JPS63302A - Production of butene-1 polymer - Google Patents

Abstract

PURPOSE:To obtain the title polymer excellent in stereoregularity and small in a content of catalyst residues, by subjecting butene-1 together with, optionally, other alpha-olefin to vapor phase polymerization in the presence of a specified catalyst. CONSTITUTION:A magnesium compound (a) which is a magnesium dialkoxide of formula I (wherein R is a 1-10C linear or branched alkyl, cycloalkyl, aryl or aralkyl) is contacted with an electron donor (b) and a tetravalent titanium halide (c) at 0-200 deg.C for 2min-24hr in a solvent to obtain a solid catalyst component (A) of a halogen/Ti (molar ratio) of 3-200 and a Mg/Ti (molar ratio) of 1-90. Component A is contacted with an organoaluminum compound (B) and an electron-donating compound (C) which is a heterocyclic compound of formula II (wherein R<1> and R<4> are each hydrocarbon and R<2>, R<3> and R<5> are each H or R<1>) to obtain a catalyst. Butene-1 together with, optionally, other olefin is subjected to vapor phase polymerization at 45-70 deg.C in the presence of this catalyst.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] This invention relates to a method for producing butene-1 polymers. More specifically, in the presence of highly active catalysts.

The present invention relates to a method for producing a butene-1 polymer, which is suitable for molding, for example, noxib, by taking advantage of gas phase polymerization.

[Prior Art and its Problems] Conventionally, as a method for producing a highly crystalline polybutene-1 polymer, there have been many proposals for carrying out 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 predicted that the process can be simplified and the production cost can be reduced. For this reason, there have been proposals suggesting the feasibility of gas phase polymerization of butene-1. However, there are various problems in implementing the proposed method on an industrial scale.

For example, butene-1 polymers have a stronger affinity for hydrocarbon solvents than polyethylene or polypropylene; therefore, when feeding the catalyst component to a gas phase polymerization system,
When a small amount of solvent is entrained, the polymers tend to aggregate together. As a result, it becomes difficult to perform long-term stable operation or operation of the device.

In addition, gas phase polymerization is carried out using titanium trichloride-based catalysts (see JP-A-60-192718), magnesium chloride-based catalysts (see JP-A-59-8205), etc., which have been widely used in the past. As a result, the catalytic activity was low, and the stereoregularity of the butene-1ffi polymer obtained was insufficient, making it impossible to fully utilize the advantages of the gas phase polymerization method.

[Object of the Invention] An object of the present invention is to provide a method for producing butene-1 polymer using a highly active polymerization catalyst.

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

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

Still another object of the present invention is to provide a method for producing a butene-1 polymer that can be suitably molded into molded articles such as pipes under stable operating conditions.

[Means for achieving the above object] The gist of the present invention for achieving the above object is to provide a solid catalyst component (A) obtained from a magnesium compound, an electron donating compound and a halide of tetravalent titanium, an organoaluminum compound ( Butene-1 under gas phase polymerization conditions in the presence of a catalyst obtained from B) and an electron-donating compound (C).
In the method for producing a homopolymer or a copolymer of butene-1 and other α-olefin, the magnesium compound has the formula Mg(OR)2() (wherein R has 1 carbon number) It is a magnesium dialkoxide represented by (representing an alkyl group, cycloalkyl group, aryl group, or aralkyl group having a linear or side chain of -10), (wherein R1 and R4 are hydrocarbon groups) ) i
2, R3 and R5 each represent hydrogen or a hydrocarbon group.

The method for producing a butene-1 polymer is characterized in that the gas phase polymerization conditions include a reaction temperature of 45 to 70°C.

In the method of this invention, as shown in FIG. 1, a specific solid catalyst component (A
), butene-1 homopolymer or butene-1 and other polymers under specific gas phase polymerization conditions in the presence of a catalyst obtained from an organoaluminium compound (B) and a specific electron-donating compound (C). A copolymer of α-olefin is produced.

Regarding one solid catalyst component (A) - The solid catalyst component (A) is made from a specific magnesium dialkoxide, an electron-donating compound, and a tetravalent titanium halide.

This particular magnesium dialkoxide is.

With the formula Mg (OR) 2 (1) (wherein R represents an alkyl group having a linear or side chain having 1 to 10 carbon atoms, a cycloalkyl group, an aryl group, and an aralkyl group) shown.

If a magnesium compound other than the formula (1), such as magnesium chloride, is used, the catalytic activity will be low and the amount of residual chlorine in the produced polymer will increase, resulting in the problem of corrosion of the molding machine.

Specific examples of the magnesium dialkoxide represented by the formula (1) include Mg (-QCH3)2.
Mg(-0C2H5)z, Mgc-OC3H7)2,
Mg (-QCs HQ)2, ME(-0C6
HI3)? , Mg (-QCs HI7)2, Mg
(-0CC3) (-0C2Hs).

The above-mentioned various magnesium dialkoxides can be used alone, or a plurality of types of magnesium dialkoxides are preferred, and magnesium jetoxide and magnesium jetoxide are particularly preferred.

As the electron-donating compound that is the raw material for the solid catalyst component (A), an organic compound containing oxygen, nitrogen, phosphorus, or sulfur can be used.

Examples of this electron-donating compound include amines,
Examples include amides, ketones, nitriles, phosphines, phosphoramides, esters, ethers, thioethers, thioesters, #anhydrides, acid halides, acid amides, aldehydes, and organic acids.

More specifically, organic acids such as aromatic carboxylic acids such as benzoic acid and p-oxybenzoic acid; acid anhydrides such as succinic anhydride, benzoic anhydride, and p-toluic anhydride;
Ketones with 3 to 15 carbon atoms such as acetone, methyl ethyl ketone, methyl isobutyl ketone, acetophenone, benzophenone, and benzoquinone; aldehydes with 2 to 15 carbon atoms such as acetaldehyde, propionaldehyde, octylaldehyde, benzaldehyde, tolualdehyde, and naphthaldehyde; Methyl formate, methyl acetate,
Ethyl acetate, vinyl acetate, f#=propyl acid, octyl acetate, cyclohegycyl acetate, ethyl propionate, ethyl acetate, ethyl valerate, methyl chloroacetate, ethyl dichloroacetate, methyl methacrylate, ethyl crotonate, ethyl pivalate, maleic acid Dimethyl acid, ethyl cyclohexanecarboxylate, methyl benzoate, ethyl benzoate,
Propyl benzoate, butyl benzoate, octyl benzoate, cyclohexyl benzoate, phenyl benzoate, benzyl benzoate, methyl toluate, ethyl toluate, amyl toluate, ethyl ethylbenzoate, methyl anisate, ethyl anisate.

Monoesters such as ethyl ethoxybenzoate, ethyl p-butoxybenzoate, ethyl 0-chlorobenzoate and ethyl naphthoate, or dimethyl phthalate, diethyl phthalate, dipropylphthalate, diimbutyl phthalate, methylethyl phthalate, methylpropylphthalate, Methyl isobutyl phthalate, ethyl propyl phthalate, ethyl isobutyl phthalate, propyl imbutyl 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 inphthalate, diisobutyl isophthalate, methyl ethyl isophthalate, methylpropyl isophthalate, methyl isobutyl isophthalate, ethylpropyl isophthalate, ethyl imbutyl isophthalate and propyl isobutyl isophthalate Aromatic diesters such as phthalates, γ-butyrolactone, δ-
C2-18 esters such as valerolactone, coumarin, phthalide, and ethylene carbonate; acetyl chloride;
A2-15 carbon acid halides such as benzyl chloride, toluyl chloride, anisyl chloride; methyl ether, ethyl ether, isopropyl ether, n-butyl ether, amyl ether, tetrahydrofuran,
Ethers having 2 to 20 carbon atoms such as anisole, diphenyl ether, and ethylene glycol butyl ether; acid amides such as acetic acid amide, benzoic acid amide, and toluic acid amide; nitributylamine, N,N'-dimethylpiperazine, tribenzylamine, aniline; Examples include amines such as pyridine, picoline, and tetramethylethylenediamine; and nitrites such as acetonitrile, benzonitrile, and tolnitrile.

Among these, preferred are esters, ethers, ketones, acid anhydrides, and the like. In particular, alkyl esters of aromatic carboxylic acids, such as benzoic acid, p-methoxybenzoic acid, p-ethoxybenzoic acid, alkyl esters of aromatic carboxylic acids having 1 to 4 carbon atoms, such as toluic acid, aromatic diesters, such as phthalic acid. Diisobutyl is preferred, and aromatic ketones such as benzoquinone, aromatic carboxylic acid anhydrides such as benzoic anhydride, and ethers such as ethylene glycol butyl ether are also preferred.

Specifically, the tetravalent titanium halide, which is one of the raw materials for the solid catalyst component (A), is TiCua
, TiBr*, TiI4, etc.; Ti(OCH3)0text3.

Ti (OC2I5)C1s, (n-C4H9
0) TiC1x, Ti(OC21(5)Brz) trihalogenated alkoxytitanium; Ti(OCH3
)2Cdan2, Ti (OC2I5)2C saw? .

(n-C4Hq O)2 TiCl2 , Ti (OC
3H7)2CJ12 Dihalogenated alkoxy titanium 7 such as Ti (OCH3)3 CJL, Ti (OC2
1(s) 3 C1, (n-C4I90) 3 Ti
C! L.

Examples include monohalogenated trialkoxytitanium such as Ti(OCH3)3Br.

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

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

The solid catalyst component (A) can be prepared, for example, by bringing the magnesium dialkoxide, the electron donating compound, and the tetravalent titanium halide into contact temporarily or stepwise in a hydrocarbon solvent. .

For example, JP-A-58-186205, JP-A-58-186205;
7-83309, JP 57-190004, JP 57-300407, JP 58-4
The method 34 described in Japanese Patent Application No. 7003 and Japanese Patent Application No. 81-43670 can be included as a suitable method for preparing the solid catalyst component (A) in the present invention.

Also, oxides of elements found in periodic table n~■.

For example, an oxide such as silicon oxide, magnesium oxide, or aluminum oxide, preferably silica oxide, or a composite oxide containing at least one type of resistive compound of an element belonging to Groups ■ to ■ of the periodic table, such as silica-alumina, and the magnesium The solid material supporting the dialkoxide, the electron donating compound, and the tetravalent titanium halide are brought into contact in a solvent at a temperature of 0 to 200°C, preferably 10 to 150°C, for 2 minutes to 24 hours. The solid catalyst component (A) can also be prepared by
870).

Furthermore, by bringing the magnesium dialkoxide into contact with the electron-donating compound, and then reacting the magnesium dialkoxide after contact with the electron-donating compound with a tetravalent titanium halide two or more times,
The solid catalyst component (A) can also be prepared (preparation method described in JP-A-57-83309).

In preparing the solid catalyst component, an organic solvent inert to the solvent, the magnesium dialkoxide, the electron-donating compound, and the tetravalent titanium halide, such as an aliphatic hydrocarbon such as hexane or heptane, is used. , aromatic hydrocarbons such as benzene, toluene, etc., or halogenated hydrocarbons such as mono- and polyhalogen compounds of saturated or unsaturated aliphatic, alicyclic and aromatic hydrocarbons having 1 to 12 carbon atoms. can be used.

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

Regarding the Ichiriki Aluminum Compound (B) - The organoaluminum compound (B) is not particularly limited and has the general formula % [However, R3 is an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group, or an aryl group] , Ma represents a real number from 1 to 3, and X represents a halogen atom such as chlorine or bromine.] Those represented by the following are widely used.

Specifically, trialkylaluminum such as trimethylaluminum, triethylaluminum, triisopropylaluminium, triisobutylaluminum, trioctylaluminum, diethylaluminum monochloride, diimpropylaluminum monochloride,
Examples include dialkylaluminum monohalides such as diisobutylaluminum monochloride and dioctylaluminum monochloride, and alkylaluminum sesquihalides such as ethylaluminum sesquichloride. Among these, trialkylaluminum is preferred, and triisobutylaluminum is particularly preferred.

Regarding one electron donor (C) - The electron donor (C) in this invention is one type.

(However, in the formula, R1 and R4 are hydrocarbon groups, preferably n-substituted or unsubstituted saturated or unsaturated hydrocarbon groups having 2 to 5 carbon atoms, and R2, l (3 and R5 are hydrogen Alternatively, a hydrocarbon group is preferably substituted with hydrogen or having 2 to 5 carbon atoms.

or an unsubstituted saturated or unsaturated hydrocarbon group, respectively.

If an electron donor (C) other than the heterocyclic compound is used, such as a silane compound or an aromatic ester, the catalyst activity will be low and the stereoregularity of the resulting polymer will also be low.

Specifically, the heterocyclic compound includes, for example, 1.
Examples include 4-cineole, 1.8-cineole, m-cineole, pinol, benzofuran, 2,3-dihydrobenzofuran (coumaran), 2H-chromene, 4H-chromene, chromane, inchromane, dibenzofuran, xanthine, and the like.

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

Among the various heterocyclic compounds, 1,8-cineole is preferred.

The method of the present invention includes the solid catalyst component (A).

Butene-1 or butene-1 and other α-olefins in the presence of a catalyst having the organoaluminum compound (B) and the specific heterocyclic compound (C) under gas phase polymerization conditions, It is something that is polymerized.

As the composition of the catalyst, the organoaluminum compound (B)
is desirably 0.1 to 1000 times the mole, preferably 1 to 500 times the mole of the tetravalent titanium halogen compound in the solid catalyst component (A).

Further, the heterocyclic compound (G) is a compound of the solid catalyst component (
0.1 to 500 times mole, preferably 0.5 to 500 times the titanium atom in the halogen compound of tetravalent titanium in A)
It is desirable that the amount is 200 times the molar amount.

As the gas phase polymerization conditions, it is important that the degree of one polymerization is 45 to 70°C, preferably 50 to 85°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 made too high, so the degree of one polymerization cannot be made sufficiently large. Removal becomes difficult. Furthermore, if the polymerization temperature is higher than 70°C, the resulting polymer particles will aggregate or adhere to the walls, making the polymerization operation difficult, and the catalyst activity will also decrease, making it difficult to perform the polymerization process smoothly. become unable.

The partial pressure of butene-1 varies depending on the polymerization temperature, but
It may be within a range in which liquefaction does not occur in a substantial amount, and in normal cases, it is about 1 to 15 kg/crn'.

In addition, for the purpose of adjusting the molecular weight of hydrogen,
g1m agent may coexist; furthermore, butene-1
Inert gases with lower boiling points, such as nitrogen, methane,
Ethane, propane, etc. can also coexist. The coexistence of these inert gases further reduces the tendency of the polymer to agglomerate, and also facilitates the removal of the heat of polymerization. The effective coexistence amount of the inert gas is 0.2 moles or more relative to butene-1.

Gas phase polymerization can be carried out using a fluidized bed or a stirred fluidized bed. Alternatively, the reaction can also be carried out while the gas components are flowing 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-olefins can be produced.

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

When producing a random copolymer, butene-1 and other α-olefins are mixed so that the butene-1 content in the copolymer is 60 to 99.5 mol%, preferably 70 to 98 mol%. All you have to do is feed it to the polymerization vessel and copolymerize it.

When producing a so-called block copolymer, a first stage polymerization process is performed in which α-olefin other than butene-1 is homopolymerized, and then a second stage polymerization process is performed in the first stage. In the presence of the obtained α-olefin homopolymer, butene-1 or butene-1 according to the present invention is copolymerized with other α-olefins.

Here, α-olefins other than butene-1 include, for example, linear monoolefins such as propylene, ethylene, hexene-1, and octene-1, branched monoolefins such as 4-methyl-pentene-1, and butadiene. Dienes can be used.

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

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

In the method of this invention, post-treatment after polymerization can be carried out by conventional methods. That is, after gas phase polymerization, a nitrogen stream or the like may be passed through the polymer powder derived from the polymerization vessel in order to remove olefins and the like contained therein.
If desired, it may be pelletized using an extruder, and at this time a small amount of wood, alcohol, etc. may be added to completely deactivate the catalyst.

As described above, butene obtained by the method of this invention
In the normal case, the polymer 1 has an intrinsic viscosity [η] (decalin solution, 135°C) of 1.0 to 7.0 dl/g, and 1.1. (insoluble content after 6 hours of Tuxhlet extraction with boiling diethyl ether) is 85% or more, and the bulk density is 0.28 g/cc or more. Furthermore, the content of catalyst residues 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 and the like.

[Effects of the Invention] According to the present invention, (1) Since a highly active catalyst is used, the amount of catalyst residue remaining in the polymerization product can be reduced, and therefore, the amount of catalyst residue remaining in the resulting butene-1 polymer can be reduced. (2) It is possible to omit the step of removing catalyst residual liquid, and since there is almost no harmful residual liquid, the problem of molding machine corrosion can be solved. (2) Polymer powder with high bulk density can be obtained. Therefore, it is convenient for powder transportation, and (3) [η1 is 1.
0 to 7.0 dll/g, stereoregularity (1,1,)
It is possible to provide a method for producing a butene-1 polymer, which has the following advantages: and, because it has excellent creep resistance, it can be molded into a molded product with a good appearance, such as a pipe.

[Examples] Next, the present invention will be explained in more detail by showing examples and comparative examples of the present invention.

(Example 1) ■ Preparation of solid catalyst component In a well-dried tofL four-eye flask, dehydrated Ml!
5 grams of n-hexane, 50 grams of magnesium jetoxide
0 g (4,4 m o 41) and 94.8 g (0,34 m o) of diimpropyl phthalate were added and the reaction was carried out for 1 hour under continuous flow.Then, the temperature was reduced to 90 °C.
and titanium tetrachloride 2.5 kg (132 m o
n) was added dropwise over a period of 50 minutes, and a two-time reaction was further carried out at 90°C. Thereafter, the temperature was raised to 30° C., the supernatant liquid was drawn out, n-hebutane 72 was added and stirred, and after stirring, the supernatant liquid was drawn out, and this operation was repeated twice to perform washing. After that, 51 kg of n-hebutane was newly added, the temperature was raised to 70°C, and 2.5 kg of titanium tetrachloride was added.
(132m o IL) was added dropwise and the reaction was carried out at 80°C for 2 hours.Then, the temperature was raised to 80°C, the supernatant liquid was taken out, and 7 g of n-hebutane was added for washing. The washing was repeated until no chlorine ions were detected to obtain a solid catalyst component.

When the amount of titanium supported was measured by colorimetric method, it was found to be 2.8
It contained li% titanium.

■ Preparation of catalyst The solid catalyst component obtained in the above
The solution was diluted to 100% and put into a catalyst preparation tank. In this catalyst preparation tank, triimbutylaluminum 30 mmol/l,
and 12 mmol/l of 1,8-cineole were supplied. Thereafter, propylene was supplied at a rate of 50 g per mm of titanium. Inside the catalyst preparation tank is 40℃
The temperature was raised to 100°C, and a reaction for preparing a catalyst was carried out.

■ Production of butene-1 homopolymer Using a fluidized polymerization vessel with a diameter of 300 mm and a volume of 1,001 mm, the Ti catalyst slurry prepared by reconsolidating the catalyst obtained in step (1) above to 3.8 mM/l in terms of Ti atoms was added to the catalyst preparation tank. to the polymerization vessel at a flow rate of 0.15 mM/hr, triisobutylaluminum at a flow rate of 60mM/hr, and cineole at a flow rate of 24mM/hr.

The partial pressure of butene-1 is 3 kg/c rrf and the partial pressure of nitrogen is 4 kg/crn', respectively: JJ! IL,
Butene-1 and N2 gases were supplied such that the superficial gas velocity was 35 cm/sec. The polymer is discharged at a constant rate so that the amount of polymer in the polymerization vessel remains constant.
J section.

The polymerization temperature was 60°C.

Intrinsic viscosity of the obtained polymer [η], r, r, bulk density, residual titanium (analysis method: fluorescent X-ray method), residual 11
! (Analysis method: fluorescent X-ray method), creep resistance (AST
Evaluation based on M 02990) etc. are shown in Table 1.

(Example 2) Gas phase polymerization was carried out in the same manner as in Actual Flow Side 1, except that the Ti catalyst slurry supply flow rate was 0.075 g/hr and the wood partial pressure was 0.08 kg/C.

Table 1 shows the properties of the obtained polymer.

(Example 3) (1) Preparation of solid catalyst component A solid catalyst component was prepared in the same manner as (2) in Example 1 above.

(2) Preparation of catalyst A catalyst was prepared in the same manner as (2) in Example 1 above.

■ Production of propylene-butene-1 copolymer Propylene and hydrogen are newly supplied to the polymerization vessel, and the propylene partial pressure is reduced to 0.3 kg/crn', and the hydrogen partial pressure is reduced to 0.
．． A propylene-butene-1 copolymer was produced in the same manner as in Example 1 except that the weight was adjusted to 09 kg/crn'. Its properties are shown in Table 1.

(Example 4) ■ Preparation of solid catalyst component 5! 500 g of fired silicon oxide (manufactured by Fuji Davison Co., Ltd., grade 352, specific surface precision 350 g/g, average particle size 54-65 m) and 1.51 g of trimethylchlorosilane were placed in a L glass container, and After reacting for 12 hours while stirring under running water, decantation with n-hebutane was repeated 5 times to dry.

Jetoxymagnesium (2
500 m m o sentence), tetra-n-butoxytitay
n-heptane solution containing (1500 mm of) 2.
5 sentences were added and the mixture was left in contact for 1 hour at room temperature. After that, 1250 ml of Improper Tool was added dropwise, stirred at 80°C for 1 hour, and then decanted with 51 mL of n-hebutane.
This was repeated several times and dried under reduced pressure at 80° C. for 1 minute to obtain a white catalyst carrier. This catalyst carrier contained 3.3% by weight of magnesium atoms.

375 g of the catalyst carrier obtained in this way was placed in a 5 sL glass container, and mixed with 2.5 g of n-hebutane, 95 mmoJJ of diisobutysifthalene, and 2250 g of titanium tetrachloride.
I added g. This mixture was stirred at 90° C. for 2 hours.

Thereafter, the supernatant liquid was removed by decantation, and the obtained solid portion was sufficiently washed with hot n-hebutane to obtain a solid catalyst component.

This catalyst contained 3.2% by weight of Ti.

(2) Preparation of catalyst In the same manner as the catalyst manufactured by YA in (2) of Example 1,
A catalyst was prepared.

(2) Production of butene-1 homopolymer A butene-1 homopolymer was produced in the same manner as the gas phase polymerization in (2) of Example 1 above. Table 1 shows the properties of the obtained polymer.

(Comparative example 1) ■ Preparation of solid catalyst component The same procedure as in Example 1 was carried out.

■ Catalyst [! 1 diphenyldimethoxysilane instead of cineole
The same procedure as in Example 1 was conducted except that m m o n /l was used.

(2) Production of butene-1 homopolymer The same procedure as in Example 1 was carried out except that instead of freshly supplied cineole, cypher dimethoxysilane was supplied at a flow rate of 3 mM/hr.

The properties of the obtained butene-1 homopolymer are shown in Table 1. Also, this /ten-1 homopolymer has a very poor hue and low stereoregularity, so it cannot be formed into a pipe. It has no commercial value, and furthermore, the powder properties of the resulting polymer are poor, making it difficult to continuously slow down one polymerization device.

(Comparative example 2) ■ Preparation of solid catalyst component It was carried out in the same manner as in Example 1 above.

■ Preparation of catalyst It was carried out in the same manner as in Comparative Example 1 above.

(2) Production of butene-1 polymer The same procedure as (2) of Comparative Example 1 was carried out except that hydrogen was additionally supplied at a flow rate of 0.02 kg/cm'.

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

(Comparative example 3) ■ Preparation of solid catalyst component It was carried out in the same manner as in Example 1 above.

■ Preparation of catalyst components The work was carried out in the same manner as in the example work described above.

■ Production of butene-1 homopolymer The flow rate of Ti catalyst slurry was 0.271/hr, the polymerization temperature was 40°C, and the feed rate of butene-1 was 2.
The same procedure as in Example 1 was conducted except that kg/crn' was used.

The resulting 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 was carried out in the same manner as in Example 1 above.

■ Preparation of catalyst components It was carried out in the same manner as in Example 1 above.

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

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

(Comparative Example 5) ■ Preparation of solid catalyst component Well-dried 10! In a four-eye L flask, add 5 g of dehydrated and purified n-hegosan and 500 g of magnesium chloride (
4,4 mol) and 132 g of ethyl benzoate (
(L38 m o n ) was added and the reaction was carried out under reflux for 1 hour.Next, the temperature was raised to 70°C, and 4.2 kg (22 m o 31) of titanium tetrachloride was added dropwise over 50 minutes, and the mixture was further refluxed. The reaction was carried out for 3 hours at a lower temperature. Thereafter, the temperature was raised to 30° C., the supernatant liquid was drawn out, 7 fL of n-hebutane was added and stirred, and the mixture was allowed to stand, and the supernatant liquid was drawn out. This operation was repeated twice to perform washing.

After that, add 5 more drops of n-hexane and lower the temperature to 70.
℃, and add 4.2 kg (22 moJl) of titanium tetrachloride to 3
It was added dropwise over 0 minutes, and the reaction was carried out under reflux for 3 hours.6
Next, the temperature was raised to 80° C., the supernatant liquid was drained, and n-hebutane 71 was added thereto for washing. The washing was repeated until no chlorine ions were detected to obtain a solid catalyst component.

When the amount of titanium supported was measured by a colorimetric method, it was found that 2.8% by weight of titanium was contained.

Further, the average particle diameter of the solid catalyst component was 20 pm, and the geometric standard deviation σg of the particle size distribution was 1.8.

■ Preparation of catalyst The procedure was carried out in the same manner as in (2) in Example 1 above.

■ Butene! Production of homopolymers 0.15 u/hr of re-prepared Ti catalyst slurry.

and triimbutylaluminum at a flow rate of 180 m
Methyl toluate was supplied to the fluidized bed polymerizer instead of cineole at a flow rate of 7.5 mM/hr, and the partial pressure of newly added hydrogen was 0.15 kg/hr.
The same procedure as in Example 1 (2) was carried out except that the temperature was adjusted to cm'.

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

[Brief explanation of drawings]

FIG. 1 is a flowchart diagram showing catalyst preparation and polymerization. Procedural amendment dated 19th May 1982

Claims (1)

[Claims] (1) Solid catalyst component (A) obtained from a magnesium compound, an electron donating compound, and a tetravalent titanium halide
, a homopolymer of butene-1 or butene-1 and other α-olefins under gas phase polymerization conditions in the presence of a catalyst obtained from an organoaluminum compound (B) and an electron-donating compound (C). In the method for producing a copolymer, the magnesium compound has the formula Mg(OR)_2(1) (wherein R is an alkyl group having a linear or side chain having 1 to 10 carbon atoms, represents a cycloalkyl group, an aryl group, or an aralkyl group), and the electron-donating compound (C) has the formula ▲ has a numerical formula, chemical formula, table, etc. ▼ (2) , R^1 and R^4 represent a hydrocarbon group, and R^2, R^3 and R^5 represent hydrogen or a hydrocarbon group, respectively. A method for producing a butene-1 polymer, characterized in that the reaction temperature is 45 to 70°C.