JPS596205A - Production of poly-1-butene - Google Patents

Abstract

PURPOSE:To obtain poly-1-butene stably at a high polymerization rate with a long running time of the continuous operation, by prepolymerizing propylene in the presence of a specified Ziegler catalyst and then polymerizing at least a portion of the 1-butene in a vapor phase. CONSTITUTION:Poly-1-butene is obtained by polymerizing 1-butene in the presence of a Ziegler catalyst which comprises (A) a highly active solid titanium catalytic component containing magnesium, titanium, a halogen and an electron donor and having an average particle diameter of 1-200mu and a geometric standard deviation sigmag of the particle diameter distribution, of below 2.1, (B) an organoaluminum compound catalytic component and optionally (C) an electron-donating catalytic component. 0.1-1,000g, per 1mmol of titanium in the solid catalytic component (A), of propylene is prepolymerized prior to the polymerization of 1-butene; and at least a portion of the 1-butene is polymerized at 40-100 deg.C in a vapor phase.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing poly-1-butene by gas phase polymerization.

Conventionally, many proposals for producing highly crystalline poly-1-butene have involved slurry polymerization using a titanium trichloride catalyst as a catalyst. On the other hand, if poly-1-butene can be produced by gas phase polymerization, the process can be simplified and production costs can be expected to be reduced.

For this reason, there have been many proposals in the past suggesting the usability of gas phase polymerization of 1-butene, but there were many problems in actually conducting it on an industrial scale. For example, poly-1-butene has a stronger affinity for hydrocarbon solvents than polyethylene or polypropylene, and if a small amount of liquid component is present in the gas phase polymerization system, the polymers tend to coagulate together, and therefore, as a gas phase polymerization In polymerization using the most typical fluidized bed or stirred fluidized bed, it has been difficult to operate stably for a long period of time. This is especially true when 1-butene, which is easily liquefied, is present in a low-fat liquid state, and the catalyst or catalyst components are often dissolved or suspended in an inert solvent before being supplied to the gas phase combination system. When there was a small amount of inert solvent entrained in the solution, the above-mentioned agglomeration tendency was noticeable. Moreover, such a tendency was particularly remarkable in polymerization at a temperature of 40"C or higher, which is an industrially advantageous polymerization temperature. Furthermore, when gas phase polymerization is carried out using the titanium trichloride catalyst that has been widely used in the past, the catalyst shape is not good, resulting in poor fluidity, similarly poor polymerization operability, and low catalytic activity. However, deashing treatment had to be performed after polymerization, making the operation complicated, and the advantages of gas phase polymerization could not be fully utilized.

The present inventors have improved the above-mentioned drawbacks in the gas-phase polymerization of 1-butene, and achieved a method that has high catalytic activity, a fast polymerization rate, good polymerization operability even at relatively high temperatures, and stable long-term continuous operation. As a result of studying possible methods, we have arrived at the present invention. That is, the present invention provides a method for producing poly-1-butene by polymerizing 1-butene in the presence of a Ziegler-type catalyst, in which (Δ) magnesium, titanium, halogen, and an electron polymer are used as the Ziegler-type catalyst. A catalyst formed from a highly active solid titanium catalyst component which is contained as an essential component and has an average particle size of 1 to 200/N and a geometric standard deviation of particle size distribution σg of less than 2.1, and a (BJ organoaluminum compound catalyst component) 0 per mmol of titanium in the solid catalyst component (A) prior to the polymerization of 1-butene.
．． A method for producing poly-1-butene, which comprises prepolymerizing 1 to 1000 g of propylene, and polymerizing at least a portion of the 1-butene in a gas phase at a temperature of 4° to 100°C. It is.

The solid titanium catalyst component (A) used in the present invention contains magnesium-titanium, halogen, and an electron donor as essential components, and the magnesium/titanium (atomic ratio) is preferably 2 to 10, particularly preferably 4
or 70. The halogen/titanium (original r-ratio) is preferably from flea to 100, particularly preferably from flea to 40. The electron donor/titanium (molar ratio) Qf is preferably in the range from 0.2 to 10, particularly preferably from 0.4 to 6. Its specific surface area is 9I or 7. m/g or more”
-1 is more preferably about 40 m/g or more, and even more preferably 1 oom/g to 8 [] Om/g. Normally, titanium compounds are not removed by simple means such as washing with Hegisan at room temperature. The χ-ray spectrum of the magnesi-cum compound, regardless of the raw material magnesium compound used for the preparation of the catalyst, or desirably shows a very poor quality compared to that of an ordinary commercially available magnesium cybaride. It is in a crystallized state.

Solid titanium catalyst component (10 means average particle size of 1 to 2
00/7. It is preferably 5 to 10,071s, particularly preferably 8 to 5,071s, and the geometric standard deviation of the particle size distribution is less than 2.1, preferably 1.95 or less.

Here, the particle size distribution of the titanium catalyst component particles can be measured by a light transmission method. Specifically, the catalyst component is diluted in an inert solvent such as decalin to a concentration of around 0.01 to 0.5%,
The particle size distribution is measured by placing the liquid in a measurement cell, shining a narrow light into the cell, and continuously measuring the intensity of the light passing through the liquid when the particles are in a settled state. Based on this particle size distribution, the standard deviation σ
g is determined from a lognormal distribution function. The average particle diameter of the catalyst is indicated by the weight average diameter, and the measurement of particle size distribution is as follows:
Sieving was carried out within a range of 10 to 20% of the weight average particle diameter, and the calculation was made.

If a solid catalyst component with an average particle size smaller than the above range is used, problems such as agglomeration of the polymer or entrainment to waste threads in the polymerization tank are likely to occur, which is undesirable. If a polymer is used, the fluidization state in the fluidized bed or the like deteriorates, causing adhesion to the vessel wall and agglomeration of the polymer, making it difficult to carry out uniform polymerization. In addition, the geometric standard deviation σg of the particle size distribution is 2.1 or more.'' If particles with such a wide distribution are used, problems such as deterioration of fluidity, polymer aggregation, and wall adhesion are likely to occur, resulting in problems in terms of operation and polymer quality. Undesirable. The titanium catalyst component is preferably spherical, such as a true sphere or an elliptical sphere.

The highly active solid titanium catalyst component (/yamama) may contain other elements, metals, functional groups, etc. in addition to the above essential components. It may also be diluted with an inorganic or organic diluent. .The component (A) also contains about 10% of titanium per mmol.
It is desirable to have a high performance capable of producing highly stereoregular poly-1-butene of 0.00 g or more.

A titanium catalyst component (
A) is, for example, a method in which a catalyst is prepared after forming a magnesium compound having an average particle size and particle size distribution, more preferably a shape as described above, or a method in which a liquid magnesium compound and a liquid titanium compound are formed. It can be obtained by a method of bringing compounds into contact to form a solid catalyst with particle properties as described above. Such methods are described, for example, in Japanese Patent No. 1iF) No. 55135102, No. 55-135103, No. 56-811, No. 56-6.
No. 7511, etc.

A few examples of these methods will be briefly described.

(1) A magnesium compound/electron donor complex with an average particle diameter of 1 to 200μ and a geometric standard deviation σg of particle size distribution of less than 2.1 is used as an electron donor and/or an organoaluminum compound or a halogen-containing silicon compound. The reaction is carried out with a halogenated titanium compound, preferably titanium tetrachloride, which forms a liquid phase under the reaction conditions, with or without pretreatment with a reaction aid.

(2) A liquid magnesium compound that does not have reducing ability and a liquid titanium compound are reacted in the presence of an electron donor, and the average particle diameter is 1 to 20071° and the geometric standard deviation σg of the particle size distribution is less than 2.1. The solid component of is precipitated. If necessary, it is further reacted with a liquid titanium compound, preferably titanium tetrachloride, or with an electron donor.

Magnesium compounds used in the preparation of the titanium catalyst component include magnesium oxide, magnesium hydroxide, hydrotalcite, magnesium carboxylate, alkoxymagnesium, allyloxymagnesium, alkoxymagnesium halide, allyloxymagnesium halide, magnesium cybaride, Examples include organomagnesium compounds, reaction products of organomagnesium compounds and electron donors, halosilanes, alkoxysilanes, cytenol, aluminum compounds, and the like.

The organoaluminum compound that may be used in the preparation of the titanium acid medium component described above can be selected from the organoaluminum compounds that can be used in the olefin polymerization described below. Further, halogen-containing silicon compounds that may be used for preparing the titanium catalyst component include silicon tetrahalides, silicon alkoxy halides, silicon argyl halides, and halopolysiloxanes.

The titanium compound used for preparing the titanium catalyst component may be titanium tetrahalide, alkoxytitanium halide, allyloxytitanium halide, alkoxytitanium, allyloxytitanium, etc. Among titanium tetrahalides, titanium tetrachloride is particularly preferred.

Electron donors that can be used to produce titanium catalyst components include alcohols, phenols, ketones, aldehydes,
Carboxylic acids, esters of organic or inorganic acids, ethers,
Oxygen-containing electron donors such as acid amides, acid anhydrides, and alkoxysilanes, nitrogen-containing electron donors such as ammonia, amines, nitriles, and isocyanates, and the like can be used.

More specifically, methanol, ethanol, propatool, pentanol, hexanol, A lid/-/l/,
Dodecanol, octadecyl alcohol, benzyl alcohol, phenylethyl alcohol, cumyl alcohol, isopropylbenzyl 7/l/:7-ruf (alcohols with 1 to 18 carbon atoms: phenol, cresol, xylenol, ethylphenol, propylphenol) , nonylphenol, cumylphenol, naphthol, etc., which may have a lower alkyl group and have 6 to 2 carbon atoms.
Phenols of o; Ketones having 6 to 15 carbon atoms such as acetatone, methyl ethyl ketone, methyl isobutyl ketone, acetophenone, and benzophenone: acetaldehyde, propionaldehyde, dikudylartehyde 1,
Aldehydes having 2 to 15 carbon atoms such as benzaldehyde, trialdehyde, and naphthaltehyde; methyl formate, methyl acetate, ethyl acetate, vinyl acetate, furovir acetate, octyl acetate, cyclohegycyl acetate, ethyl propionate, methyl butyrate, etynopecyl valerate, methyl acetate ,
Ethyl dichloroacetate, methyl methacrylate, ethyl crotonate, ethyl cyclohexanecarboxylate, methyl benzoate, ethyl benzoate, benzoate, propyl succinate, ben, @, butyl frate, octyl benzoate, cyclohexyl benzoate, benzoate phenyl acid, hensyl benzoate, methyl toluate, ethyl toluate, amyl toluate, ethyl ammonium, e, ethyl frate, methyl anisate, ethyl anisate,
Organic acid esters having 2 to 30 carbon atoms, such as ethyl ethoxybenzoate, diisobutyl phthalate, diethyl phthalate, di2-ethylhexyl phthalate, γ-butyrolactone, δ-valerolactone, coumarin, phthalide, and ethylene carbonate; acetyl chloride , C2-C15 acid halides such as benzoyl chloride, toluyl chloride, anisyl chloride; C2-C20 acid halides such as methyl ether, ethyl ether, isopropyl ether, butyl ether, amyl ether, tetrahydrofuran, anisole, diphenyl ether, etc. Ethers; Acid amides such as acetic acid amide, benzoic acid amide, and toluic acid amide; Amines such as methylamine, ethylamine, diethylamine, tributylamine, piperidine, tribenzylamine, aniline, pyridine, picoline, and tetramethylethylenediamine; Nitriles such as tonitrile, benzonitrile and trinitrile; alkoxysilanes such as ethyl silicate and diphenyldimethoxysilane; and the like. Two or more types of these electron donors can be used.

Electron donors preferably contained in the titanium catalyst component include organic or inorganic acid esters, ethers, ketones,
Those having no active hydrogen such as tertiary amines, acid halides, acid anhydrides, and alkoxysilanes are particularly preferred, and organic acid esters are particularly preferred, with aromatic carboxylic acid esters being the most preferred. Representative examples of suitable aromatic carboxylic acid esters include those having 8 to 24 carbon atoms, particularly alkyl esters such as benzoic acid, lower alkylbenzoic acid, lower alkoxybenzoic acid, and phthalic acid.

The organoaluminum compound (B) used in the present invention is
Compounds having at least one t4-carbon bond in the molecule can be used, such as (1) a hydrocarbon group containing usually 1 to 15, preferably 1 to 4 atoms, which may be the same or different from each other. It's okay.

X is halogen, m is [1<m≦6, n is D≦n<3
, p is a number of 0≦p<3, q is a number of 0≦q<3, and m + n + p + q = 3) (11) General formula M'A/R2
(Here, Ml is Li.

Na, and R1 is the same as above)
Examples include complex alkylated products of group metals and aluminum.

As the organoaluminum compound belonging to the above (1), -cooked ones can be exemplified. General formula R4A, 0CoR2
), -m (where R1 and R2 are the same as above. m is preferably a number of 1.5≦m≦6. General formula R',
, Aiχ3-m (wherein R1 is the same as above.
l+ is preferably 2≦m<3), the general formula “ ” (
OR2) nxq (Same as above.x is halogen, 0<m≦6, D≦n<3.0≦q
, < 3, and m 10n 10p + q = 3)
Examples include those expressed as .

Among aluminum compounds belonging to (1), more specifically, trialkylaluminum such as triethylaluminum and tributylaluminium, trialkenylaluminum such as triisoprenylaluminum, dialkylaluminum alkoxide such as diethylaluminum ethoxide, diptylaluminum butoxide, etc. , ethylaluminum sesquiethoxide, butylaluminum sesquibutoxide, as well as alkylaluminum heptase alkoxides, as well as Aβ25Ae (OR2).

Partially alkoxylated alkylaluminiums having an average composition such as Alkylaluminum sesquihalides like sesquipromide, partially halogenated alkyl aluminum such as alkyl aluminum cybarides like edyl aluminum dichloride, propyl aluminum dichloride, butyl aluminum bromide etc., diethylaluminum hydride, dibutyl aluminum Dialkyl aluminum hydride such as hydride, partially hydrogenated alkyl aluminum such as ethyl aluminum dihydride, alkyl aluminum halide such as probyl aluminum dihydride, ethyl aluminum ethoxy chloride, butyl aluminum butoxy chloride, ethyl aluminum ethoxy promide Partially alkoxylated and norogenated alkylaluminums such as Moreover, as a compound similar to (1), an organic aluminum compound in which two or more aluminum atoms are bonded via an oxygen atom or a nitrogen atom may be used. Examples of such compounds include (C2Hs) 2A (l OA
l (C2Hs) 2, etc. can be exemplified. Said (
As a compound belonging to 11), LiA e(C2H
Examples include s) 4 and LiA5(C7)T15) 4. Among these, it is particularly preferable to use trialkylaluminum or a mixture of trialkylaluminum and alkyl aluminum halide or aluminum rhamno1lide.

In the polymerization of the present invention, an electron donor catalyst component (C) is preferably present in addition to the components (A) and (B).

Suitable examples of the electron donor catalyst component (C) that can be used in the polymerization include esters of organic or inorganic acids, ethers, ketones, tertiary amines, acid rides, acid anhydrides, and alkoxysilanes. Available. Particularly suitable are organic acid esters and alkoxysilanes, and among them aromatic carboxylic acid esters. As representative examples of such aromatic carboxylic acid esters, those having 8 to 18 carbon atoms are preferred, and esters of benzoic acid, lower alkylbenzoic acid, and lower alkoxybenzoic acid are particularly preferred. Specific examples of these include, for example, the above-mentioned electron donors that can be used in preparing the solid titanium catalyst component (A) 1.4.

Such an electron donor (C) may be used by forming a complex with an organoaluminum compound before use, or may be used by forming a complex with a Lewis acid such as aluminum chloride. .

In the present invention, propylene is 0.1 to 1000 g, preferably 1 to 500 g, per 1 m+no 1 of titanium in the titanium catalyst component (/1) used for polymerization of 1-butene.
g is prepolymerized to produce polypropylene on the catalyst component (A). The presence of the organoaluminum compound catalyst component (B) is of course necessary in the prepolymerization treatment, but it is not necessary to use the entire amount used in the polymerization of 1-butene at this stage; for example, titanium in component (A) 1 m
CB) component per mo1 in terms of aluminum atom is 0.
5 to 1. It may be used at a ratio of about 0.0mmo]. Furthermore, when the electron donor catalyst component (C) described above is used in the polymerization of 1-butene, part or all of it may be present in this prepolymerization step, but the amount is limited to an amount that does not deactivate the catalyst. For example, the amount of component (C) can be in the range of 0 to 1.0 mmol per mmol of aluminum in component (13), although it varies depending on the type. The prepolymerized amount of propylene is preferably about o, ooi to 10% by weight, particularly 0.01 to 1% by weight, in the poly-1-butene to be produced.

If the amount of propylene prepolymerized is too small, or if an olefin other than propylene is prepolymerized, an unsatisfactory effect on agglomeration of poly-1-butene particles during gas phase polymerization will not be exhibited. On the other hand, if the amount of propylene prepolymerized is too large, the excellent properties of poly-1-butene will no longer be maintained, so it should be avoided, but if the amount is appropriate, such as in duplicate, the operability in gas phase polymerization will be remarkable. Not only is the physical property of poly-1-butene improved to a certain extent, but also the crystal transformation rate of poly-1-butene can be accelerated.

Prepolymerization of propylene is preferably carried out in an inert solvent. Suitable examples of inert solvents include, for example, bronogun,
These include butane, pentane, hegizane, heptane, Amethane, tecan, kerosene, etc. To such inert solvent 14, approximately 0.5 to 5 mmol of the titanium catalyst component, the organoaluminum compound catalyst component (T3), and the electron donor catalyst component (C) which may be used as necessary are added in the proportions described above. It is usually good to polymerize propylene at about 0 to 50''C.

At this time, a small amount of other a-A fins may be copolymerized as long as high crystalline polypropylene can be produced.
Generally, it is preferable to carry out homopolymerization of propylene. Further, hydrogen may be present in order to adjust the molecular weight of polypropylene. The prepolymerization treatment may also be performed by gas phase polymerization in addition to the slurry polymerization described above. After completing the prepolymerization treatment, the polymerization mixture may be used as it is for polymerization of 1-butene, or may be subjected to operations such as concentration and drying before being used for polymerization of 1-butene.

According to the present invention, gas phase polymerization of 1-butene is performed using a catalyst prepolymerized with propylene, but prior to this gas phase polymerization, a step of slurry polymerization of 1-butene is provided. Good too. However, in this case, it is preferable that 10% or more of the total amount of 1-butene be polymerized by gas phase polymerization.

The gas phase polymerization of 1-butene is carried out at a temperature of 4o to 1oo"c1, preferably 50 to 80"C. At temperatures lower than 40"C, the partial pressure of 1-butene cannot be increased too high to prevent liquefaction, so the polymerization rate cannot be increased sufficiently, and it is difficult to remove the polymerization heat industrially. This is not preferred because it is not easy to carry out. Furthermore, high polymerization temperatures exceeding 100°C are not preferred because poly-1-butene particles tend to aggregate or stick to walls, making it difficult to carry out a smooth polymerization operation.

The catalyst concentration in the gas phase polymerization system is o, o o i to Q, 8 mmol in terms of titanium atoms per polymerization volume of 14,
In particular, 0.005 to 0.7 mmol of titanium catalyst component (A) and 4 to 100010 mmol of titanium in component (A) in terms of aluminum atoms.
0 O, in particular 5 to 400 mmol] of the organoaluminium compound catalyst component (13), and an electron donor catalyst component of 0 to 0.0 O, in particular 0.05 to 0.511 mol, per mmol of aluminum atom in component (B). A polymer component prepolymerized and containing at least components (A) and (B) in an amount corresponding to (C), and an additional amount of component (B) and/or component (
C).

The partial pressure of 1-butene varies depending on the polymerization temperature, but is within a range where liquefaction does not occur in a substantial amount, and is usually between 1 and 1.
It is about 5kQ/(7). During polymerization, a small amount of other A
A highly crystalline, highly stereoregular 1-butene copolymer containing 1-butene as a main component may be produced by coexisting a reflex. Further, a molecular weight regulator such as hydrogen may be present in order to control the molecular weight. Furthermore, is there a substance with a lower boiling point than 1-butene? Gases such as nitrogen, methane, ethane, propane, etc. can also be present. The coexistence of these inert gases further reduces the tendency of the polymer to agglomerate, and also facilitates the removal of polymerization heat. The effective coexistence amount of the inert gas is 0.2 moles or more relative to 1-butene.

Gas phase polymerization can be carried out using a fluidized bed or an agitated fluidized bed. Alternatively, the reaction can be carried out while the gas component is flowing through a tubular polymerization vessel.

When performing slurry polymerization of 1-butene prior to gas phase polymerization, conditions should be selected so that poly-1-butene is not softened or dissolved by the liquid medium. As the liquid medium, it is preferable to select 1-butene itself or an easily vaporized inert hydrocarbon such as propane or butane in order to carry out gas phase polymerization in a later step, and the polymerization humidity is 0 or more.
It should be carried out at a low temperature of around 50°C. and liquid phase 14
The concentration of each catalyst component and other polymerization conditions are the same as those described for gas phase polymerization.

According to the present invention, even if a small amount of liquid components are mixed into the gas phase polymerization system along with a catalyst, there is little agglomeration of polymers or adhesion of polymers to walls despite the relatively high polymerization temperature. , stable continuous polymerization is possible. As described above, the presence of a liquid component generally accelerates the reaction rate of gas phase polymerization, and therefore can be said to be a rather preferable embodiment in the present invention.

Next, examples will be shown.

Example 1 [Catalyst synthesis] Anhydrous +, t, gC127,2 in a 200 +J flask
gs decane 23me and 2-ethylhexanol 23
After adding J and carrying out a heating reaction at 120°C for 2 hours to obtain a homogeneous solution, 1.68 m/m of ethyl benzoate was added.

Ttc, g4200+J was placed in a 40 [1 md flask, and the entire amount of the above homogeneous solution was added dropwise over 1 hour while the flask was kept cooled at 220°C, and then the temperature was raised to 80°C.

After stirring at 80'C for 2 hours, the solid part was collected by filtration,
Suspend this in 200 ml of fresh rIC14,
The mixture was stirred at ℃ for 2 hours. After the stirring was completed, the solid portion collected by hot filtration was thoroughly washed with hot kerosene and hexane to obtain a titanium catalyst component. The catalyst has T i 4.5 wt%,
Contains 60 wt% CD, 18 wt% Mg, and has an average particle size of 1
5/7, 0g1.25, specific surface area was 195m/g.

[Catalyst pretreatment]

The obtained catalyst slurry was
After resuspending in hexane at 15 mmol/l, p
- Methyl toluate was added at a concentration of 5 mriol/I2, and propylene was added at a concentration of 3 mriol/I2 per 1 g of titanium catalyst component.
The treatment was carried out at 40°C.

[Overlapping]

A fluidized bed polymerization vessel with a diameter of 500 mm and a reaction volume of 100 mm was used, and a 0.36 mmol catalyst slurry stirrer and an E1 catalyst drum, which had been readjusted to 3.6 mmol/4-hexane in terms of Tj-atoms, were used. Triethylaluminum was fed at a rate of 7.5 mmol/hr, and triethylaluminum was fed at a rate of 7.5 mmol/hr. On the other hand, 1-butene, hydrogen and nitrogen are mixed in a water bed/1-
Butene ratio, = 0. . 5, Nitsutsu/1-7・i-a (
F9 ratio, -1 ratio, gas superficial velocity is 350 n/s
It was fed at a rate of ec. The polymer was extracted so that the amount of poly-1-butene in the polymerization vessel remained approximately constant. The polymerization temperature was 72°C and the polymerization pressure was 4.1 kg/cm2. and melt index (190°C1 load 1
0A:q) 70g/10min, bulk specific gravity 390kg/m,
Filter white poly-1-butene powder with an average particle size of 34071,
5 at a rate of g/hr. The amount of aggregates with a particle size of 1 mm or more was within 1%.

Example 2 In the polymerization of Example 1, the following conditions were changed.

Amount of prepolymerization of Prohitsun...1゛1 5 per 1g of catalyst component
g Catalyst component supply amount TiCatalyst component 0.421/hr Triisobutylaluminum 45mm01/hrp-) Methyl tolyate 9 mmol/hr Supply gas...
1-Butene, hydrogen and propane Hydrogen/1-butene (mole ratio) = 0.03 Propane/1-butene (mole ratio) = 0.
8 gas superficial velocity 37>/sθC Polymerization conditions...pressure 4.7k(j/(:NG temperature
Result at 71°, bulk specific gravity 450kq/m - melt index 2
Poly-1-butene white powder with an average particle size of 290 ti was obtained at a rate of 4.2 kg/hr. Particle size is 1
There were no aggregates larger than 2 mm.

Comparative Example 1 In Example 1, when the catalyst pretreatment was omitted, the interior of the polymerization vessel melted 6 hours after the start of catalyst supply, making it impossible to operate. When the melt was examined after opening, it was found that each grain was not round and had a highly uneven surface.

Comparative Example 2 In Example 1, the catalyst pretreatment was changed from propylene to 1-butene.
Agglomerates larger than mm began to form, and after 10 hours, operation became impossible due to blockage in the line for extracting the produced powder.

When the polymerization vessel was opened, a large amount of polybutene aggregates were found directly above the dispersion plate.

To Comparative Example [Catalyst Synthesis] Commercially available anhydrous Magui chloride, 20 g of Si and Edil benzoate 6. Oml was charged in a nitrogen atmosphere into a stainless steel container with an internal volume of 800+J and an internal diameter of 100 mm containing 100 balls made of stainless steel (SO3-302) with a diameter of 15 rnm, and placed in a vibration mill device of Nocuff G. Co-pulverization was carried out for 50 hours. The obtained solid treated product was suspended in titanium tetrachloride and reacted at 100°C for 2 hours, after which the solid components were separated and washed repeatedly with hexane. A compositional analysis of the obtained solid catalyst component revealed that ri per 1 g of solid.
71mg, Mg 210+ngs chlorine 670mg,
It was 88 mg of C1 aromatic acid.

Moreover, the catalyst average particle diameter of the obtained ``1''1 catalyst component was 17.
87, the geometric standard deviation σF of the catalyst particle size distribution is 2.24,
The specific surface area of the catalyst was 185 m/g.

<Polymerization> When carried out in the same manner as in Example 2,
After some time, the polymerization humidity suddenly rose to 90'C, making it impossible to operate. When the polymerization vessel was opened, about 5 kq of molten polymer was obtained.

Applicant: Mitsui Petrochemical Industries, Ltd. Agent Yama ［''　　　　　和

Claims (1)

[Scope of Claims] (1) In a method for producing poly-1-butene by polymerizing 1-butene in the presence of a Ziegler-type catalyst, (A) magnesium, titanium, halogen, and an electron-donating The average particle size is 1 to 200 II, and the geometric standard deviation of the particle size distribution is σg.
is less than 2.1 and a highly active solid titanium catalyst component (B
) an organoaluminum compound catalyst component, and prior to the polymerization of 1-butene, the solid catalyst component (0.1 to 100
While prepolymerizing 0g of propylene, 1-
At least a portion of the butene is at a temperature of 40 to io o C.
Polymerization is carried out in a gas phase at a temperature of
Method for producing 1-butene. (2) A claim in which the polymerization of 1-butene is carried out entirely in a gas phase (method described in 2). (3) A claim in which the polymerization of 1-butene is first carried out in a slurry state and then in a gas phase ( 1) The method described.