JPH01168707A - Preparation of butene-1 polymer - Google Patents

Abstract

PURPOSE:To obtain stably a polymer having a high stereoregurality and a low content of catalyst residue and being suitable for pipes, etc., by (co) polymerizing butene-1 by means of vapor phase polymn. using a specified highly active polymn. catalyst and regulating vapor phase polymn. conditions. CONSTITUTION:A solid catalyst component having a mean particle diameter of 5-200mum, a geometrical standard deviation of particle size distribution of less than 2.1 and a molar ratio of an electron donating compd. to an Mg compd. of 0.01 or larger is prepd. from an Mg compd. (e.g., formula I), an electron donating compd. and a tetravalent titanium halide. A catalyst is prepd. from this solid catalyst component, an org. aluminum compd. and an electron doner of an ether compd. of formula II (wherein R<1> is a hydrocarbon group and at least one R<1> is an arom. or alicyclic hydrocarbon group; R<2> is a hydrocarbon group; n is 1-3) (e.g., alpha-cumyl methyl ether). Butene-1 is (co)polymerized by means of vapor phase polymn. in the presence of this catalyst under a condition where the molar ratio of hydrogen to butene-1 is 0.001-0.1, to obtain a butene-1 polymer.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] This invention relates to a method for producing butene-1 polymers. More specifically, the present invention relates to a method for producing a butene-1 polymer suitable for molding, for example, pipes, by taking advantage of gas phase polymerization in the presence of a highly active catalyst.

[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 possibility 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 can be carried out using titanium trichloride-based catalysts (see JP-A-60-192716) and magnesium chloride-based catalysts (see JP-A-59-6205), which have been widely used in the past. If this process is carried out, the catalytic activity becomes low and the stereoregularity of the butene-1 polymer obtained is insufficient, making it impossible to fully utilize the advantages of the gas phase polymerization method.

In particular, butene-1 polymers obtained by conventional production methods are still insufficient for use in pipes.

[Object of the Invention] An object of the present invention is to provide a method for producing a butene-1ff1 complex 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 structure of the present invention for achieving the above object includes a solid catalyst component (A) obtained from a magnesium compound, an electron donating compound, and a halide of tetravalent titanium, and an organoaluminum compound. A homopolymer of butene-1 or a copolymer of butene-1 and other α-olefins is produced under gas phase polymerization conditions in the presence of a catalyst obtained from (B) and an electron donor (C). In the method of manufacturing.

The solid catalyst component (^) has an average particle size of 5 to 200p,
m, the geometric standard deviation (6 g) of the particle size distribution is less than 2.1, and the electron donating compound/magnesium (molar ratio) is 0.
．． 01 or more, and the electron donor (C) has the formula % formula % (1) (wherein R1 is a saturated or unsaturated hydrocarbon group, and at least one of the n R1 R1 is an aromatic hydrocarbon group or a cyclic aliphatic hydrocarbon group. R is a hydrocarbon group. n is 1 to 3).

As the gas phase polymerization conditions, hydrogen/butene-1 (molar ratio)
is 0.001 to 0.1.
1! This is a method of manufacturing a combination.

In the method of this invention, as shown in FIG. Producing a homopolymer of butene-1 or a copolymer of butene-1 and other α-olefins under specific gas phase polymerization conditions in the presence of a catalyst obtained from the donor compound (C). .

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

There are no particular restrictions on the magnesium compound, and those used are those used as raw materials for the preparation of highly active catalysts for stereoregular polymerization of lower α-olefins and for the production of ethylene alone or copolymers such as linear polyethylene. be able to.

As such a magnesium compound, for example, the following general formula % formula % (2) (in formula 1, X is a halogen atom: carbon number 1 to 20
Alkyl group; aliphatic, alicyclic, aromatic alkoxy group such as a linear or side chain alkoxy group having 1 to 10 carbon atoms, cycloalkoxy group, arylalkoxy group, nialyloxy group, alkylaryl An aryloxy group such as an oxy group; or a substituted alkoxy group or a substituted aryloxy group in which these are substituted with a hetero atom such as a halogen atom; Examples include compounds represented by ), which may be different types of groups.

Examples of the halogen atom for X include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, and among these, a chlorine atom is particularly preferred.

A specific example of the magnesium compound represented by the formula (2) is 1Mg (-Ct Hs ) t.

M g (Cm Hs ) (-C4Ht) t
.

Mg (-C4)19 ) (Cs Ht*) t
.

M g (-C41(s) (-Ca H4F)
*.

Mg (-0CH3)t, Mg (-QCs
Hs)tMg (-QCyuHy)t,
Mg (-0C4Hs)*, Mg (-Q
Cs HI3)*, Mg (-0Ca Hay)
tMg (0CHs) (QCs Hs
).

M g Cl t , M g Br *,
M g I t , MgC1 (OCHi ),
MgC1 (QCs Hs ), MgO (QC3
Ht), MgO sentence (QC-Hs), etc.

These various magnesium compounds can be used alone or in combination of two or more.

Note that among these, magnesium chloride compounds, lower alkoxymagnesium compounds, etc. are preferable, and in particular,
MgC2, Mg (C4Ht) (CIl Hst), Mg
(QC)13) and Mg (oc2H5)* are preferred.

As the electron-donating compound that is the raw material for the solid catalyst component (^), 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, acid 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, nathaldehyde: Methyl formate, methyl acetate,
Ethyl acetate, vinyl acetate, propyl acetate, octyl acetate, cyclohexyl acetate, ethyl propionate, ethyl butyrate, ethyl valerate, methyl chloroacetate, ethyl dichloroacetate, methyl methacrylate, ethyl crotonate, ethyl pivalate, dimethyl maleate, 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 toluate Ethyl benzoate, methyl anisate,
Monoesters such as ethyl anisate, ethyl ethoxybenzoate, ethyl p-butoxybenzoate, ethyl 0-chlorobenzoate and ethyl naphthoate, or dimethyl phthalate, diethyl phthalate, dipropylphthalate, diisopropylphthalate, diisobutyl phthalate, methyl ethyl Phthalate, methylpropyl phthalate, methyl isobutyl phthalate, ethylpropyl phthalate, ethyl isobutyl phthalate, propyl isobutyl phthalate, dimethyl terephthalate, diethyl terephthalate, dipropyl terephthalate, diisopropyl terephthalate, diisobutyl terephthalate, methyl ethyl terephthalate, methylpropyl terephthalate, methyl isobutyl Terephthalate, ethylpropyl terephthalate, ethyl isobutyl terephthalate, propyl isobutyl terephthalate, dimethyl isophthalate, diethyl isophthalate, dipropylisophthalate, diisopropylisophthalate, diisobutyl isophthalate, methyl ethyl isophthalate,
Aromatic diesters such as methyl pro and isophthalate, methyl isobutyl isophthalate, ethyl propyl isophthalate, ethyl isobutyl isophthalate and propyl isophthalate, γ-butyrolactone, δ-valerolactone, coumarin, phthalide, ethylene carbonate, etc. carbon number Esters having 2 to 18 carbon atoms; acid halides having 2 to 15 carbon atoms such as acetyl chloride, benzyl chloride, toluyl chloride, anisyl chloride; methyl ether, ethyl ether, isopropyl ether, n-butyl ether, amyl ether, tetrahydrofuran, Ethers with 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; Tributylamine, N,N'-dimethylpiperazine, tribenzylamine, aniline Examples include amines such as pyridine, picoline, and tetramethylethylenediamine, and nitriles such as niacetonitrile, 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 and diisopropyl phthalate are 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. You may use more than one species in combination.

Specifically, the tetravalent titanium halide, which is one of the raw materials for the solid catalyst component (A), is as follows.

TiC sentence, TiBr4. Tetrahalogenated titanium such as Ti1n; T i (OCHz) Cdan3, T
i (QC,H5)C12, (n-C,H2O)TiC
trihalogenated alkoxytitanium such as jL3, Ti(QCsHs)Br3; Ti(QCHz)2
C12,Ti (OCz H5)! C sentence 2, (HC4
Hg O)2 T1Cu*, Ti (OC31(?
)2 dihalogenated alkoxy titanium such as cx2;
T; (QC)i, )3C, Ti(OC2H,), C
Standing, (n-C4Hs O)3 TiCjL, Ti (O
Examples include monohalogenated trialkoxytitanium such as CHz):l Br.

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.

As the preparation procedure for the solid catalyst component (A), for example,
The magnesium compound, the electron donating compound, and the tetravalent titanium halide may be brought into contact with each other temporarily or stepwise in a hydrocarbon solvent.

As a preparation procedure for the solid catalyst component (A), for example, JP-A-56-166205, JP-A-57-63309
No. 190004, JP 57-190004, JP 57
-: The preparation procedure described in JP-A No. 100407, JP-A-58-4700:1, and Japanese Patent Application No. 61-43670 is the preferred preparation procedure for the solid catalyst component (A) in the present invention. can be included as.

Also, oxides of elements belonging to groups ■ to ■ of the periodic table.

For example, an oxide such as silicon oxide, magnesium oxide, or aluminum oxide, preferably silicon oxide, or a composite oxide containing at least one of the oxides of elements belonging to Groups 1 to 2 of the periodic table, such as silica-alumina, and the above magnesium compound. The solid material supporting the electron-donating compound and the tetravalent titanium halide in a solvent,
at a temperature of 0 to 200°C, preferably lO to tso'c,
The solid catalyst component (A) can also be prepared according to the preparation procedure of contacting for 2 minutes to 24 hours (Japanese Patent Application No. 61-43).
610).

Furthermore, the solid may be prepared by contacting the magnesium compound with the electron-donating compound, and then reacting the magnesium compound after contact with the electron-donating compound with a halide of tetravalent titanium two or more times. Catalyst component (A) can also be prepared (Japanese Patent Application Laid-Open No. 57-6
Preparation method described in Publication No. 3309).

In addition, in preparing the solid catalyst component, as the solvent, the magnesium compound, the electron donating compound, and 4.
An organic solvent inert to halides of titanium, such as aliphatic hydrocarbons such as hexane and heptane, aromatic hydrocarbons such as benzene and toluene, or 1 carbon number.
Halogenated hydrocarbons such as mono- and polyhalogen compounds of ~12 saturated or unsaturated aliphatic, alicyclic and aromatic hydrocarbons can be used.

Although the solid catalyst component (A) can be prepared according to conventionally known preparation procedures, in the method of the present invention, the solid catalyst component (A) has an average particle size of 5 to 2.
00ILm, and the geometric standard deviation of the particle size distribution is 6g.
is less than 2.1, preferably 1.95 or less.

Here, a light transmission method was employed to measure the particle size distribution of the solid catalyst component particles. Specifically, the particle size distribution was measured as follows. That is, 0.0% with an inert solvent such as decalin. Dilute the catalyst component to a concentration of 0.5% to 0.5%, place it in a measurement cell, shine a narrow light into the cell, and continuously measure the intensity of light passing through the liquid in a sedimented state with one particle. to measure the particle size distribution.

Based on this particle size distribution, a standard deviation of 6 g is determined from a lognormal distribution function. The average particle diameter of the catalyst is shown as the weight average diameter, and the particle size distribution is measured at 1% of the weight average particle diameter.
Calculations were made by sieving in the range of 0 to 20%.

If this average particle diameter is less than 5 pm, it may cause troubles due to agglomeration of the produced polymer or entrainment of particles into the polymerization tank exhaust gas system, while if it exceeds 200 pm, the fluidization condition of the fluidized bed during gas phase polymerization may be affected. becomes worse, adhesion to the vessel wall,
Causes polymer aggregation.

Further, the geometric standard deviation 6g is 2.1 or more,
Even if the average particle size is in the range of 5 to 200 ILm, the fluidization state of the fluidized bed during gas phase polymerization deteriorates, causing adhesion to vessel walls and polymer aggregation.

Preferably, these solid catalyst components (A) have relatively regular shapes such as spherical, ellipsoidal, and flaky shapes.

In order to obtain the solid catalyst component (A) having a specific average particle size and geometric standard deviation as described above, the average particle size is in the range of 5 to 200 lm, and the geometric standard deviation of the particle size distribution is 6 g. It is preferable to prepare a magnesium compound having the above shape with a particle size of less than 2.1, preferably 1.95 or less, and suspend and support it in an excess liquid titanium compound or a hydrocarbon solution of the titanium compound.

Alternatively, by selecting the reaction conditions of the titanium compound, electron donating compound, and magnesium compound, catalyst particles having a narrow particle size distribution such that the average particle size of the generated catalyst component satisfies the above range may be formed. , as the reaction conditions.

For example, the amount of compound, temperature, contact time, etc. may be mentioned.

The solid catalyst component (A) used in the method of the present invention
has a halogen/titanium (molar ratio) of 6 to 200, preferably 7 to 100, and a magnesium/titanium (molar ratio) of 1 to 90. Preferably, it is 5 to 70, and it is important that the electron donating compound/magnesium (molar ratio) is 0.01 or more, preferably 0.03 to 1.

If the ratio of each of these components is outside the above range, the catalyst activity and the stereoregularity of the resulting polymer may be insufficient.

About the organoaluminum compound (B) - The organoaluminum compound (B) is not particularly limited and has the general formula % [where Ba represents an alkyl group, cycloalkyl group, or aryl group having 1 to 10 carbon atoms]. , V 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, triisopropylaluminum, triisobutylaluminum, trioctylaluminum, diethylaluminum monochloride, diisopropylaluminum monochloride,
Examples include dialkylaluminum heptivalides such as diisobutylaluminum monochloride and dioctylaluminum monochloride, and alkylaluminum sesquihalides such as ethylaluminum sesquichloride. Among these, trialkylaluminum is preferred, and triisobutylaluminum is particularly preferred.

In addition, these compounds may be used alone,
Two or more types may be used in combination.

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

R”, C(OR”),, (1) (However, 1
In the formula, R1 is a saturated or unsaturated hydrocarbon group, and n
At least one 1% I of R1 is an aromatic hydrocarbon group or a cycloaliphatic hydrocarbon group. R-value is a hydrocarbon group. nLtl~3. ) is an ether compound represented by ,
It may not be possible to obtain molded products suitable for use in vibrators, etc., and under conditions where the hydrogen/butene molar ratio is low,
Catalytic activity decreased significantly and the amount of residual halogen in one polymer increased.

It causes corrosion of the molding machine.

Specifically, as the ether compound, for example, α
-cumyl methyl ether, 1,1-diphenylethyl ethyl ether, diphenyldimethoxymethane, phenyltrimethoxymethane, diphenyljethoxymethane, dicyclohexyldimethoxymethane, phenyltriethoxymethane, pentylphenyl ether, benzyl ethyl ether, etc. It will be done.

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

Among the various ether compounds, diphenyldimethoxymethane is preferred.

The method of the present invention includes the specific solid catalyst component (A);
Butene-1 in the presence of a catalyst comprising the organoaluminum compound (B) and the specific ether compound (C).
Alternatively, butene-1 and other α-olefins are monopolymerized under gas phase polymerization conditions.

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 ether compound (C) is 0.1 to 500 times mole, preferably 0.1 to 500 times the mole of titanium atoms in the halogen compound of tetravalent titanium in the solid catalyst component (^).
It is desirable that the amount is 5 to 200 times the molar amount.

As the gas phase polymerization conditions, it is desirable that the polymerization temperature is 45 to 70°C, preferably 50 to 65°C.

When the polymerization temperature is lower than 45°C, the partial pressure of butene-1 cannot be made too high in order to prevent liquefaction, so it may not be possible to make the degree of one polymerization sufficiently large. Heat removal may be difficult. In addition, if the temperature of the polymerization vessel is higher than 70°C, the polymer particles produced may aggregate or adhere to the walls, making the polymerization process difficult, and the catalyst activity will also decrease, making it difficult to perform the polymerization process smoothly. You may not be able to do it.

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.In the normal case, it is about 1-15 kg/cm''.

One of the important points in the method of this invention is that the gas phase polymerization is carried out at a hydrogen/butene-1 (molar ratio) of 0.001 to 0.
This point is carried out within the range of 1. If this hydrogen/butene-1 (molar ratio) is outside the specified range, the catalyst activity will decrease or the residual halogen in one polymer will increase. Further, in some cases, it may become difficult to control the molecular weight of the polymer.

In the method of the present invention, it is possible to adjust the molecular weight of the polymer to a suitable range by using hydrogen, but if necessary, the molecular weight Wt! of a polymer other than hydrogen can be adjusted. Five agents may be used as appropriate.

Furthermore, an inert gas having a boiling point lower than that of butene-1, such as nitrogen, methane, ethane, propane, etc., may also be present. 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, butene is used as a heptamer.
What is necessary is to supply only 1 together with hydrogen etc. to a polymerization vessel and polymerize it by a conventional method.

When producing a random copolymer, butene-1 and other α-olefins are used as heptadmers, and the butene-1 content in the copolymer is 60 to 99.5 mol%, preferably 70 to 70%. It may be fed to a polymerization vessel together with hydrogen or the like so that the concentration is 98 mol %, and copolymerized.

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, examples of α-olefins other than butene-1 include propylene, ethylene, linear monoolefins such as 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, other olefins such as propylene, ethylene, and hexene-1 are preferred.

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 is carried out.

This can be done by conventional methods. That is, in the polymer powder extracted from the polymerization vessel after gas phase polymerization.

In order to remove the olefins contained in the catalyst, a stream of nitrogen or the like may be passed through it, or if desired, it may be pelletized using an extruder, in which case a small amount of water may be added to completely deactivate the catalyst. , alcohol, etc. can also be added.

As described above, butene obtained by the method of this invention
Normally, a polymer has an intrinsic viscosity [η] (decalin solution, 135°C) of 1. o~7. .

dn/g, 1.1. (6 with boiling diethyl ether)
The insoluble content (after time-extraction extraction) is 95% or more, and the bulk density is 0.28 g/cc or more.

Moreover, the content of catalyst residual liquid in the obtained boria is significantly reduced.

As a result, the butene-1 polymer obtained by the method of the present invention can be used as a suitable material for various types of vibrators.

[Effects of the Invention] According to the present invention, (1) the catalyst activity is extremely high, and the amount of catalyst residue remaining in the polymerization product can be reduced; therefore, the catalyst residue from the butene-1 polymer obtained is (2) Since there is almost no harmful residual liquid, the problem of molding machine corrosion can be solved. (2) Since a polymer powder with a high bulk density can be obtained, It is convenient for transportation, and (3) [η] 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 advantages such as excellent creep resistance and can be suitably used for pipes, for example.

[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 Well-dried 10! In a four-piece L flask, add 5 g of dehydrated n-hebutane and 5 Hg of magnesium jetoxide.
(4,4mo sentence) and moro-butyl phthalate 15
Add 3 g (0.55 m on) and 1 ml under rapid flow.
Then, the temperature was raised to 90°C, 2.5 kg of titanium tetrachloride (viewed at 132 mm) was added dropwise over 50 minutes, and the reaction was further carried out at 90°C for 2 hours. After that, the temperature was raised to 30°C, the supernatant liquid was extracted, and n
- 7 g of hebutane was added and stirred, and then allowed to stand, the supernatant liquid was drawn out, and this operation was repeated twice to perform washing. After that, 5 grams of n-hebutane were newly added, the temperature was raised to 70°C, and 2.5 kg of titanium tetrachloride (132 moj.
L) was added dropwise, and the reaction was carried out at 90°C for 2 hours. Next, the temperature was raised to 80° C., the supernatant liquid was taken out, and n-butane was added to wash it. The washing was repeated until no chlorine ions were detected to obtain a solid catalyst component. The average particle size of this solid catalyst component was 3 Spm, and the geometric standard deviation (6 g) of the particle size distribution was 1.3. In addition, when the amount of titanium supported was measured by colorimetric method, it was found to be 2.6% by weight.
contained titanium.

■ Preparation of catalyst The solid catalyst component obtained above was mixed into 2 mmojLTi/I
The solution was diluted to 1.5 L and placed in a 1IJ1 preparation tank. In this catalyst preparation tank, 30 mm of triisobutyl aluminum was added.
o l/Jl, and diphenyldimethoxymethane B m o m/t were fed. Thereafter, propylene was supplied at a rate of SOg per l m m o n of titanium. Catalyst style! lIJ! The temperature inside the reactor was raised to 40°C, and a reaction for preparing a catalyst was carried out. After 15 minutes of reaction, the reaction product was filtered and dried to obtain a catalyst component.

■ Production of butene-1 homopolymer A fluidized bed polymerization vessel with a diameter of 300 mm and a volume of 100 mm was used. The catalyst obtained in step (1) was transferred from the catalyst storage tank to the polymerization vessel in terms of Ti atoms (1.3 m m o fL/hr, with a feed rate of 60 mmo of triisobutylaluminum
At a flow rate of 6/h, ・diphenyldimethoxymethane 6
Each was supplied to the polymerization vessel at a flow rate of mmou/hr-.

The partial pressure of butene-1 was adjusted to 3 kg/cm', the partial pressure of nitrogen was adjusted to 4 kg/cm', and the superficial gas velocity was 35 kg/cm'.
Butene-1, N2 gas, and N2 gas were supplied at a rate of cm/sec. The discharge of the polymer was adjusted so that the amount of polymer in the polymerization vessel was constant.

The polymerization temperature was 55°C.

The intrinsic viscosity of the obtained polymer [η1, 1.1. , bulk density, residual titanium (analytical method: fluorescent X-ray method), residual chlorine (analytical method: fluorescent X-ray method), creep resistance (A S T M
D 2990, etc. are shown in Table 1.

(Example 2.3) In Example 1, H2/butene-1 (molar ratio) was
The same procedure was carried out except that the values were changed to those shown in the table.

The results are shown in Table 1.

(Comparative Example 1) In Example 1■, methyl toluate was used instead of diphenyldimethoxymethane: 1.8 mmol/
1, and in Example 1■, instead of diphenyldimethoxymethane, 7.5 mmol/h of methyl toluate was used.
The same procedure as in Example 1 was carried out except that the water was supplied at a flow rate of .

The results are shown in Table 1.

(Comparative Example 2) In Example 1■, 1 mmol of diphenyldimethoxysilane was used instead of diphenyldimethoxymethane.
/ 9. In Example 1■, 3 m of diphenyldimethoxysilane was used instead of diphenyldimethoxymethane.
The same procedure as in Example 1 was conducted except that the solution was supplied at a flow rate of mol/hr.

The results are shown in Table 1.

(Comparative Examples 3 and 4) In Example 1, Ha/butene-1 (molar ratio) was
The same procedure was carried out except that the values were changed to those shown in the table.

The results are shown in Table 1.

(Comparative Example 5) In Example 1■, the amount of di-n-butyl phthalate added was changed from 153g (0.55mol) to 7.6g (0.
The same procedure as in Example 1 was carried out except that 128 aol) was used. Note that the solid catalyst component contained 3.0% by weight of titanium.

The results are shown in Table 1.

(Example 4) Example 1 except that butene-1, propylene, N2 gas, and N2 gas were supplied in the proportions shown in Table 1 to produce a butene-1/propylene copolymer in Example 1■. This was done in the same manner as in step 1.

The results are shown in Table 1.

(Example 5) ■Preparation of solid catalyst component Anhydrous MgCIR86.8g, diisobutyl phthalate)
-33.2g and vinyltriethoxysilane 13.9g
g was placed in a vibration mill with contents [11] and heated to 60 g under nitrogen atmosphere.
Shattered over time.

25g of co-milled product was crushed at 500c under nitrogen atmosphere.
210 cc of T i C414
brought into contact with.

Treatment with T i Cl 4 was carried out at 80 °C for 2 h with stirring at 1100 rp, after which excess T i C
l 4 and the product dissolved therein were removed by siphon at 80°C.

This operation was followed by five washes using 20Occ of n-hebutane at 65°C for each wash.

@Preparation of catalyst The same procedure as in Example 1 (2) was carried out except that the conditions shown in Table 2 were used.

(2) Production of butene-1 homopolymer The same procedure as in Example 1 (2) was carried out except that the conditions shown in Table 2 were used.

The results are shown in Table 1.

(Example 6. Comparative Example 6) The same procedure as in Example 5 was carried out except that Ht-butene-1 (molar ratio) was changed to the value shown in Table 2.

The results are shown in Table 1.

(Example 7) ■ Preparation of solid catalyst component A calcined silicon oxide (manufactured by Fuji Davison, Grate 952, specific surface M;
35Gm2/g, average grain N': 54-65 ILm)
Add 50Og and 1.5 g of trimethylchlorosilane,
After reacting for 12 hours with stirring under reflux, decantation with n-hebutane was repeated 5 times to dry.

Jetoxymagnesium (2
2.5 mmol of n-hebutane solution containing 500 mmol) and tetra-n-butoxytitanium (1500 mmol) was added, and the mixture was brought into contact at room temperature for 1 hour. After that, 1250 ml of isopropanol was added dropwise and heated to 80℃ for 1 hour.
After stirring for an hour, decantation was repeated three times with 5 g of n-hebutane, and drying was carried out under reduced pressure at 80"C for 1 hour to obtain a white catalyst carrier. This catalyst carrier contained 3.3% by weight of Contains magnesium atoms.

375 g of the catalyst carrier thus obtained was placed in a 5-mm glass container, and 2.51 g of n-hebutane, 95 mmol of diisopropylphthalate, and 2250 g of titanium tetrachloride were added.
I added g. This mixture was stirred at 90° C. for 2 hours. Thereafter, the supernatant liquid was removed by decantation, and the resulting solid portion was thoroughly washed with hot n-hebutane to obtain a solid catalyst component. This catalyst contained 3.2% by weight of Ti.

(2) Preparation of catalyst The catalyst was prepared in the same manner as in Example 1 (2) except for the conditions shown in Table 2.

(2) Production of butene-1m autopolymer The same procedure as in Example 1 (2) was carried out except for the conditions shown in Table 2.

The results are shown in Table 2.

4. Brief Description of the Figures The first is a flowchart diagram showing catalyst preparation and polymerization.

Patent applicant: Idemitsu Petrochemical Co., Ltd. Agent: Patent Attorney Naoki Fukumura Procedural amendment March 15, 1989

Claims (1)

[Claims] (1) Magnesium compound, electron donating compound and 4
A solid catalyst component obtained from a titanium halide (A
), organoaluminum compound (B) and electron donor (
C) under gas phase polymerization conditions in the presence of the catalyst obtained from
In the method for producing a homopolymer of butene-1 or a copolymer of butene-1 and other α-olefins, the solid catalyst component (A) has an average particle size of 5 to 200 μm.
, the geometric standard deviation (6 g) of the particle size distribution is less than 2.1,
and electron donating compound/magnesium (molar ratio) is 0.
01 or more, and the electron donor (C) has the formula R^1_nC(OR^2)_4_-_n(I) (wherein R^1 is a saturated or unsaturated hydrocarbon group; , at least one R^1 among n R^1s is an aromatic hydrocarbon group or a cycloaliphatic hydrocarbon group.R^2
is a hydrocarbon group, and n is 1-3. ), and the gas phase polymerization conditions include hydrogen/butene-1 (molar ratio).
is 0.001 to 0.1.
1 Polymer manufacturing method.