JPH072790B2 - Method for producing α-olefin polymer - Google Patents

Description

Description: TECHNICAL FIELD The present invention relates to a novel method for producing an α-olefin polymer. More specifically, the present invention relates to a method for producing the polymer using a supported Ziegler-Natta catalyst, wherein the carrier is a compound represented by the general formula AlX ₃ (X is a halogen) and Mg (OH) ₂ Alternatively, the solid product (I) obtained by the reaction with MgO, the titanate ester and the aliphatic alcohol are dissolved in an inert hydrocarbon solvent, and the resulting solution is represented by the general formula SiX ₄ (X is a halogen). Using a solid product (II) obtained by mixing and reacting the compound described above with an aromatic dicarboxylic acid diester, the solid product (II) is reacted with a compound represented by the general formula TiX ₄ (X is a halogen). When at least the aromatic dicarboxylic acid diester is not used in the reaction for producing the solid product (II), the solid product (III) obtained by reacting the solid product (II) with the organosilicon compound component and the organoaluminium compound are obtained. Using a catalyst obtained by combining the beam compound component relates α- olefin polymer production method.

However, in the present invention, the α-olefin polymer is
In addition to homo-copolymers of α-olefins having 3 or more carbon atoms,
It also includes a copolymer of an α-olefin having 3 or more carbon atoms and an α-olefin having 2 or more carbon atoms, and a copolymer with a certain copolymer component is a copolymer of a certain copolymer component in the copolymer. It is said that the component ratio is less than 50 mol%.

[Conventional technology]

Conventionally, as a catalyst for α-olefin polymerization, a combination of a solid titanium halide and an organoaluminum compound is well known, and a catalyst that gives a polymer having high polymerization activity and high stereoregularity is energetic. Has been pursued by.

Furthermore, as a recent tendency, a transition metal compound such as titanium halide is supported on a carrier such as a magnesium compound,
Many proposals have been made that the polymerization activity of olefins can be dramatically increased.

However, in recent years, in addition to the above-mentioned high activity and high stereoregularity, the activity persistence decreases with the passage of polymerization time, and the ester odor in the polymer produced by the aromatic carboxylic acid ester used for the polymerization time increases. Is a big problem. Moreover, conventional supported catalysts are used for polymerization at a relatively low temperature because it is necessary to suppress a decrease in polymerization activity, which is also related to problems such as heat removal from the polymerization reactor, but this may increase productivity. It left the problem of difficulty.

By the way, conventionally, as a catalyst carrier for producing an α-olefin polymer, a compound having a complicated composition prepared by a chemical reaction between a trivalent metal halide such as aluminum chloride and a divalent metal compound such as magnesium hydroxide is used, Attempts have been made to improve the polymerization activity and stereoregularity of the resulting supported catalyst.

For example, in Japanese Examined Patent Publication No. 57-51845, a solid catalyst obtained by mixing a complex obtained by reacting an electron donor with a transition metal compound with the above-mentioned carrier equivalent and pulverizing it is used as an α-
An olefin polymer is produced, but the polymerization activity and stereoregularity are still insufficient, and the polymerization temperature is 60 ° C.
Low temperatures of the order of magnitude are preferred, which is disadvantageous for industrial production.

In Japanese Examined Patent Publication No. 57-51843, a solid catalyst is prepared by reacting the corresponding carrier with an electron donor such as alcohol or ester and then reacting with a transition metal compound. However, even if the catalyst is used, the polymerization activity and stereoregularity are not sufficient,
Moreover, the polymerization temperature is low, and there are the same problems as described above.

Further, in JP-B-58-8686, a solid catalyst obtained by reacting the above carrier equivalent with an electron donor and an electron acceptor one or more times is preliminarily polymerized with an α-olefin in the presence of organoaluminum. To obtain a solid catalyst component for polymerization.

JP-A-56-133303 discloses an α-olefin polymer obtained by combining the solid catalyst component obtained in JP-B-58-8686 with a trialkylaluminum component and a reaction product of an electron donor and an electron acceptor. Is produced by using a reaction product of an electron donor and an electron acceptor.

Above 2 head (Japanese Patent Publication No. 58-8686 and Japanese Patent Publication No. 56-133303)
, The isotactic index defined as the proportion of n-hexane insoluble matter at 20 ℃ was relatively low at 96-98%, and IR-τ (stereoregularity index by infrared spectroscopy) was low and insufficient. Since the polymerization is carried out using an ester such as methyl p-toluate or a reaction product of methyl p-toluate and aluminum trichloride after the prepolymerization treatment, the produced polymer has an ester odor. Therefore, there is a problem that a post-treatment process for removing the ester odor is required.

[Object of the Invention]

The present inventors have conducted earnest studies in order to solve the problems of the above-described conventional techniques, and have completed the present invention.

As is clear from the above description, the object of the present invention is to reduce the polymerization activity with the passage of the polymerization time even during high temperature polymerization, and to increase the polymerization activity to such an extent that removal of the residual catalyst in the polymer is not necessary. A method for producing an α-olefin polymer which is a highly stereoregular polymer and has no ester odor in the polymer.

[Constitution / Effect of Invention]

 The present invention has the following main configuration [1].

[1] The following substances A, B and C, A: a compound represented by the general formula AlX ₃ (X is halogen) and Mg
A solid product (I) obtained by reacting (OH) ₂ or MgO with a titanate ester and an aliphatic alcohol are heated and mixed in an inert hydrocarbon solvent to dissolve, and a solution thus obtained is generally used. A compound represented by the formula SiX ₄ (X is halogen) is mixed and reacted to form a solid support (II), and the solid product (II) is reacted with a compound represented by the general formula TiX ₄ (X is halogen). A solid product (III) obtained by reacting with an aromatic dicarboxylic acid diester in either or both of the above steps, B: the general formula Si ▲ R ¹⁰ _t ▼ (OR ¹¹ ) _4-t where R ¹⁰ and R
¹¹ is an alkyl group having 1 to 20 carbon atoms, an aryl group or a cycloalkyl group having 3 to 20 carbon atoms, and t is a number of 0 to 3), C: an organoaluminum compound, A method for producing an α-olefin polymer, characterized in that the α-olefin is polymerized in combination.

The configuration and effects of the present invention will be described in detail below.

First, a method for producing a supported solid catalyst component supporting a transition metal compound will be described.

The solid product (I) can be obtained by reacting a compound represented by the general formula AlX ₃ (X is halogen) with Mg (OH) ₂ or MgO.

As AlX ₃ , aluminum trichloride (anhydrous), aluminum tribromide (anhydrous), or the like is used. Solid product (I)
The production method, (1) _- AlX ₃ and Mg (OH) ₂ or MgO and a ball mill, in a pulverizer such as vibration mill, a method of performing the reaction while grinding, (2) AlX ₃ and Mg (OH) ₂ Alternatively, there is a method of pulverizing and mixing with MgO and then reacting by heating.
The amount ratio of AlX ₃ and Mg (OH) ₂ or MgO, compared AlX ₃ 1 mol of Mg (OH) ₂ or MgO0.01~20 mol, preferably 0.05 to 10 mol. When the reaction is carried out while crushing, the crushing reaction conditions are room temperature (20 ° C) to 500 ° C, preferably 50 to 300 ° C, 5 to 100 hours for the ball mill and 10 minutes to 50 hours for the vibration mill. . When heating after crushing, use a ball mill for 5 to 100 hours and a vibration mill for 10 minutes to 50 hours.
After crushing for an hour, heat at room temperature (20 ° C) to 500 ° C for 10 minutes to 50 hours. A solid product (I) is thus obtained.

The solid product (I) is mixed with titanic acid ester and aliphatic alcohol in an inert hydrocarbon solvent and heated to dissolve.

Examples of the titanic acid ester include orthotitanic acid ester represented by Ti (OR ¹ ) ₄ and R ² [O-Ti (OR ³ ) (O
R ⁴ )] _m OR ⁵ is a polytitanate ester.
Here, R ¹ , R ² , R ³ , R ⁴ and R ⁵ are an alkyl group having 1 to 20 carbon atoms, an aryl group or a cycloalkyl group having 3 to 20 carbon atoms, and m is a number of 2 to 20. is there. Specifically, orthotitanic acid such as methyl orthotitanate, ethyl orthotitanate, n-propyl orthotitanate, n-butyl orthotitanate, i-amyl orthotitanate, phenyl orthotitanate and cyclohexyl orthotitanate. Ester, methyl polytitanate, ethyl polytitanate, polytitanate
n-Propyl, polytitanate i-propyl, polytitanate n-
Polytitanate esters such as butyl, i-butyl polytitanate, n-amyl polytitanate, phenyl polytitanate and cyclopentyl polytitanate can be used.

As the aliphatic alcohol, an aliphatic alcohol having 1 to 18 carbon atoms can be used. Specifically, methyl alcohol, ethyl alcohol, n-propyl alcohol,
In addition to monohydric alcohols such as i-propyl alcohol, n-butyl alcohol, i-amyl alcohol, n-hexyl alcohol, n-heptyl alcohol, n-octyl alcohol and 2-ethylhexyl alcohol, ethylene glycol, trimethylene glycol, Polyhydric alcohols such as glycerin can also be used. Among them, carbon number 4
-10 fatty alcohols are preferred. As the inert hydrocarbon solvent, pentane, hexane, heptane, nonane,
Aliphatic hydrocarbons such as decane and kerosene, aromatic hydrocarbons such as benzene, toluene and xylene, halogenated hydrocarbons such as carbon tetrachloride, 1,2-dichloroethane, chlorobenzene can be used. Of these, aliphatic hydrocarbons are preferable.

As the aromatic dicarboxylic acid diester, phthalic acid ester and terephthalic acid ester are used, and specifically, dimethyl phthalate, dimethyl terephthalate, diethyl phthalate, diethyl terephthalate, di-n-propyl phthalate, and di-terephthalate are used. n-propyl, diisopropyl phthalate, diisopropyl terephthalate, di-n-butyl phthalate, -n-butyl terephthalate, diisobutyl phthalate, diisobutyl terephthalate, dihexyl phthalate,
Examples thereof include dicyclopropyl phthalate, diphenyl phthalate and diphenyl terephthalate.

Specifically, the solid product (I), the titanic acid ester and the aliphatic alcohol are mixed and suspended in an inert hydrocarbon solvent in any order, and the suspension is stirred. Heat to dissolve,
The titanate ester and the aliphatic alcohol are heated in an inert hydrocarbon solvent with stirring, and the solid product (I) is added to the solution and dissolved. Alternatively, the solid product (I) is suspended in an inert hydrocarbon solvent while heating, and the titanate ester and the aliphatic alcohol are added to the suspension to dissolve the suspension. And the like.

Either method can be adopted, but the method is preferable because the operation is extremely simple. The solution after heating is completely dissolved into a uniform solution. A small amount of insoluble matter may remain in some cases, but a uniform solution is preferable. A small amount of insoluble matter may be removed by filtration to obtain a uniform solution. It is necessary to heat the suspension in order to dissolve it. Heating temperature is 40 ~ 200 ℃, preferably 50 ~ 150 ℃
The heating time is 5 minutes to 7 hours, preferably 10 minutes to 5 hours. The amount of titanic acid ester used is 0.1 to 50 mol, preferably 0.3 to 30 mol in the case of orthotitanic acid ester with respect to 1 gram atom of divalent metal in the solid product (I), for example, 1 to 30 mg of polytitanic acid ester. In the case of, the amount used is the same as that of the orthotitanate in terms of a unit corresponding to the orthotitanate. The amount of the aliphatic alcohol used is 0.3 to 100 mol, preferably 0.5 to 7 per 1 gram atom of magnesium in the solid product (I).
It is 0 mol. The larger the total amount of titanic acid ester and aliphatic alcohol used relative to the solid product (I), the greater the solubility of the solid product (I) in an inert hydrocarbon solvent.
In addition to having to use very large amounts of SiX ₄ to resolidify the solid product (I) equivalent in the resulting solution, the resolidification itself is difficult. On the other hand, if the total amount of titanic acid ester and aliphatic alcohol used is too small, the solid product (I) will not be soluble in the inert hydrocarbon solvent, and a uniform reaction cannot be carried out.
The object of the present invention cannot be achieved. The total amount of titanic acid ester and aliphatic alcohol used is narrower than the above-mentioned total usable amount range, and is 1.0 to 100 mol, preferably 2 to 50 mol per 1 gram atom of magnesium in the solid product (I). Is.

The amount of the inert hydrocarbon solvent used is 0.1 to 6, preferably 0.2 to 4, with respect to 1 gram atom of magnesium in the solid product (I).

Next, the above-mentioned solution is reacted with SiX ₄ and an aromatic dicarboxylic acid diester to obtain a solid product (II). That is, as a method for obtaining the solid product (II), the above solution containing the equivalent of the solid product (I) is reacted with only SiX ₄ to precipitate a solid, and SiX ₄ and an aromatic dicarboxylic acid. There is a method of reacting with a diester to precipitate a solid. As the latter method, (i) aromatic dicarboxylic acid diester is further added and reacted, and then SiX ₄ is added to precipitate a solid, (ii) aromatic With diesters of dicarboxylic acids
SiX ₄ is added and reacted to precipitate a solid, (iii) SiX ₄
Can be used to precipitate a solid, and then an aromatic dicarboxylic acid diester is added and reacted, or a combination of two or more thereof.

After thus obtaining a solid, the solid is washed with an inert hydrocarbon solvent to obtain a solid product (II).

As SiX ₄ , silicon tetrachloride or silicon tetrabromide may be used alone or in combination of two or more.

Among them, silicon tetrachloride is preferable.

The aromatic dicarboxylic acid diester and SiX ₄ may be used as they are or after being diluted with a solvent. In that case, the same solvent as the above-mentioned inert hydrocarbon solvent can be used.

The reaction temperature for reacting SiX ₄ or SiX ₄ and an aromatic dicarboxylic acid diester with a solution containing the above-mentioned solid product (I) equivalent is 30 to 150 ° C., preferably 50 to 130 ° C., and the reaction time is one step. Every 5 minutes to 5 hours, preferably 10 minutes
3 hours.

The amount of the aromatic dicarboxylic acid diester used is 0.02 to 0.8 mol, preferably 0.05 to 0.6 mol, per 1 gram atom of the divalent metal such as magnesium in the solid product (I) used. This amount of aromatic dicarboxylic acid diester may be used at one time or may be used in several stages.

The amount of SiX ₄ used is 0.1 to 100 mol, preferably 1 to 50 mol, per 1 gram atom of the divalent metal in the solid product (I) used. By adding SiX ₄ to the homogeneous solution in which the solid product (I) is dissolved and reacting, solid is precipitated. When the aromatic dicarboxylic acid diester is reacted, the time of addition may be the same as or before or after the solid precipitation as described above.

When the solid is precipitated in this manner, the solid can be subsequently subjected to the reaction of TiX ₄ described below.
However, it is preferable to wash the deposited solid once with the above-mentioned inert hydrocarbon solvent. This is because unreacted substances or by-products existing in the solution in which the solid is precipitated may interfere with the above reaction on the solid. After the washing, a solid product (II) is obtained.

Next, the solid product (II) is reacted with TiX ₄ and at least the aromatic dicarboxylic acid diester is reacted with at least the solid product (I).
When not used in the production reaction of I), be sure to react it to obtain a solid product (III). When the aromatic dicarboxylic acid diester is used in the reaction for producing the solid product (II),
The reaction of the solid product (II) with TiX ₄ in obtaining the solid product (III) may be omitted, but may be done as such.

Specific examples of TiX ₄ include titanium tetrachloride.

The method for producing the solid product (III) will be described first in the case where the aromatic dicarboxylic acid diester is not used in the reaction. The reaction between the solid product (II) and TiX ₄ is carried out by adding TiX ₄ to a suspension of the solid product (II) in the above-mentioned inert hydrocarbon, or by adding the solid product (II) into TiX ₄ ( II) may be added and reacted. The amount of TiX ₄ used is 1 to 1000 mol, preferably 5 to 500 mol, per 1 gram atom of the divalent metal in the solid product (I) used.

The reaction temperature of the solid product (II) and TiX ₄ is 40 to 150 ° C., preferably 50 to 130 ° C., the time is 5 minutes to 5 hours, preferably 1
0 minutes to 3 hours. After the reaction, solids are separated by filtration or a decantation method, and the solids are thoroughly washed with an inert solvent to remove unreacted substances or by-products.

When the aromatic dicarboxylic acid diester is reacted with the solid product (II) together with TiX ₄ , the same reaction temperature and reaction time as those in the above method are sufficient together.
The amount of the aromatic dicarboxylic acid diester used is as specified in the case of the solid product (II) forming reaction.

The solid product (III) obtained as described above is easily deactivated by a trace amount of oxygen or water, so that the production of the solid product (III), storage, or use may result in contamination by oxygen or water. You have to be careful not to.

The solid product (III) can be used as a catalyst for producing an α-olefin polymer by combining it as a solid catalyst component with an organoaluminum compound and an organosilicon compound.

As the organoaluminum compound, a general formula AlX _s R ⁹
_3-s (where X is Cl, R ⁹ is an alkyl group having 1 to 20 carbon atoms, an aryl group or a cycloalkyl group having 3 to 20 carbon atoms, and s is a number of 0 to 2), Specifically, in addition to the single use of triethylaluminum, two types of organic aluminum such as triethylaluminum and tri-i-butylaluminum, triethylaluminum and diethylaluminum chloride, triethylaluminum and ethylaluminum sesquichloride, etc. It is also preferable to use a mixture of compounds or a mixture of three kinds of organic aluminum compounds such as triethylaluminum, tri-i-butylaluminum and ethylaluminum sesquichloride.

Examples of the organosilicon compound include phenylalkoxysilane and alkylalkoxysilane. Specific examples of phenylalkoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, phenyltri-n-propoxysilane, phenyltriisopropoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, diphenylmethoxyethoxysilane,
Examples thereof include triphenylmethoxysilane and triphenylethoxysilane. In addition, specific examples of the alkylalkoxysilane include tetramethoxysilane, tetraethoxysilane, trimethoxyethylsilane, trimethoxymethylsilane, triethoxymethylsilane, ethyltriethoxysilane, and ethyltriisopropoxysilane.

The solid product (III), the organoaluminum compound and the organosilicon compound may be combined by a method in which the solid product (III), the organoaluminum compound and the organosilicon compound are independently supplied to a polymerization vessel. The solid product (II) and the solid product (III) are independently fed to the polymerization reactor.
I), supplying a mixture of an organoaluminum compound and an organosilicon compound to a polymerization vessel, and any method can be adopted. In some cases, or is preferred. When combining the three as described above, it is also possible to dissolve or suspend each component or any component in a liquid aliphatic hydrocarbon such as butane, pentane, hexane, heptane, nonane, decane or kerosene. it can. The temperature in the case of mixing before feeding to the polymerizer as in the above cases and is -50 to + 50 ° C, preferably -30.
~ + 30 ° C, the time is 5 minutes to 50 hours, preferably 10 minutes to 30 hours.

The amount of the organoaluminum compound used is 10 to 1000 mol, preferably 50 to 500 mol, per 1 mol of titanium atom contained in the solid product (III) as the solid catalyst component. The amount of the organosilicon compound used is 0.01 to 1 mol, preferably 0.05 to 0.7 mol, per 1 mol of the organoaluminum compound. When a mixed organoaluminum compound or a mixed organosilicon compound is used, the total number of moles of each may fall within the above range.

In the method of the present invention, an α-olefin polymer is produced using a solid product (III) as a solid catalyst component, a catalyst obtained by a combination of an organoaluminum compound and an organosilicon compound, and an α-olefin having 3 or more carbon atoms. To do. Examples of the α-olefin having 3 or more carbon atoms include propylene, butene-1, pentene-1, hexene-1, octene-1, decene-1, 4-methylpentene-1, 3-methylpentene-1, methyl-1. , 4-hexadiene or the like can be used. In the polymerization of these α-olefins, not only homopolymerization but also other α-olefins having 2 or more carbon atoms
It also includes copolymerization with one or more olefins. Examples of the α-olefin having 2 or more carbon atoms include ethylene, butadiene, isoprene, and 1,4-pentadiene, in addition to the α-olefin having 3 or more carbon atoms described above. The amount of those other α-olefins used is the amount contained in the copolymer of less than 50 mol%.

The polymerization can be carried out in the liquid phase or the gas phase. When the polymerization is carried out in the liquid phase, an inert hydrocarbon solvent such as hexane, heptane, nonane, decane or kerosene may be used as the polymerization medium, but the α-olefin itself may be used as the reaction medium. . When carrying out the polymerization in the gas phase, in principle no reaction medium is used, but it is also possible to use either the catalyst or any of its components dissolved or suspended in the abovementioned inert hydrocarbons. The polymerization is carried out by bringing the catalyst into contact with the α-olefin in the polymerization vessel. Polymerization temperature is 40 ~ 200 ℃, preferably 50 ~ 1
The temperature is 50 ° C., and the polymerization pressure is atmospheric pressure to 100 kg / cm ² (G), preferably 5 to 50 kg / cm ² (G). The polymerization can be carried out in any of a batch type, an anti-continuous type and a continuous type, but industrially the continuous type polymerization is preferred.

It is also possible to carry out the polymerization by multistage polymerization under different polymerization conditions. To control the molecular weight of the polymer,
It is effective to add a molecular weight regulator such as hydrogen to the polymerization system.

The production and storage of the solid catalyst components described above, the preparation of the catalyst and the production of the polymer must be carried out under an atmosphere of an inert gas such as nitrogen or helium, but in some cases even under a monomer atmosphere or under vacuum conditions. It can be carried out.

The main effects of the present invention are as follows. First, the polymerization activity is extremely high, and it is not necessary to remove the residual catalyst in the polymer. The polymer purification step is not required, which is extremely economical. Second, the stereoregularity of the polymer is extremely high. A high isotactic index (hereinafter abbreviated as II) indicates this, and a high IR-τ also indicates this. Even at the time of high temperature polymerization, there is little decrease in the polymerization activity due to the passage of the polymerization time, that is, the polymerization activity persistence is high, which is very convenient when producing a copolymer, particularly a block copolymer. Since the obtained polymer is odorless, it does not require a post-treatment step for removing the ester odor in the polymer as in the conventional case. Therefore, the industrial production of the α-olefin polymer can be carried out economically and stably.

The present invention will be described below with reference to examples and comparative examples.

Among the properties defining the polymers shown in the examples and comparative examples, the definitions or measuring methods for those requiring special explanation are as follows.

(1) II (isotactic index) is the ratio of the total polymer weight minus the total weight of the solvent-soluble polymer at the time of polymerization and the boiling hexane-soluble polymer, relative to the total polymer amount.

(2) IR-τ is 997 cm in infrared spectrophotometer
^-1 (Crystalline band) and 972cm ^-1 (Amorphous band)
Is the absorbance ratio of (A997 / A972).

Example 1 (1) Preparation of supported solid catalyst component Aluminum trichloride (anhydrous) 200 g and magnesium hydroxide
When 58 g was reacted while being pulverized with a vibration mill at 250 ° C. for 3 hours, the reaction occurred while generating hydrogen chloride gas. After completion of heating, the mixture was cooled in a nitrogen stream to obtain a solid product (I).

In a glass flask, 30 ml of purified decane, 5.0 g of solid product (I), 17.1 g of n-butyl orthotitanate, and 19.6 g of 2-ethyl-1-hexanol were mixed and stirred at 110 ° C.
It was heated for 2 hours to dissolve. The homogeneous solution was heated to 70 ° C, 51 g of silicon tetrachloride was added dropwise over 2 hours with stirring to precipitate a solid, and the mixture was stirred at the same temperature for 1 hour, and then 2.5 g of di-n-butyl phthalate was added to 70 ° C. The solid product was washed with purified hexane to give a solid product (II).
Got The total amount of the solid product (II) was mixed with 50 ml of titanium tetrachloride diluted with 50 ml of 1,2-dichloroethane, reacted at 100 ° C. for 2 hours with stirring, washed with purified hexane, and washed with 25
The solid product (III) was obtained by drying at ℃ for 1 hour under reduced pressure.
This solid product (III) was used as a supported solid catalyst component.

The above-mentioned operations and the same operations in the following Examples and Comparative Examples were all performed under a purified nitrogen atmosphere.

The composition analysis result of this solid catalyst component is Ti3.4% by weight (hereinafter referred to as%), Mg15.5%, C153.1%, Al1.5%,
Di-n-butyl phthalate 18.3%, butoxy group 3.2% and 2
-Ethylhexanoxy group was 1.3%.

(2) Production of α-olefin polymer To an autoclave having an internal volume of 3 and substituted with propylene, purified hexane 1.5, triethylaluminum 3.0 mmol, solid catalyst component 13.5 mg, and diphenyldimethoxysilane 0.45 mmol were added, and the temperature was raised to 80 ° C. , Hydrogen 150 ml
Was added, and propylene was continuously introduced at a total pressure of 7.0 kg / cm ² (G) to carry out polymerization at 80 ° C. for 2 hours. Thereafter, the hexane-insoluble matter was filtered off and dried to obtain 204 g of odorless powdery polypropylene.

The filtrate at the time of the above filtration was concentrated to obtain 2.1 g of a polymer which was soluble in the polymerization solvent, and the obtained powdery polypropylene was extracted with boiling n-hexane for 6 hours to obtain 0.8 g of the dissolved product. Then, II was calculated, while IR-τ, melt flow rate (MFR), and bulk density (BD) were measured.

The results obtained are as shown in Table 1.

Example 2 An experiment was conducted in the same manner as in Example 1 except that the polymerization time was 4 hours. The results obtained are as shown in Table 1.

Example 3 (1) Preparation of supported solid catalyst component In the same manner as in Example 1 except that 56 g of magnesium oxide was used in place of magnesium hydroxide in (1) of Example 1, a solid product (III ) Was obtained, and this was used as a supported solid catalyst component.

At the time of polymerization, polymerization was carried out for 4 hours in the same manner as in Example 2 except that 0.45 mmol of phenyltriethoxysilane was used instead of diphenyldimethoxysilane. The results obtained are as shown in Table 1.

Example 4 A supported solid catalyst component was prepared in the same manner as in Example 1 except that diisobutyl phthalate was used instead of di-n-butyl phthalate in (1) of Example 1.

An experiment was conducted in the same manner as in Example 2 during the polymerization.

The results obtained are as shown in Table 1.

Comparative Example 1 (1) Preparation of Supported Solid Catalyst Component Di-n-butyl phthalate added in (1) of Example 1 after dropping silicon tetrachloride into the solid product (I) to precipitate a solid. A supported solid catalyst component was obtained in the same manner as in (1) of Example 1 except that 3.4 g of ethyl p-toluate was used instead of.

The composition analysis result of this solid catalyst component is Ti3.2%, Mg16.5
%, Cl56.3%, Al1.8%, ethyl p-toluate 10.5%,
It was 3.5% butoxy group and 1.5% 2-ethylhexanoxy group.

(2) Production of α-Olefin Polymer Purified hexane (1.5) was placed in an autoclave having an internal volume of 3 and substituted with propylene, 3.0 mmol of triethylaluminum, 15.5 mg of a solid catalyst component, and 0.45 mmol of methyl p-toluate were added, and the mixture was heated to 70 ° C. After the temperature was raised to 150 ml and 150 ml of hydrogen was added, polymerization was carried out at 70 ° C. for 2 hours while continuously introducing propylene so that the total pressure was 7.0 kg / cm ² (G). Then, the hexane-insoluble matter was filtered off and dried to obtain 194 g of powdery polypropylene. The powdery polypropylene had an ester odor.

The results obtained for this powdered polypropylene are the first
As shown in the table.

Comparative Example 2 An experiment was conducted in the same manner as in Comparative Example 1 except that the polymerization time was 4 hours. The results obtained are as shown in Table 1.

Comparative Examples 3 to 4 An experiment was conducted in the same manner as Comparative Example 1 except that the polymerization temperature and time were 80 ° C. and 2 hours (Comparative Example 3), and 80 ° C. and 4 hours (Comparative Example 4). went. The results obtained are as shown in Table 1.

Example 5 (1) Preparation of supported solid catalyst component Aluminum trichloride (anhydrous) 130 g and magnesium hydroxide
When 58 g was subjected to reaction while being heated and pulverized at 150 ° C. for 5 hours in a vibrating ball mill, the reaction occurred while generating hydrogen chloride gas. After completion of heating, the mixture was cooled in a nitrogen stream to obtain a solid product (I).

In a glass flask, 30 ml of purified nonane, 5.0 g of solid product (I), 17.1 g of n-butyl orthotitanate, and 19.6 g of 2-ethyl-1-hexanol were mixed, and stirred while stirring.
The mixture was heated at ℃ for 3 hours to completely dissolve it. 70 the homogeneous solution
C., 51 g of silicon tetrachloride was added dropwise to this homogeneous solution over 3 hours to precipitate a solid, and the mixture was stirred at the same temperature for 1 hour, and the solid was washed with purified hexane to give a solid product (I
I) got. The solid product (II) was diluted with 50 ml of 1,2-dichloroethane to 50 ml of titanium tetrachloride and 3.2 g of diisobutyl phthalate was added, and the mixture was reacted at 100 ° C for 2 hours, followed by decantation at the same temperature to form a liquid phase. Excluding parts
Titanium tetrachloride 50 diluted with 50 ml of 1,2-dichloroethane again
Add ml and heat at 100 ° C for 2 hours. After completion of the reaction, the solid part was collected by hot filtration, washed with purified hexane, and dried at 25 ° C. under reduced pressure for 1 hour to obtain a solid product (III). This solid product (III) was used as a supported solid catalyst component. The Ti content of this solid catalyst component was 3.2 ° C.

(2) Manufacture of α-olefin polymer Purified hexane 1.5, triethylaluminum 3.0 mmol, in an autoclave with an internal volume of 3 substituted with propylene,
15.0 mg of solid catalyst component and 0.45 mmol of diphenyldimethoxysilane were added, the temperature was raised to 70 ° C., 150 ml of hydrogen was added, and then propylene was continuously introduced so that the total pressure was 7.0 kg / cm ² (G). While conducting the polymerization at 80 ° C for 2 hours. Then, the hexane-insoluble matter was filtered off and dried to obtain 228 g of powdery polypropylene.

The results obtained for this powdered polypropylene are the second
As shown in the table.

Example 6 An experiment was conducted in the same manner as in Example 5 except that the polymerization time was 4 hours.

The obtained results are as shown in Table 2.

Example 7 An experiment was conducted in the same manner as in Example 5 except that the polymerization temperature was 80 ° C. and the polymerization time was 4 hours.

The obtained results are as shown in Table 2.

Comparative Example 5 (1) Preparation of supported solid catalyst component The same operation as in Example 5 was performed to obtain a solid product (III) as a solid catalyst component.

(2) Manufacture of α-olefin polymer Purified hexane 1.5, triethylaluminum 3.0 mmol, in an autoclave with an internal volume of 3 substituted with propylene,
After adding 18 mg of solid catalyst component and 0.45 mmol of methyl p-toluate, heating to 70 ° C. and adding 150 ml of hydrogen,
Polymerization was carried out at 70 ° C. for 2 hours while continuously introducing propylene so that the total pressure was 7.0 kg / cm ² (G).

The obtained results are as shown in Table 2.

Comparatively 6 to 7 The polymerization time was 4 hours (Comparative Example 6), and the polymerization temperature was 80 ° C. and the polymerization time was 4 hours (Comparative Example 7).
The experiment was performed in the same manner as in Comparative Example 5 except for the above.

The obtained results are as shown in Table 2.

[Brief description of drawings]

FIG. 1 is a manufacturing process diagram (flow chart) for explaining the method of the present invention.

Claims (14)

[Claims] 1. The following substances A, B and C, A: a compound represented by the general formula AlX ₃ (X is a halogen) and Mg.
A solid product (I) obtained by reacting (OH) ₂ or MgO with a titanate ester and an aliphatic alcohol are heated and mixed in an inert hydrocarbon solvent to dissolve, and a solution thus obtained is generally used. A compound represented by the formula SiX ₄ (X is a halogen) is mixed and reacted to obtain a solid product (II),
A solid product obtained by reacting the solid product (II) with a compound represented by the general formula TiX ₄ (X is a halogen) and an aromatic dicarboxylic acid diester in any of the above steps or both steps ( III), B: General formula Si ▲ R ¹⁰ _t ▼ (OR ¹¹ ) _4-t where R ¹⁰ and R
¹¹ is an alkyl group having 1 to 20 carbon atoms, an aryl group or a cycloalkyl group having 3 to 20 carbon atoms, and t is a number of 0 to 3), C: an organoaluminum compound, A method for producing an olefin polymer having a general formula, which comprises polymerizing an α-olefin in combination. 2. AlX ₃ and Mg (OH) ₂ or MgO are mixed with AlCl ₃
At a reaction temperature of 20 to 500 ° C., a reaction time of 10 minutes to 100 at a ratio of Mg (OH) ₂ or MgO of 0.01 to 20 mol per 1 mol.
The method according to claim 1, wherein the solid product (I) is obtained by reacting while mixing for a period of time and pulverizing. 3. A titanic acid ester of the general formula Ti (OR ¹ )
_And / or a polytitanate represented by the general formula R ² [OTi (OR ³ ) (OR ⁴ )] _m OR ⁵ (wherein R ² , R ³ , R ⁴ and R ⁵ are The method according to claim 1, wherein the alkyl group having 1 to 20 carbon atoms, the aryl group, or the cycloalkyl group having 3 to 20 carbon atoms, and m is the number of 2 to 20. 4. The method according to claim 1, wherein an aliphatic alcohol having 1 to 18 carbon atoms is used as the aliphatic alcohol. 5. When obtaining a solution in which the solid product (I) is dissolved, 0.1 to 50 mol of titanic acid ester as an orthotitanic acid ester and a fat relative to 1 gram atom of magnesium in the solid product (I). Group alcohol 0.3-100
The method of claim [1] using moles. 6. The method according to claim 1, wherein a phthalic acid ester and a terephthalic acid ester are used as the aromatic dicarboxylic acid diester. 7. The solution obtained in the step is reacted with 1 to 50 mol of SiX ₄ per 1 gram atom of magnesium in the solid product (I) used for its production, and the precipitated solid is treated with an inert hydrocarbon. The method according to claim 1, wherein the solid product (II) is obtained by washing with a solvent. 8. SiX ₄ is added to the solution obtained in step 50 to 130 ° C.
The method according to claim [1], wherein the reaction is carried out for 10 minutes to 3 hours. 9. The solution obtained in the step contains 1 to 50 mol of SiX ₄ and 0.02 to 0.8 mol of an aromatic dicarboxylic acid diester per 1 gram atom of magnesium in the solid product (I) used for its preparation. The method according to claim [1], wherein a solid product (II) is obtained by reacting and washing the precipitated solid with an inert hydrocarbon solvent. 10. The method according to claim 1, wherein SiX ₄ and an aromatic dicarboxylic acid diester are reacted with the solution obtained in the step at 50 to 130 ° C. for 10 minutes to 3 hours. 11. The solution obtained in the step (i) is reacted with an aromatic dicarboxylic acid diester and then reacted with SiX ₄ .
Either (ii) a method in which an aromatic dicarboxylic acid diester and SiX ₄ are simultaneously reacted, or (iii) a method in which SiX ₄ is reacted and then an aromatic dicarboxylic acid diester is reacted, or a combination of two or more of these methods is used. The method according to claim [1]. 12. The solid product (II) is reacted with 1 to 1000 mol of TiX ₄ per gram atom of magnesium in the solid product (I) used in the production at 50 to 130 ° C. for 10 minutes to 3 hours. The method according to claim 1, wherein the reaction product is washed with an inert hydrocarbon solvent to obtain a solid product (III). 13. A solid product (II) containing from 0.02 to 0.8 mol of an aromatic dicarboxylic acid diester with 1 to 1000 mol of TiX ₄ per gram atom of magnesium in the solid product (I) used in its production. Is reacted at 50 to 130 ° C. for 10 minutes to 3 hours, and the reaction product is washed with an inert hydrocarbon solvent to obtain a solid product (III). The method according to claim [1]. 14. An organic aluminum compound represented by the general formula Al
X _s R ⁹ _3-s (where X is Cl, R ⁹ is an alkyl group having 1 to 20 carbon atoms, an aryl group, or a cycloalkyl group having 3 to 20 carbon atoms, and s is a number of 0 to 2). The method of claim [1].