtained is referred to as solid product (I). The solid product (I) is then reacted with a dry donor (hereinafter abbreviated as ED) and an electron acceptor (hereinafter abbreviated as EA).

ED used in this reaction is an organic compound having an atom of any one of oxygen, nitrogen, sulfur and phosphorus, that is, alcohols, ethers, esters, aldehydes, fatty acids, ketones, nitriles, amines, isocyanates, azos Compounds, phosphines, phosphates, phosphinites, thioethers, thioalcohols, and polysiloxanes. Specific examples include methanol, ethane, propanol, butanol, pentanol, hexanol, octanol, phenol, cresol, chisylenol, ethylphenol, naphthol, cumyl alcohol, diethyl ether, di n-propyl ether, di n-butyl Ethers such as ether, di i-amyl ether, di n-pentyl ether, di n-hexyl ether, di n-octyl ether, di i-octyl ether, ethylene glycol monomethyl ether, diphenyl ether and tetrahydrofuran , Ethyl acetate, butyl formate, amyl acetate, vinyl butyrate, vinyl acetate, methyl benzoate, ethyl benzoate, propyl benzoate, butyl benzoate, octyl benzoate, 2-ethylhexyl benzoate, methyl toluate, ethyl toluate, 2-ethyl toluate Esters such as hexyl, ethyl aniseate, propyl aniseate, ethyl cinnamon, naphthoate methyl, ethyl naphthoate, propyl naphthoate, butyl naphthoate, 2-ethylhexyl naphthoate, ethyl phenylate , Acetoaldehyde Aldehydes such as aldehyde, benzaldehyde, formic acid, acetic acid, propionic acid, butyric acid, fish acid, succinic acid, acrylic acid, fatty acids such as maleic acid, benzoic acid, ketones such as methyl ethyl ketone, methyl isobutyl ketone benzophenone, and nitriles such as acetnitrile. , Amines such as methylamine, diethylamine, tributylamine, triethanolamine, pyridine and aniline, isocyanates such as phenyl isocyanate and toluyl isocyanate, azo compounds such as azobenzene, ethyl phosphine triethyl phosphine, tri n- Phosphines such as butyl phosphine, tri n-octylphosphine, triphenylphosphine, dimethyl phosphite, di n-octyl phosphite, tri n-butyl phosphite, phosphites such as tri n-butyl phosphite, and ethyl di Phosphinites such as ethyl phosphite, ethyl dibutyl phosphite and phenyl diphenyl phosphite, diethylthio ether, diphenylthio ether, and Thioethers such as butylphenylthioether, ethylene sulfide and propylene sulfide, thioalcohols such as ethylthioalcohol, n-propylthioalcohol and thiophenol can be cited. Moreover, as polysiloxane, general formula

A chain (鎖 狀 (or cyclic siloxane polymer is used), and R ₁ , R ₂ is a hydrocarbon residue such as hydrogen, alkyl group, halogen, alkoxy group or aryloxy group, fatty acid residue, etc. In general, those in which two or more kinds are distributed and bound in a molecule in various ratios are generally used.

Usually, as a specific example of what is preferably used, Lower polymers, such as octamethyl trisiloxane octaethyl cyclotetrasiloxane, Alkyl siloxane polymers, such as dimethyl polysiloxane, ethyl polycyclosiloxane, and methyl ethyl polysiloxane, hexaphenyl cyclotrisiloxane, di Aryl siloxane polymers, such as phenyl polysiloxane, Alkyl aryl silicate polymers, such as diphenyl octamethyl tetrasiloxane and methylphenyl polysiloxane, etc. can be mentioned. These various polysiloxanes can also be mixed and used. Moreover, it is important that these polysiloxanes are in a liquid state at the time of reaction, and it is necessary that the polysiloxane itself is in a liquid state under reaction conditions or dissolved in a solvent. The viscosity of such polysiloxane is in the range of 10 to 10,000 centistokes at 25 ° C, more preferably 10 to 2,000 centistokes.

Various ED as mentioned above can be used not only individually but in mixture of various things.

Next, EA used in this invention is represented as a halide of the element of group III-V of a periodic table. Specific examples include AlCl ₃ (anhydrous), SiCl ₄ , SnCl ₂ , SnCl ₄ , TiCl ₄ , ZrCl ₄ , PCl ₃ , PCl ₅ , VCl ₄ , SbCl ₅ , SCl ₂ , NnCl ₂ , FeCl ₂ , NiCl _2, etc. Can be. You may mix and use these. However, TiCl ₄ must be used only once.

There are various methods of reacting ED and EA to the solid product (I), as described below. However, in any reaction step, the solid product (I) may be suspended in the presence or absence of a solvent. The reaction may be performed while grinding using a grinder.

At the time of reacting ED and EA to the solid product (I), either or both of them are reacted in a plurality of times. Furthermore, the ED and EA may be plural kinds, but at least one of the EA is titanium tetrachloride. Although it is an important feature in this invention, the following method is mentioned as a specific or representative thing of the reaction order.

① Method of reacting EA ₂ (TiCl ₄ ) after ED and EA ₁ reaction to solid product (I)

② Method of reacting ED and EA ₂ (TiCl ₄ ) once or twice after EA ₁ is reacted with solid product (I).

③ ED ₁ and EA ₁ reaction to the solid product (1), this time a method of reacting ED ₂ and EA ₂ (TiCl ₄ ).

④ ED ₁ and EA (TiCl ₄ ) are reacted with the solid product (I), followed by ED ₂ .

⑤ After the reaction method of the ED ₁ in the solid product (I), reacting a ₂ ED and EA (TiCl ₄₎

⑥ After ED ₁ is reacted with solid product (I), ED ₂ is reacted and EA (TiCl 4) is reacted once or twice.

⑦ After ED ₁ is reacted with solid product (I), ED ₂ is reacted and ED ₃ is reacted with EA (TiCl ₄ ) again.

⑧ After ED reaction with solid product (I), EA (TiCl ₄ ) reaction twice

⑨ After reacting ED with solid product (I), EA ₁ is reacted, and EA ₂ (TiCl ₄ ) is reacted again.

As described above, reacting one or both of ED and EA by dividing into a plurality of times generally means dividing ED or EA into two or three times each, and even finer division further complicates the operation while increasing the effect. Do not. In the state of the reaction described above, for example, the reaction of ED and EA to the solid product (I) means the reaction in the presence of the solid product (I) and ED and EA, or the solid product (I), ED, and EA. It means any of the reaction with the complex compound. A solvent may be added as needed at any time of these reactions, and the solvent used may be n-pentane, n-hexane, n-heptane, n-octane, i-octane, n-nonane, n-decane, or the like. Aliphatic hydrocarbons such as aliphatic hydrocarbons, benzene, toluene, xylene, ethylbenzene, cumene, carbon tetrachloride, chloroform, dichloroethane, trichloroethylene, tetrachloroethylene, tetrafluorocarbons, coolobenzene, ortho (ortho) It is a so-called inert solvent, such as halogenated hydrocarbons, such as dichlorobenzene.

The amount of ED, EA, and solvent used is preferably in the range of 1 to 5,000 g of ED, 1 to 5,000 g of EA, and 0 to 5,000 ml of solvent based on 100 g of solid product (I) in each reaction step.

The reaction conditions are from 0 to 500 ° C, preferably from 20 to 200 ° C, in the reaction stages of the respective reaction stages. The reaction time varies depending on the reaction method, and the reaction in suspension is 1 minute to 10 hours, grinder. Reaction by is about 5 to 200 hours as a bowl mill and about 10 minutes to 50 hours as a vibration mill.

After completion of the reaction, the unreacted reaction solution containing ED or EA is removed by reduced pressure or atmospheric pressure, or separated by filtration or decantation, and then washed and dried as a solvent if necessary. To obtain a solid product (II). In this case, it may be used in the next reaction without being separated as a solid and leaving it as it is in the suspended phase as it is added. Moreover, it is most preferable to remove unreacted material etc. for each reaction step.

The solid product (II) thus obtained is then combined with an organoaluminum compound to serve as a catalyst for α-olefin polymerization.

The organoaluminum compound used in this reaction represents a general formula AlRnR'n'X _3- (n + n '), wherein R and R' represent a hydrocarbon group or an alkoxy group such as an alkyl group, an aryl group, an alkylyl group or a cycloalkyl group. , X represents a halogen which is fluorine, chlorine, cancellation and oxo, and n, n 'represents an arbitrary number of O <n + n' ≤ 3), and specific examples thereof include trimethylaluminum and triethyl Aluminum, tri n-propylaluminum, tri n-butylaluminum, tri i-butylaluminum, tri n-hexyl aluminum, tri i-hexyl aluminum, tri 2-methylpentyl aluminum, tri n-octyl aluminum, tri n-decyl aluminum Trialkylaluminum, leuthiethylaluminum monochloride, di n-propylaluminum monochloride, di i-butylaluminum monochloride, diethylaluminum monofluoride diethylaluminum monobromide, diethylaluminum Alkyl aluminum hydrides, such as diethyl aluminum monohalide tube, such as mono iodide, and diethyl aluminum hydride, methyl aluminum sesquichloride, ethyl aluminum sesquichloride, ethyl aluminum dichloride, i-butyl aluminum dichloride, etc. Alkyl aluminum halides, and the like, and alkoxy alkyl aluminums such as monoethoxydiethyl aluminum and diethoxy monoethyl aluminum may also be used.

The amount ratio between these organoaluminum compounds and the solid product (II) is in the range of 50 to 5,000 g of the organoaluminum compound with respect to 100 g of the solid product (II), and is immediately mixed by mixing both in an inert gas. It has an activity as a polymerization catalyst of? -olefin, and can be used in the same manner as a conventional Ziegler and Natta type catalyst.

The polymerization reaction may be carried out in liquefied α-olefin monomers such as liquefied propylene and liquefied butene-1, in addition to being carried out in hydrocarbon solvents such as n-hexane, n-heptane, n-octane, benzene and toluene, without using a solvent. . The polymerization temperature is room temperature (20 °) to 200 ° C, and the polymerization pressure is normal pressure (0 kg / cm ² G) to 50 kg / cm ² G, which is usually performed for about 5 minutes to 10 hours. At the time of polymerization, adding an appropriate amount of hydrogen for molecular weight control is the same as in the conventional polymerization method.

) 모노올레핀류, 부타디엔, 이소프렌, 클로로프렌 등의 디올레핀류, 스틸렌 등이며, 본 발명의 방법에서 이들 제각기의 단독중합뿐 만이 아니고 상호간에 다른 α-올레핀과 조합하여, 예를들면 프로필렌과 에틸렌, 부텐-1과 에틸렌, 프로필렌과 부텐-1과 같이 조합(組合)하여 공중합을 행하게 할 수도 있다.Α-olefins provided for use in the process of the present invention are linear monoolefins such as ethylene, propylene, butene-1, hexene-1, octene-1, decene-1, 4-methyl-pentene-1, 2- Branched chains such as methyl-pentene-1 and 3-methylbutene-1 (

) Diolefins such as monoolefins, butadiene, isoprene, chloroprene, styrene, and the like, in the process of the present invention, not only homopolymerization of these groups, but also in combination with other α-olefins, for example, propylene and ethylene, Copolymerization may be performed in combination with butene-1 and ethylene and propylene and butene-1.

The 1st effect obtained by the polymerization method of this invention is that the highly crystalline alpha-olefin polymer is obtained in manufacture of the polymer of alpha-olefin. For example, in the production of the polymer of propylene, in the method according to the inventors described above, the isotactic polypropylene content, which is crystalline as a normal heptane insoluble, was 75-96%. In the invention, it is improved to about 92 to 97%.

The second effect of the present invention is the fact that the shape of the polymer of propylene is improved in particular. In the method according to the present invention of the present inventors, the shape of the particles of the ethylene polymer was good and reached up to 0.45 in the apparent specific gravity (BD) of the accumulation, but in the propylene polymer, the shape was bad, and it was 0.08 to BD. It was only 0.18 and had no particles. In the present invention, BD has reached 0.35, and the particle shape is also improved to be almost spherical.

)시킨다든지하는 나쁜 영향이 보이지 않았다는 사실이다.The third effect of the present invention is that the amount of the α-olefin polymer per solid product (II) is sufficiently high, and in particular, in the polymerization of propylene, 5 × 10 ³ to 2 × 10 as a general polymerization condition. ₄ g (polymer) / g (solid product (II)), and even if the removal of the remaining catalyst in the polymer, that is, the deliming step, was omitted, the polymer was not colored and the physical properties of the polymer were damaged. Molds during the molding of polymers or

The fact that there was no bad effect of letting it go.

The fourth effect of the present invention is the fact that the transition metal is very effectively used, and it is 1 × 10 ^{4 to} 5 × 60 ⁶ g (polymer) / g (transition metal atom) as a polymerization of a typical propylene. Will. EMBODIMENT OF THE INVENTION Hereinafter, this invention is demonstrated in detail as an Example is shown.

Example 1

(1) Preparation of (II) of Solid Product (I)

When 80 g of aluminum trichloride (anhydrous) and 58 g of magnesium hydroxide were pulverized at 180 ° C. for 10 hours, the reaction was carried out with the generation of hydrogen chloride gas. After completion of heating, the mixture was cooled in a nitrogen stream to obtain a solid product (I).

In a vibrating mill, 100 g of solid product (I) and 20 g of titanium tetrachloride which were EA were added, and reacted while pulverizing at 120 ° C. for 5 hours, and under reduced pressure, unreacted titanium tetrachloride was removed and cooled.

Again, 12.0 g of a complex of titanium tetrachloride and ethyl benzoate as ED [1: 1 (molar ratio, equal to or less)] was added, and the reaction was carried out while grinding at 40 DEG C for 120 hours using a vibrating mill, and the solid product (II) was added. Got it. The content of titanium atom in 1 g of solid product (II) was 19.5 mg.

(2) Preparation of Propylene Polymer

또, 얻어진 폴리머의 BD는 0.35이며, 형상은 대폭적으로 개성되고 있었다. 결과는, 종합하여 다른 실시예와 함께 제1표에 나타냄.After replacing the 1.5 liter stainless steel reactor with nitrogen gas, 1 liter of n-hexane, 480 mg of triisobutylaluminum, and 12 mg of solid product (II) obtained in the above-mentioned (I) were added, and 75 ml of hydrogen and 12 kg of propylene partial pressure were added. The polymerization reaction of propylene was carried out at 60 ° C. for 5 hours as cm 2 G. After the completion of the polymerization reaction, the solvent was evaporated to remove the polymer. 5 g of the obtained polymer was extracted with a boiling point (98 ° C.) of n-heptane using a Soxhlet extractor using 50 ml of n-heptane, the n-heptane soluble component was made into atactic flopylene, and the rest of the It was set as tactic polypropylene. Isotactic index was obtained as follows. Isotactic

Moreover, BD of the obtained polymer was 0.35 and the shape was largely individualized. The results are collectively shown in the first table together with the other examples.

Example 2

Into a ball mill (made of SUS 304) having a diameter of 100 mm and a volume of 785 ml, 80 stainless spheres having a diameter of 10 mm were placed, and 20 g of solid product (I) obtained in Example 1, 3 g of silicon tetrachloride as EA ₁ , ED 4.0 g of ethyl cinnamon was added thereto, followed by reaction while grinding at 40 ° C. for 75 hours. After completion of the reaction, after removing the unreacted substances a reduced pressure, and the titanium tetrachloride as EA ₂ Put 80g, it was going again, 40 hours milling a 80 ℃ reaction. After completion of the reaction, in a nitrogen-substituted dry box, the product was filtered off, washed three times with 50 ml of n-hexane I, and dried to obtain solid product (II).

Propylene was polymerized in the same manner as in Example 1 using solid product (II). Results shown in Table 1

Example 3

After adding 3 g of aluminum trichloride as EA ₁ and 1.7 g of dimethylpolysiloxane as ED _{1 to} a bowl mill, a complex obtained by mixing and adding 20 g of solid product (I) as in Example 1 was further pulverized at 30 ° C. for 48 hours. , 8 g of a tetrahydrofuran complex (1: 2) as titanium tetrachloride as EA ₂ and ED ₂ were added, and the resultant was further subjected to pulverization reaction at 50 ° C. for 60 hours to obtain a solid product (II).

Using this solid product (II), propylene polymerization was conducted in the same manner as in Example 1. Results shown in Table 1

Example 4

80 g of aluminum trichloride (anhydrous) and 30 g of magnesium oxide were pulverized for 48 hours at 120 ° C. with a bowl mill to react to obtain a solid product (I).

After reacting 20 g of a solid product (I) with 5 g of a complex (1: 1) of titanium tetrachloride (EA) and phenyl acetic acid (ED) with a vibrating mill while grinding for 30 minutes at room temperature (20 ° C.), It was suspended in the mixed solution of 50 ml of n-haptan and 180 g of titanium tetrachloride, and reacted at 100 degreeC for 4 hours. After completion of the reaction, the solid product (II) was obtained by filtration in a dry box, washing with 150 ml of n-hexane three times, and drying.

Propylene was polymerized in the same manner as in Example 1 using solid product (II). The results are shown in the first table.

Example 5

60 g of aluminum trichloride (anhydrous) and 20 g of hydrotalcite (Mg ₆ Al ₂ (OH) ₁₆ CO ₃ .4H ₂ O) were heated at 100 ° C. for 2 hours, 40 g using a vibration mill, at 1,250 ° C. The solid product (I) was obtained by time pulverizing and reacting. In 200 ml of n-hexane, 20 ml of methylhydrogen polysiloxane and 50 g of the above-mentioned solid product (I) were added as ED ₁ , reacted at 40 ° C for 1 hour, filtered, washed with n-hexane and dried.

To 20 g of this dry solid, 3 g of methyl toluate as ED ₂ and 6 g of titanium tetrachloride as EA were placed in a bowl mill, and after 20 hours of grinding reaction at 80 ° C., the mixture was kept at 80 ° C. under reduced pressure for 2 hours to remove unreacted product. , Solid product (II) was obtained.

Propylene was polymerized in the same manner as in Example 1 using solid product (II). The results are shown in Table 1.

Example 6

60 g of iron trichloride (anhydrous) and 70 g of aluminum magnesium oxide (MgAl ₂ O ₄ ) were reacted in a vibration mill at 320 ° C. for 5 hours to obtain a solid product (I).

20 g of solid product (II) was suspended in 180 ml of toluene, 10 g of ethanol was added as ED ₁ , and after 1 hour of reaction at 30 ° C., 150 ml of toluene was added to decantation twice. After making the total amount 180 ml, 8 g of benzophenone was added as ED ₂ , reacted at 60 ° C. for 30 minutes, then decanted, decanted by adding 150 ml toluene, and the total amount was 60 ml. 100 ml of titanium tetrachloride, EA, ED _3-di n- butyl ether was added to 20m工, after 1 h at 130 ℃, separated by filtration, washed with n- hexane to give a solid product (ⅱ) by drying.

Propylene was polymerized in the same manner as in Example 1 using solid product (II). The results are shown in Table 1.

Example 7

80 g of aluminum trichloride (anhydrous) and magnesium chloride (hexahydrate) (MgCl ₂ · 6H ₂ O) 65

g was reacted while pulverizing at 80 DEG C for 20 hours in a vibration mill to obtain a solid product (I).

3 g of n-butyl ether (ED ₁ ) was added to 20 g of the solid product (I) and reacted for 30 minutes at 40 ° C., followed by 2 g of benzoic acid (ED2), followed by reaction at 60 ° C. for 30 minutes. This was suspended in a mixed solution of 120 g of titanium tetrachloride and 30 ml of n-hexane, and reacted at 75 ° C for 3 hours. After the completion of the reaction, the unreacted product was ligated under reduced pressure to obtain a solid product (II).

Using the solid product (II), propylene was polymerized in the same manner as in Example 1. The results are shown in Table 1.

Comparative Example 1

The same experiment as in Example 1 was carried out except that the solid product (I) and the titanium tetrachloride reacted in two separate portions were simultaneously reacted.

That is, 100 g of solid product (I) obtained in Example 1, 20 g of titanium tetrachloride, and 12 g of a complex of titanium tetrachloride and ethyl benzoate (1: 1) were mixed at the same time. After the reaction was carried out while pulverizing at 40 ° C. for 120 hours, unreacted titanium tetrachloride was removed under reduced pressure to obtain a solid product (II). This solid product (II) was used, and propylene was then integrated in the same manner as in Example 1. As shown in the first table, the results are much inferior to those in Example 1 in terms of polymer amount, isotactic index, and BD.

Comparative Example 2

In Example 6, the same experiment as in Example 6 was conducted except that the solid product (I) was reacted by dividing three kinds of ED three times.

That is, 200 g of solid product (I) as obtained in Example 6 was suspended in 180 ml of toluene and added simultaneously with 10 g of ethanol, 8 g of benzophenone, 100 ml of titanium tetrachloride, and 20 ml of di-n butyl ether, and 1 hour at 30 ° C. After reacting at 130 degreeC for 30 minutes at 130 degreeC for 1 hour, it filtered, washed with n-hexane, and dried, and obtained solid product (II).

Propylene was polymerized in the same manner as in Example 6 except that this solid product (II) was used. The results are shown in the first table, but it is clear that even in this case, the results are much inferior to that of the sixth embodiment in all cases.

[Table 1]

Example 8

Propylene-ethylene was copolymerized using the solid product (II) obtained in Example 1.

Into a polymerization vessel, 80 mg of hydrogen was added using 10 mg of solid product (II) as obtained in Example 1 and 420 mg of triethyl aluminum, and fed eight times at a polymerization temperature of 60 ° C. every 10 minutes at 10 g of ethylene. In the course of this, the polymerization reaction was carried out at a propylene partial pressure of 10 kg / cm 2 for 4 hours. After the reaction, a propylene-ethylene copolymer was obtained through the same operation as in Example 1. The polymer yield per 1 g of solid product (II) was 20,800 g (polymer), and the isotactic index was 92.0.

Example 9

In the same manner as in Example 8, copolymerization of propylene-butene-1 was performed.

Instead of using ethylene in Example 8, except for using butene-120 g, propylene-butene-1 copolymerization was performed in the same manner as in Example 8. The polymer yield per 1 g of solid product (II) was 20,300 g (polymer), and the isotactic index was 91.0.

Example 10

Ethylene was polymerized using the solid product (II) obtained in Example 2.

Using 8 mg of solid product (II) obtained in Example 2 and 480 mg of triisobutyl aluminum, the polymerization reaction was carried out at a hydrogen partial pressure of 5 kg / 2 cm 2 G, an ethylene partial pressure of 5 kg / cm 2 and 85 ° C. for 5 hours. After completion of the reaction, the polymer was obtained in the same manner as in Example 1. The polymer yield was 18,800 g (polymer) / g (solid product (II)). BD was 0.40 and MI was 6.5.

Example 11

The polymerization of butene-1 was carried out using solid product (II) obtained in Example 3.

02 g of solid product (II) obtained in Example 3 and 380 mg of triethylaluminum were used at 70 ° C. for 4 hours to feed 480 g of butene-1 continuously, followed by further polymerization for 2 hours. After completion of the reaction, the solvent was dried and 2.73 g of polybutene was obtained. The polymer yield was 13,650 g (polymer) / g (solid product (II)).

Example 12

133 g of aluminum trichloride (anhydrous) and 40 g of magnesium oxide were pulverized with a bowl mill for 24 hours, heated at 120 ° C. for 2 hours, cooled, and further ground for 10 hours to obtain a solid product (I).

12 g of ethyl benzoate (ED) and 4.5 g of silicon tetrachloride (EA ₁ ) were mixed at room temperature (20 ° C.), and 40 g of solid product (I) were pulverized at 35 ° C. for 48 hours with a boil mill, 20 g of the obtained powder was suspended in 180 g of titanium tetrachloride (EA ₂ ), and after reacting at 80 ° C. for 2 hours, the upper clear solution was removed as decant, followed by 180 g of titanium tetrachloride. Was added and after 1 hour of reaction at 80 ° C., the clear upper liquid was removed as decant. 150 ml of n-hexane was added, and the operation of removing the cananthrosi was half-normized, followed by filtration and drying in a dry box to obtain a solid product (II).

Using this solid product (II), propylene was polymerized in the same manner as in Example 1. The results are shown in the first table.

Example 13

To 20 g of solid product (I) obtained by the same operation as in Example 12, 2 g of cumyl alcohol (ED ₁ ) and 5 g of ethyl benzoate (ED ₂ ) were pulverized at 40 ° C. for 48 hours as a bromyl, followed by tetrachloride. 9 g of silicon (EA ₁ ) was added thereto, and 20 g of the powder obtained by pulverization reaction as a bowl mill was further suspended in 240 g of titanium tetrachloride (EA2), and reacted at 100 ° C. for 2 hours, and then the clear liquid was removed as decant. Then, 150 ml of n-hexane was added, and the operation of removing the upper clear liquid was repeated twice, followed by filtration in a dry box and drying to obtain a solid product (II). Using this solid product (II), propylene was polymerized in the same manner as in Example 1. The results are shown in Table 1.

Example 14

After 40 g of the solid product (I) obtained in the same manner as in Example 12, 12 g of methyl benzoate (ED ₁ ) was pulverized at a temperature of 30 ° C. for 24 hours, followed by 15 g of silicon tetrachloride (EA ₁ ), followed by 48 hours. After 20 g of the powder obtained by the reaction is suspended in 350 g of titanium tetrachloride (EA ₂ ), the reaction is carried out at 80 ° C. for 2 hours, and the upper clear solution is removed as decant and 200 ml of tetrachloroethylene is added to decant. Then, 200 ml of n-hexane was added, and the operation of decanting was repeated twice, and then a solid product (II) was obtained by subjecting n-hexane to reduced pressure under reduced pressure.

Propylene was polymerized in the same manner as in Example 1 using the solid product (II). The results are shown in Table 1.

Example 15

20 g of the powder obtained by pulverizing and reacting 16 g of benzoic acid i-propyl (ED ₁ ) at 45 ° C. for 48 hours with a bor mill in 40 g of the solid product (I) obtained by the same operation as in Example 12 was suspended in 190 g of titanium tetrachloride (EA). After 4 hours of reaction at 70 DEG C, the reaction solution is separated and separated by filtration, and the obtained solid is suspended again in 220 g of titanium tetrachloride. After the reaction at 90 DEG C for 1 hour, the reaction solution is removed as decant. 250 ml of n-hexane was added, and the operation of decanting was repeated twice, and the solid product (n) was obtained by distilling n-hexane under reduced pressure.

Propylene was polymerized in the same manner as in Example 1 using the solid product (II). The results are shown in Table 1.

Example 16

12 mg of solid product (II) obtained in Example 12 and 480 mg of triisobutyl aluminum were suspended in 500 g of propylene without solvent, 90 ml of hydrogen was added, and polymerization was carried out at a polymerization temperature of 65 ° C. under a pressure of 26,5 kg / cm 2 G for 3 hours. The reaction was carried out. After the completion of the polymerization reaction, the remaining propylene was removed to obtain 58 g of propylene polymer. The polymer yield per 1 g of solid product (II) was 13,170 g, the polymer yield per 1 g of titanium atom was 0.69 × 10 ^6, and the isotactic index 92.0, polymer BD 0.30, and MFR were 4.8.

Claims (1)

The solid product (I) obtained by reacting a halide of a trivalent metal with a hydroxide, oxide, carbonate, a double salt containing these, or a hydroxide of a divalent metal compound, at least one electron donor and at least one species In obtaining the solid product (II) by reacting the electron acceptor, at least one of the electron donor or the electron acceptor is reacted by dividing one or both times several times, moreover, at least one of the electron acceptor is titanium tetrachloride and the solid product thus obtained ( A method for producing an α-olefin polymer characterized by polymerizing an α-olefin in the presence of a catalyst combining II) and an organoaluminum compound.