JPH0723409B2 - Method for producing butene-1 polymer - Google Patents

Description

TECHNICAL FIELD The present invention relates to a method for producing a butene-1 polymer. More specifically, it relates to a method for producing a butene-1 polymer suitable for molding, for example, a pipe by taking advantage of gas phase polymerization in the presence of a highly active catalyst.

[Prior Art and its Problems] Conventionally, as a proposal for a method for producing a highly crystalline polybutene-1 polymer, there have been many methods of performing solution polymerization or slurry polymerization using titanium trichloride as a catalyst. On the other hand, if the butene-1 polymer can be produced by gas phase polymerization, it is expected that the process can be simplified and the production cost can be reduced. Therefore, there have been some proposals suggesting the possibility of gas phase polymerization of butene-1. However, there are various problems in implementing the method according to this kind of proposal on an industrial scale.

For example, butene-1 polymer has a stronger affinity for hydrocarbon solvents than polyethylene and polypropylene. Therefore, when a small amount of solvent is accompanied when the catalyst component is supplied to the gas phase polymerization system, the polymers are likely to aggregate. As a result, it becomes difficult to perform stable operation or operation of the device for a long period of time.

Further, gas phase polymerization is carried out using a titanium trichloride-based catalyst (see JP-A-60-192716) and a magnesium chloride-based catalyst (see JP-A-59-6205) which have been widely used in the past. And the catalytic activity becomes low, and the resulting butene-1 is obtained.
The stereoregularity of the polymer was also insufficient, and the advantages of the gas phase polymerization method could not be fully utilized.

OBJECT OF THE INVENTION An object of the present invention is to provide a method for producing a butene-1 polymer using a highly active polymerization catalyst.

Another object of the present invention is to provide a method for producing a butene-1 polymer having high stereoregularity by a gas phase polymerization method.

Still another object of the present invention is to provide a method for producing butene-1 having a low catalyst residue content.

Still another object of the present invention is to provide a method capable of producing a butene-1 polymer which can be suitably molded into a molded article such as a pipe under stable operating conditions.

[Means for Achieving the Object] The gist of the present invention for achieving the object is a solid catalyst component (A) obtained from a magnesium compound, a carboxylic acid ester and a halide of tetravalent titanium, an organoaluminum compound ( In the presence of a catalyst obtained from B) and the electron-donating compound (C), a homopolymer of butene-1 or a copolymer of butene-1 and another α-olefin is produced under gas phase polymerization conditions. In the method for producing, the magnesium compound is represented by the formula Mg (OR) ₂ (1) (wherein R is a linear or side chain alkyl group having 1 to 10 carbon atoms, a cycloalkyl group, an aryl group). Group and an aralkyl group.), Wherein the electron-donating compound (C) has the formula (In the formula, R ¹ and R ⁴ represent a hydrocarbon group, and R ² , R ³ and R ⁵ represent hydrogen or a hydrocarbon group, respectively). As a condition, the reaction temperature is 45 to 70 ° C., which is a method for producing a butene-1 polymer.

In the method of the present invention, as shown in FIG. 1, a specific solid catalyst component (A), an organoaluminum compound (B) and a specific electron obtained from a magnesium dialkoxide, a carboxylic acid ester and a halide of tetravalent titanium are used. In the presence of a catalyst obtained from the donor compound (C), a homopolymer of butene-1 or a copolymer of butene-1 and other α-olefin is produced under specific gas phase polymerization conditions. .

-Regarding Solid Catalyst Component (A)-The solid catalyst component (A) is prepared from a specific magnesium dialkoxide, a carboxylic acid ester, and a halide of tetravalent titanium.

This specific magnesium dialkoxide is represented by the formula Mg (OR) ₂ (1) (wherein R is a linear or side chain alkyl group having 1 to 10 carbon atoms, a cycloalkyl group, an aryl group). And represents an aralkyl group.).

When a magnesium compound other than the above formula (1) is used, for example, magnesium chloride, the catalyst activity is low and the amount of residual chlorine in the produced polymer is large, which causes a problem of corrosion of the molding machine.

Specific examples of the magnesium dialkoxide represented by the formula (1) may, for _{example, Mg (-OCH 3) 2,} Mg (-OC
_{2 H 5) 2, Mg (} -OC 3 H 7) 2, Mg (-OC 4 H 9) 2, Mg (-O
_{C 6 H 13) 2, Mg} (-OC 8 H 17) 2, _{Mg (-OCH 3) (- OC} 2 H 5), And so on.

The various magnesium dialkoxides can be used alone or in combination of two or more.

Among these, magnesium dialkoxide in which R is a lower alkyl group is preferable, and magnesium dimethoxide and magnesium diethoxide are particularly preferable.

An organic compound containing oxygen, nitrogen, phosphorus or sulfur can be used as the carboxylic acid ester which is a raw material of the solid catalyst component (A).

Examples of this electron donor include methyl formate, methyl acetate, ethyl acetate, vinyl acetate, propyl acetate, octyl acetate, cyclohexyl acetate, ethyl propionate,
Ethyl acetate, ethyl valerate, methyl chloroacetate, ethyl dichloroacetate, methyl methacrylate, ethyl crotone, ethyl pivalate, dimethyl maleate, ethyl cyclohexanecarboxylate, methyl benzoate, ethyl benzoate, propyl benzoate, benzoic acid Butyl, octyl benzoate, cyclohexyl benzoate, phenyl benzoate,
Benzyl benzoate, methyl toluate, ethyl toluate, amyl toluate, ethyl benzoate, methyl anisate, ethyl anisate, ethyl ethoxybenzoate,
Monoesters such as ethyl p-butoxybenzoate, ethyl o-chlorobenzoate and ethyl naphthoate, or dimethylphthalate, diethylphthalate, dipropylphthalate, diisobutylphthalate, methylethylphthalate, methylpropylphthalate, methylisobutylphthalate, ethylpropyl. Phthalate, ethyl isobutyl phthalate, propyl isobutyl phthalate,
Dimethyl terephthalate, diethyl terephthalate, dipropyl terephthalate, diisobutyl terephthalate, methyl ethyl terephthalate, methyl propyl terephthalate, methyl isobutyl terephthalate, ethyl propyl terephthalate, ethyl isobutyl terephthalate, propyl isobutyl terephthalate, dimethyl isophthalate, diethyl isophthalate, dipropyl isophthalate, Examples thereof include aromatic diesters such as diisobutylisophthalate, methylethylisophthalate, methylpropylisophthalate, methylisobutylisophthalate, ethylpropylisophthalate, ethylisobutylisophthalate and propylisobutylisophthalate.

Of these, preferred are alkyl esters of aromatic carboxylic acids such as benzoic acid, p-methoxybenzoic acid, p.
-Alkoxy esters of aromatic carboxylic acids such as ethoxybenzoic acid and toluic acid having 1 to 4 carbon atoms, aromatic diesters such as diisobutyl phthalate are preferred.

As the halide of the tetravalent titanium, which is one of the raw materials of the solid catalyst component (A), specifically, TiCl ₄ , TiB
Titanium tetrahalides such as r ₄ , TiI ₄ ; Ti (OCH ₃ ) C
_{l 3, Ti (OC 2 H} 5) Cl 3, (n-C 4 H 9 O) TiCl 3, Ti (OC 2 H 5) Br
Trihalogenated alkoxy titanium such as ₃ ; Ti (OCH ₃ ) ₂ C
_{l 2, Ti (OC 2 H} 5) 2 Cl 2, (n-C 4 H 9 O) 2 TiCl 2, Ti (OC 3 H 7)
Dihalogenated alkoxytitanium such as ₂ Cl ₂ ; Ti (OCH ₃ ) _{3
Cl, Ti (OC 2 H 5} ) 3 Cl, (n-C 4 H 9 O) 3 TiCl, Ti (OCH 3) 3 Br
Examples thereof include monohalogenated trialkoxy titanium and the like.

These may be used alone or in combination of two or more.

Of these, it is preferable to use a high halogen content,
It is particularly preferable to use titanium tetrachloride.

The solid catalyst component (A) can be prepared, for example, by temporarily or stepwise contacting the magnesium dialkoxide, the carboxylic acid ester and a halide of tetravalent titanium in a hydrocarbon solvent.

For example, JP-A-56-166205 and JP-A-57-63309.
The preparation methods described in Japanese Patent Application Laid-Open No. 57-190004, Japanese Patent Application Laid-Open No. 57-200407, Japanese Patent Application Laid-Open No. 58-47003, Japanese Patent Application No. 61-43670, etc. Can be included as a suitable method for preparing the solid catalyst component (A).

Further, oxides of elements belonging to Groups II to IV of the periodic table, for example, oxides of silicon oxide, magnesium oxide, aluminum oxide, etc., preferably silicon oxide, or II to IV of the periodic table.
In a solvent, a solid oxide obtained by supporting the magnesium dialkoxide on a composite oxide containing at least one oxide of an element belonging to the group, such as silica-alumina, the carboxylic acid ester, and the halide of tetravalent titanium are used in a solvent. At a temperature of 0 to 200 ° C, preferably 10 to 150 ° C for 2 minutes to
The solid catalyst component (A) can also be prepared by contacting for 24 hours (preparation method described in Japanese Patent Application No. 61-43670).

Furthermore, by contacting the magnesium dialkoxide with the carboxylic acid ester and then reacting the magnesium dialkoxide after contacting the carboxylic acid ester with a halide of tetravalent titanium two or more times, the solid catalyst component (A) can also be prepared (preparation method described in JP-A-57-63309).

In the preparation of the solid catalyst component, as the solvent, an organic solvent inert to the magnesium dialkoxide, the carboxylic acid ester, and the halide of tetravalent titanium, for example, an aliphatic hydrocarbon such as hexane or heptane, or benzene is used. , Aromatic hydrocarbons such as toluene, or halogenated hydrocarbons such as mono- or polyhalogen compounds of saturated or unsaturated aliphatic, alicyclic and aromatic hydrocarbons having 1 to 12 carbon atoms. it can.

In any case, the solid catalyst component (A) thus prepared has a halogen / titanium (molar ratio) of 3 to 200, preferably 4 to 100, and a magnesium / titanium (molar ratio) of 1 to 90. , Preferably 5 to 70 is desirable.

- organic aluminum compound for (B) - Examples of the organoaluminum compound (B), is not particularly limited, the general formula ^{_{AlR 3 vX 3- v Al 2 R}} 3 3 X 3 v [ However, R ³ is 1 to carbon atoms 10 represents an alkyl group, a cycloalkyl group or an aryl group, v represents a real number of 1 to 3, and X represents a halogen atom such as chlorine or bromine. ] Are widely used.

Specifically, trialkyl aluminum such as trimethyl aluminum, triethyl aluminum, triisopropyl aluminum, triisobutyl aluminum, trioctyl aluminum and diethyl aluminum monochloride, diisopropyl aluminum monochloride,
Examples thereof include dialkyl aluminum monohalides such as diisobutyl aluminum monochloride and dioctyl aluminum monochloride, and alkyl aluminum sesquihalides such as ethyl aluminum sesquichloride. Among these, trialkylaluminum is preferable, and triisobutylaluminum is particularly preferable.

-About the electron-donating compound (C) -The electron-donating compound (C) in the present invention has the formula: (However, in the formula, R ¹ and R ⁴ are hydrocarbon groups, preferably substituted or unsubstituted saturated or unsaturated hydrocarbon groups having 2 to 5 carbon atoms, and R ² , R ³ and R ⁵ Represents a hydrogen or a hydrocarbon group, preferably hydrogen or a substituted or unsubstituted saturated or unsaturated hydrocarbon group having 1 to 5 carbon atoms).

When an electron-donating compound (C) other than the heterocyclic compound such as a silane compound or an aromatic ester is used, the catalytic activity is low and the stereoregularity of the resulting polymer is low.

As the heterocyclic compound, specifically, for example, 1,
4-cineole, 1,8-cineole, m-cineole, pinol, benzofuran, 2,3-dihydrobenzofuran (coumarane), 2H-chromene, 4H-chromene, chromane, isochroman, dibenzofuran, xanthene and the like can be mentioned.

These various heterocyclic compounds may be used alone or in combination of two or more.

Among the various heterocyclic compounds described above, 1,8-cineole is preferable.

-Regarding Polymerization-The method of the present invention comprises butene-1 or butene-1 in the presence of a catalyst having the solid catalyst component (A), the organoaluminum compound (B), and the specific heterocyclic compound (C). Butene-1 and other α-olefins are polymerized under gas phase polymerization conditions.

As the composition of the catalyst, the organoaluminum compound (B) is used.
Is 0.1 to 1000 times mol, preferably 1 to 500 times, the mol of the tetravalent titanium halogen compound in the solid catalyst component (A).
The amount of the heterocyclic compound (C) is preferably 0.1 to 500 times, and preferably 0.1 to 500 times the molar amount of the titanium atom in the halide of tetravalent titanium in the solid catalyst component (A). It is preferably 0.5 to 200 times mol.

As the gas phase polymerization conditions, a polymerization temperature is 45 to 70 ° C, preferably
It is important to be between 50 and 65 ° C.

When the polymerization temperature is lower than 45 ° C., it is necessary to prevent liquefaction, and the partial pressure of butene-1 cannot be increased so much.
The polymerization rate cannot be increased sufficiently, and it becomes difficult to remove the heat of polymerization on an industrial scale. Further, when the polymerization temperature is higher than 70 ° C, the generated polymer particles aggregate or adhere to the wall, which makes the polymerization operation difficult, and also reduces the catalytic activity to allow a smooth polymerization operation. become unable.

The partial pressure of butene-1 varies depending on the polymerization temperature,
It may be within the range where liquefaction does not occur in a substantial amount, and in the usual case, it is about 1 to 15 kg / cm ² .

Further, for the purpose of controlling the molecular weight, a molecular weight modifier such as hydrogen may coexist. Furthermore, an inert gas having a boiling point lower than that of butene-1, for example, nitrogen, methane, ethane, propane or the like can be made to coexist. The coexistence of these inert gases further reduces the tendency of the polymer to aggregate, and facilitates removal of the heat of polymerization. The effective coexisting amount of the inert gas is 0.2 mol times or more with respect to butene-1.

Gas phase polymerization can be carried out using a fluidized bed or a stirred fluidized bed. Alternatively, it can be carried out while circulating the gas component through the tubular polymerization vessel.

According to the method of the present invention, a homopolymer of butene-1 or a random or block copolymer of butene-1 and other α-olefin can be produced.

When producing a homopolymer, only butene-1 may be fed to the polymerization vessel and polymerized by a conventional method.

When producing a random copolymer, butene-1 and other α-olefin, butene-1 content in the copolymer is 60 ~ 99.5 mol%, preferably 70 ~ 98 mol% It may be supplied to the polymerization vessel and copolymerized.

In the case of producing a so-called block copolymer, after the first-stage polymerization treatment for homopolymerizing an α-olefin such as propylene or butene-1, the first-stage polymerization treatment is performed as the second-stage polymerization treatment. Butene-1 or butene-1 according to the present invention in the presence of a homopolymer of α-olefin obtained by eye.
And other α-olefins are copolymerized.

Here, as the α-olefin other than butene-1, for example, linear monoolefin such as propylene, ethylene, hexene-1, octene-1, branched monoolefin such as 4-methyl-pentene-1, butadiene, etc. Dienes can be used.

In order to obtain a butene-1 polymer having preferable physical properties, propylene is preferable as the other α-olefin.

When the gas phase polymerization method is adopted, the step of recovering the polymerization solvent can be omitted and the drying step of the produced polymer can be greatly simplified.

In the method of the present invention, post-treatment after polymerization can be carried out by a conventional method. That is, after the gas phase polymerization, the polymer powder discharged from the polymerization vessel may be passed through a nitrogen stream or the like in order to remove the olefin and the like contained therein.
If desired, pelletizing may be carried out by an extruder, and in this case, a small amount of water, alcohol, etc. may be added to completely deactivate the catalyst.

As described above, butene obtained by the method of the present invention
In general, one polymer has an intrinsic viscosity [η] (decalin solution, 135 ° C) of 1.0 to 7.0 dl / g, and II (insoluble matter after Soxhlet extraction with boiling diethyl ether for 6 hours) is 95. % Or more, and the bulk density is 0.28 g / cc or more. Further, the content of the catalyst residue in the obtained polymer is further reduced.

As a result, the butene-1 polymer obtained by the method of the present invention is used as a suitable material for various pipes.

EFFECTS OF THE INVENTION According to the present invention, (1) since a highly active catalyst is used, the amount of the catalyst residue remaining in the polymerization product can be reduced, and therefore, the butene-1 polymer obtained can be used. The step of removing the catalyst residue can be omitted, and since there is almost no harmful residue, the problem of molding machine corrosion can be solved, and (2) since a polymer powder having a large bulk density can be obtained, It is convenient for powder transportation, and (3) [η] is 1.0 to 7.0 dl / g, and stereoregularity (I.
I.) and the excellent creep resistance, it can be molded into a molded product having a good appearance, such as a pipe.

It is possible to provide a method for producing a butene-1 polymer having advantages such as the following.

EXAMPLES Next, the present invention will be described more specifically by showing Examples and Comparative Examples of the present invention.

(Example 1) Preparation of solid catalyst component In a well-dried 10-necked four-necked flask, dehydrated and refined n
-Hexane 5, magnesium diethoxide 500g (4.4m
ol) and diisopropyl phthalate 94.6g (0.34mol)
Was added and the reaction was carried out under reflux for 1 hour. Then, the temperature was raised to 90 ° C., 2.5 kg (132 mol) of titanium tetrachloride was added dropwise over 50 minutes, and the reaction was further performed at 90 ° C. for 2 hours. Then, the temperature was raised to 30 ° C., the supernatant was removed, n-heptane 7 was added and stirred, and the mixture was allowed to stand, then the supernatant was removed, and this operation was repeated twice for washing. Then, n-heptane 5 was newly added, the temperature was raised to 70 ° C., 2.5 kg (132 mol) of titanium tetrachloride was added dropwise, and the mixture was heated at 90 ° C. for 2 hours.
A time reaction was performed. Then, the temperature was adjusted to 80 ° C., the supernatant was extracted, and n-heptane 7 was added to wash. The washing was repeated until chlorine ions were no longer detected, and a solid catalyst component was obtained. When the amount of supported titanium was measured by a colorimetric method, it contained 2.6% by weight of titanium.

Preparation of catalyst The solid catalyst component obtained above was diluted to 2 mmol Ti / l and charged into a catalyst preparation tank. The catalyst preparation tank was supplied with 30 mmol / triisobutylaluminum and 12 mmol / l 1,8-cineole. After that, per 1 mmol of titanium
Propylene was supplied at a rate of 50 g. The temperature inside the catalyst preparation tank was raised to 40 ° C., and the reaction for catalyst preparation was carried out.

Production of butene-1 homopolymer Using a fluidized bed polymerizer having a diameter of 300 mm and a volume of 100, the catalyst obtained above was re-prepared to 3.6 mmol / in terms of Ti atom. At a flow rate of 0.15 / hr. And triisobutylaluminum at 60 mmol / hr.
At a flow rate of 1.8-cineole and a flow rate of 24 mmol / hr.

Adjust the partial pressure of butene-1 to 3 kg / cm ² and the partial pressure of nitrogen to 4 kg / cm ² , and supply butene-1 and N ₂ gas so that the gas superficial velocity is 35 cm / sec. did. The polymer discharge was adjusted so that the amount of polymer in the polymerizer was constant.

The polymerization temperature was 60 ° C.

Intrinsic viscosity [η], II, bulk density, residual titanium (analytical method; fluorescent X-ray method), residual chlorine (analytical method: fluorescent X-ray method), creep resistance (in accordance with ASTM D2990) of the obtained polymer The results are shown in Table 1.

(Example 2) The supply flow rate of the Ti catalyst slurry was 0.075 / hr., And the hydrogen partial pressure was
Gas phase polymerization was performed in the same manner as in Example 1 except that the amount was 0.06 kg / cm ² .

Table 1 shows various properties of the obtained polymer.

(Example 3) Preparation of solid catalyst component A solid catalyst component was prepared in the same manner as in Example 1 above.

Preparation of catalyst A catalyst was prepared in the same manner as in Example 1.

Production of Propylene-Butene-1 Copolymer Propylene and hydrogen are newly supplied to the polymerization vessel and the propylene partial pressure is 0.3 kg / cm ² , and the hydrogen partial pressure is 0.0
A propylene-butene-1 copolymer was produced in the same manner as in Example 1 except that the rate was adjusted to 9 kg / cm ² . The various properties are shown in Table 1.

(Example 4) Preparation of solid catalyst component In a glass container of 5 substituted with argon, calcined silicon oxide (manufactured by Fuji Davison, grade 952, specific surface area 350 m ²
/ g, average particle size 54-65 μm) (500 g) and trimethylchlorosilane 1.5 were added and reacted under reflux with stirring for 12 hours, followed by decantation with n-heptane 5 times and drying.

Diethoxy magnesium (2500 mm
ol) and n-heptane solution 2.5 containing tetra-n-butoxytitanium (1500 mmol) were added, and the mixture was contacted at room temperature for 1 hour. Thereafter, 1250 ml of isopropanol was added dropwise, the mixture was stirred at 80 ° C. for 1 hour, decantation was repeated 3 times with n-heptane 5, and dried under reduced pressure at 80 ° C. for 1 hour to obtain a white catalyst carrier. The catalyst carrier contained 3.3% by weight of magnesium atoms.

375 g of the catalyst carrier thus obtained was placed in a glass container (5), and then n-heptane (2.5), diisobutylphthalate (95 mmol) and titanium tetrachloride (2250 g) were placed. The mixture was stirred for 2 hours at 90 ° C. Then, the supernatant was removed by decantation, and the solid portion obtained was thoroughly washed with hot n-heptane to obtain a solid catalyst component.
This catalyst contained 3.2% by weight of Ti.

Preparation of catalyst A catalyst was prepared in the same manner as the preparation of the catalyst in Example 1 above.

Production of Butene-1 Homopolymer Butene-1 homopolymer was produced in the same manner as the gas phase polymerization in Example 1. Table 1 shows various properties of the obtained polymer.

Comparative Example 1 Preparation of Solid Catalyst Component The same procedure as in Example 1 was performed.

Preparation of catalyst The procedure of Example 1 was repeated except that 1 mmol / mol of diphenyldimethoxysilane was used instead of 1.8-dineol.

Production of Butene-1 Homopolymer The same procedure as in Example 1 was repeated except that diferdimethoxysilane was supplied at a flow rate of 3 mmol / hr. Instead of freshly supplied 1.8-cineole.

Various properties of the obtained butene-1 homopolymer are shown in Table 1. Further, this butene-1 homopolymer has very poor hue and low stereoregularity, so that it has no commercial value when formed into a pipe. Furthermore, since the powder property of the obtained polymer is bad, it was difficult to continuously operate the polymerization apparatus.

Comparative Example 2 Preparation of Solid Catalyst Component The same procedure as in Example 1 was carried out.

 Preparation of catalyst The procedure of Comparative Example 1 was repeated.

Production of Butene-1 Polymer The same procedure as in Comparative Example 1 was carried out except that hydrogen was additionally supplied at a flow rate of 0.02 kg / cm ² .

Since the obtained polymer has a small molecular weight and a large amount of residual metal, it could not be used at all as a material for pipes.

Comparative Example 3 Preparation of Solid Catalyst Component The same procedure as in Example 1 was performed.

 Preparation of catalyst component The same procedure as in Example 1 was performed.

Production of butene-1 homopolymer Ti catalyst slurry flow rate was 0.27 / hr. And polymerization temperature was 40
℃ and outside in which the partial pressure of butene-1 and 2 kg / cm ² was carried out in the same manner as in Example 1.

The obtained polymer contained a large amount of residual metal and was unsuitable as a material for pipe molding.

(Comparative example 4) Preparation of solid catalyst component It carried out like Example 1 above.

 Preparation of catalyst component The same procedure as in Example 1 was performed.

Production of butene-1 homopolymer Ti catalyst slurry flow rate was 0.48 / hr. And polymerization temperature was 75
The same procedure as in Example 1 was carried out except that the temperature was set to ° C.

The obtained polymer had a small molecular weight and a large amount of residual metal, and could not be used as a material for pipe molding.

(Comparative Example 5) Preparation of solid catalyst component In a well-dried 10-necked four-necked flask, dehydrated and refined n
-Hexane 5, magnesium chloride 500g (4.4mol) and ethyl benzoate 132g (0.38mol) were added and refluxed to 1
A time reaction was performed. Then, the temperature was raised to 70 ° C., 4.2 kg (22 mol) of titanium tetrachloride was added dropwise over 50 minutes, and the reaction was further performed under reflux for 3 hours. Then, the temperature was adjusted to 30 ° C., the supernatant was removed, n-heptane 7 was added, and the mixture was stirred, allowed to stand and then the supernatant was removed, and this operation was repeated twice for washing. After that, new n-hexane 5 was added to bring the temperature to 70 ° C., and titanium tetrachloride 4.2 k
g (22 mol) was added dropwise over 30 minutes, and the mixture was reacted under reflux for 3 hours. Then, the temperature was adjusted to 80 ° C., the supernatant was extracted, and n-heptane 7 was added to wash. The washing was repeated until chlorine ions were no longer detected, and a solid catalyst component was obtained. When the amount of supported titanium was measured by a colorimetric method, it contained 2.6% by weight of titanium.

The average particle size of the solid catalyst component was 20 μm, and the geometric standard deviation σg of the particle size distribution was 1.8.

 Preparation of catalyst The procedure was as in Example 1 above.

Production of butene-1 homopolymer Re-prepared Ti catalyst slurry at a flow rate of 0.15 / hr. And triisobutylaluminum at a flow rate of 160 mmol / hr.
Methyl toluate 7.5 mmol / h instead of 1.8-cineole
It was carried out in the same manner as in Example 1 except that the flow rate was supplied to the flow rate bed polymerizer at a flow rate of r. and the partial pressure of newly added hydrogen was adjusted to 0.15 kg / cm ² .

Various properties of the obtained polymer are shown in Table 1.

[Brief description of drawings]

FIG. 1 is a flow chart showing catalyst preparation and polymerization.

Claims (1)

[Claims] 1. In the presence of a catalyst obtained from a solid catalyst component (A) obtained from a magnesium compound, a carboxylic acid ester and a halide of tetravalent titanium, an organoaluminum compound (B) and an electron donating compound (C). , Butene-1 homopolymer or butene-
In the method for producing a copolymer of 1 and an α-olefin other than this, the magnesium compound is represented by the formula Mg (OR) ₂ (1) (wherein, R is a straight chain having 1 to 10 carbon atoms). Represents an alkyl group, a cycloalkyl group, an aryl group and an aralkyl group having a ring-like or side chain), and the electron-donating compound (C) is represented by the formula: (In the formula, R ¹ and R ⁴ represent a hydrocarbon group, and R ² , R ³ and R ⁵ represent hydrogen or a hydrocarbon group, respectively). As a condition, a reaction temperature is 45 to 70 ° C., a method for producing a butene-1 polymer.