JPS63308006A - Production of butene-1 polymer - Google Patents

Abstract

PURPOSE:To produce a butene-1 polymer suitable as molded articles for pipes, etc., under a stable operation condition, by carrying out (co)polymerization in the presence of a catalyst obtained from a specific solid catalyst component, an organo-aluminum compound and an electron donor under a specific gaseous phase polymerization condition. CONSTITUTION:Butene-1 is (co)polymerized in the molar ratio of hydrogen/ butene-1 of 0.001-0.1 in the presence of a catalyst obtained from (A) a solid catalytic component which is prepared from a Mg compound [e.g. Mg(OCH3)2], an electron donative compound (e.g. benzoic acid or acetone) and a tetravalent Ti halide and has 5-200mum average particle diameter, <2.1, especially <=1.95 geometrical standard deviation of (deltag) of particle size distribution and >=0.01, especially 0.03-1 molar ratio of the electron donative compound/Mg, (B) an organo-aluminum compound (e.g. trimethyl aluminum) and (C) an electron donor comprising a heterocyclic compound shown by the formula (R<1> and R<4> are hydrocarbon group; R<2>, R<3> and R<5> are H or hydrocarbon group).

Description

[Detailed description of the invention] [Industrial application field] This publication IJI relates to a method for producing butene-1 polymers.

More specifically, in the presence of highly active catalysts.

This invention relates to a method for producing 9 m of butene-1 polymer suitable for molding, for example, pipes, 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 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-11 conjugates 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, monopolymers tend to aggregate together. As a result, long-term stable operation or equipment
It becomes difficult to perform movements.

In addition, gas phase polymerization is carried out using titanium trichloride-based catalysts (see JP-A-80-112718), 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-11 polymer obtained was insufficient, making it impossible to fully utilize the advantages of the gas phase polymerization method.

In particular, butene-1i1 combinations obtained by conventional production methods are still insufficient for use in pipes.

Objective of Part II] The objective 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 obtain stereoscopic control 1] # by gas phase polymerization method.
The object of the present invention is to provide a method for producing a butene-11 complex with high properties.

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

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 constitution of the present invention for achieving the above [1] is as follows: a solid catalyst component (A) obtained from a magnesium compound, an electron donating compound, and a tetravalent titanium halide; Homopolymerization of butene-1 or copolymerization of butene-1 and other α-olefins under gas phase polymerization conditions in the presence of a catalyst obtained from an aluminum compound (B) and an electron donor (G) In the method for producing a composite, the solid catalyst component (A) has an average particle size of 5 to 200 #L.
m, the geometric standard deviation (68) 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 (in the formula, 1(+ and R4 are hydrocarbon groups, R2, f13
and R5 each represent hydrogen or a hydrocarbon group,
) is a heterocyclic compound represented by
is 0.001-0.1.
This is a method for producing a single polymer.

In the method of this invention, as shown in FIG. Butene-10 polymer or butene-1
and other α-olefins are produced.

Regarding one solid catalyst component (A) - The solid catalyst component (A) is a magnesium compound and an electron! It is prepared from a j-type compound and a tetravalent titanium halide.

There are no particular restrictions on the magnesium compound, and one that is used as a raw material for the preparation of a highly active catalyst for the stereoregular polymerization of ordinary lower α-olefins and for the production of ethylene alone or copolymers such as linear polyethylene is used. be able to.

As such a magnesium compound, for example, the following general formula % formula % (2) (wherein, X is a halogen atom; carbon number 1 to IO
Aliphatic, alicyclic, aromatic alkoxy groups such as alkoxy groups, cycloalkoxy groups, and aryl alkoxy groups having a linear or side chain;
, 7-aryloxyno such as alkylaryloxy group,
Alternatively, it represents a substituted alkoxy group or a t-substituted aryloxy group in which a hetero atom such as a halogen atom is substituted.

In the formula, X may be the same type of group or different types of )^. ) can be mentioned.

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.

As a specific example of the magnesium compound represented by the formula (2), for example, Mg (-0CH3)yMg (
-0C7 Hs) 2, Mg (-0C3 I7
)2Mg (-0C4 I9)2, Mg (-OC
& H2S) 7Mg (-0CB HBr) 7.

Mg (-0CHx) (-0C2 Hs
), MgCfL? , MgB r2 , Mg I2
, MgCl (MCH3), MgCl (
OC2 I5 ), MgC COC3H+ ), M
gCI COCs I9), 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,
MgCl2, Mg (OCH3), Mg (OC2H
s)2 is 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 the electron-isolated compounds include amines, amides, ketones, nitriles, phosphines, phosphoramides, esters, ethers, thioethers, thioesters, acid anhydrides, and acid halides. , acid amides, aldehydes, organic acids, etc.

More specifically, organic acids such as aromatic carboxylic acids such as benzoic acid and p-oxybenzoic acid; acid anhydrides such as succinic anhydride, ben98ic anhydride, and P-)ruyl anhydride;
Ketones having 3 to 15 carbon atoms such as acetone, methyl ethyl ketone, methyl imbutyl ketone, acetophenone, benzophenone, and benzoquinone;
Aldehydes with M number 2 to 15: methyl formate, methyl acetate, ethyl acetate, vinyl acetate, propyl acetate, /'it
Octyl acid, cyclohexyl acetate, ethyl propionate, ethyl butyrate, ethyl valerate, methyl chloroacetate, ethyl dichloroacetate, methyl methacrylate, ethyl crotonate, ethyl pivalate, dimethyl maleate, ethyl cyclohexanecarcibonate, methyl benzoate , ethyl benzoate, propyl benzoate, butyl benzoate, octyl benzoate, cyclohexyl benzoate, phenyl benanoate, benzyl benzoate, methyl toluate, ethyl toluate, amyl toluate, ethyl ethyl benzoate, Monoesters such as methyl anisate, ethyl anisate, ethyl ethoxybenzoate, ethyl p-butoxybenzoate, ethyl 0-chlorobenzoate and ethyl naphthoate, or dimethyl phthalate, diethyl phthalate, dipropylphthalate, Diisopropyl phthalate, diisobutyl phthalate, methyl ethyl phthalate, methyl propyl phthalate, methyl isobutyl phthalate, ethyl propyl phthalate, ethyl isobutyl phthalate, propyl imbutyl phthalate, dimethyl terephthalate, diethyl terephthalate, dipropyl terephthalate, diisopropyl terephthalate, diisobutyl terephthalate, methyl ethyl terephthalate , methylpropyl terephthalate, methylisobutyl terephthalate,
Ethylpropyl terephthalate, ethyl isobutyl terephthalate, propyl isobutyl terephthalate, dimethyl isophthalate, diethyl inphthalate, dipropylisophthalate, diisopropylisophthalate,
Aromatic diesters such as diisobutyl isophthalate, methyl ethyl isophthalate, methyl propyl isophthalate, methyl isobutyl inphthalate, ethyl propyl isophthalate, ethyl isobutyl isophthalate and propyl isobutyl isophthalate, γ-butyrolactone, δ-rolactone coumarin, phthalide,
2 to 18 esters on frame 2 (such as ethylene carbonate);
Acid halides having 2 to 15 carbon atoms such as acetyl chloride, benzyl chloride, toluyl chloride, anisyl chloride: ethyl ether, ethyl ether, isopropyl ether, n-butyl ether, amyl ether, tetrahydrofuran, anisole, diphenyl ether,
2-2 carbon atoms such as ethylene glycol butyl ether
0 ethers; acid amides such as acetic acid amide, ben9oic acid amide, toluic acid amide, nitributylamine, N,
Examples include amines such as N'-dimethylpiperazine, tribenzylamine, aniline, pyridine, picoline, and tetramethylethylenediamine, and nitrites such as ni-heptonitrile, 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 alkyl esters of aromatic carboxylic acids having a carbon number of 1 to 4, aromatic diesters, such as ben9oic acid, p-methoxybenzoic acid, p-ethoxybenzoic acid, toluic acid. For example, diisobutyl phthalate 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; these may be used alone. However, two or more types may be used in combination.

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

TiC1<, TiBr4. Tetrahalogenated titanium such as TiIn; Ti(OCH3)C
.

Ti (OC2Hs)C13, (n-Cs H90)
Trihalogenated alkoxytitanium such as Ttcix, Ti(OC2H5)Br3; Ti(QCH:+)
2C sentence 2. Ti(OC7H5)2Cu2゜(n-C4H
90)2 T:C12,Ti (OC3H7)2c
Dihalogenated alkoxytitanium such as 12; Ti(O
CHxh C1,Ti(OCzH5hCl.

(n-Cs Hq O) I TLCI , Ti (QC
)(3) Monohalogenated trialkoxytitanium such as IBr can be exemplified. These may be used alone, or in combination with Type L.

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 the preparation procedure for the solid catalyst component (A), for example, JP-A-45B-188205, JP-A-57-833
09-J- Publication, JP 11457-190004, JP 57-300407, JP 58
The preparation/r order described in Publication No. 47003 and Japanese Patent Application No. 61-43670 can be included as a suitable preparation procedure for the solid catalyst component (A) in the present invention.

In addition, oxides of elements belonging to groups ■ to ■ of the periodic table, such as oxides of silicon oxide, magnesium oxide, and aluminum oxide, preferably silicon oxide, or oxides of elements belonging to groups ■ to ■ of the periodic table.
A solid material in which the magnesium compound is supported on a composite oxide, such as silica-alumina, containing at least one oxide of an element belonging to the group A, the electron donating compound, and the tetravalent titanium halide are mixed in a solvent. , 0-20
At a temperature of 0°C, preferably 10-150°C, for 2 minutes to 24
The solid catalyst component (A
) can also be prepared (Patent Application Sho 8l-43E170
(preparation method described in the specification).

Furthermore, according to preparation rll+, the magnesium compound and the electron-donating compound are brought into contact with each other, and then the magnesium compound after contacting with the electron-donating compound and the halide of tetravalent titanium is reacted two or more times. Catalyst component (A) can also be prepared (4￥ open/close 5
7-8: 1309).

In addition, in preparing the solid catalyst component, as the solvent,
41 which is inert to the magnesium compound described in 17i, the electron donating compound and the halide of tetravalent titanium.
Organic solvents such as aliphatic hydrocarbons such as hexane and heptane, aromatic hydrocarbons such as benzene and toluene, or saturated or unsaturated aliphatic, alicyclic and aromatic hydrocarbons having carbon a1 to a12. and halogenated hydrocarbons such as polyhalogen compounds.

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
The geometric standard deviation of the particle size distribution (rg
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 around 1 to 0.5%, put it in a settling cell, shine a narrow light on the cell, and collect the sedimentary fKj with particles.
The particle size distribution is determined by continuously measuring the intensity of light passing through the liquid.

Based on this particle size distribution, the standard deviation σg is determined from a lognormal distribution function. The average particle diameter of the catalyst is ↑11'
The measurement of the particle size distribution, which is indicated by +i-average diameter, was calculated by sieving in the range of 10 to 20% of the average particle diameter.

If this 11 average particle diameter is less than 5 pm, it may cause troubles due to agglomeration of the produced polymer or entrainment of the particles into the t-combiner tank exhaust gas system.On the other hand, if it exceeds 20Q7zm, the fluid state of the fluidized bed during gas phase polymerization may ym becomes worse, causing adhesion to the vessel wall and polymer aggregation.

In addition, if the geometric standard deviation (rg) is less than 2.1, even if the average particle size is in the range of 5 to 2004 m, the fluidization state of the fluidized bed in gas phase polymerization will deteriorate and the vessel wall will deteriorate. This may cause adhesion to the product or polymer aggregation.

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

With the specified average particle size and geometric standard deviation as described above,
In order to obtain the solid catalyst component (A), magnesium in the above-mentioned shape is prepared in advance, which has an average particle size in the range of 5 to 200 μm and a geometric standard deviation σg of the particle size distribution of less than 2.1, preferably 1.95 or less. It is preferable to prepare the compound in advance and suspend it in an excess liquid titanium compound or a hydrocarbon solution of the titanium compound to support it.

Alternatively, by selecting reaction conditions between a titanium compound, an electron-donating compound, and a magnesium compound, narrow catalyst particles with a particle size of 41 are formed so that the average particle size of the catalyst component to be produced satisfies the range L. The above reaction conditions may also be as follows.

Examples include compound rA, temperature, contact time, etc.

The solid catalyst component (^) used in the method of the present invention
Desirably, the halogen/titanium (molar ratio) is 6 to 200, preferably 7 to 100, the magnesium/titanium (molar ratio) is 1 to 90, preferably 5 to 7°, and the electron- Donor 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 become insufficient.

Regarding the organoaluminum compound (Japanese) - The organoaluminum compound (B) is not particularly limited and has the general formula % or A-view? R6 x3 [However, R6 represents a cycloalkyl group, a cycloalkyl group, or an aryl group having 1 to 10 carbon atoms, and M represents a real number of 1 to 3, or represents a halogen atom such as chlorine or bromine,
] is widely used.

Specifically, trialkylaluminum such as trimethylaluminum, triethylaluminum, triisopropylaluminum, I-liisobutylaluminum, and trioctylaluminum, and diethylaluminum monochloride, diimpropylaluminum monochloride, diimbutylaluminum monochloride, and dioctylaluminum monochloride. Examples include dialkylaluminum monohalides such as, and alkylaluminum sesquihalides such as ethylaluminum sesquichloride. Among these, trialkylaluminum is preferred, and triimbutylaluminum is particularly preferred.

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

-About the electron body (C)- (wherein, R1 and R4 represent a hydrocarbon group, preferably a substituted or unsubstituted saturated or unsaturated hydrocarbon group having 2 to 5 carbon atoms, R2R3 and R5 are hydrogen or) R hydrogen group, preferably hydrogen or a carbon number of 2
-5 substituted or unsubstituted saturated or unsaturated hydrocarbon groups, respectively).

If a substance other than the above-mentioned specific heterocyclic compound, such as a silane compound or an aromatic ester, is used as the electron donor (C), the stereoregularity of the raw 1 &ffi combination will not improve, resulting in molded products such as pipes. In addition, under conditions where the hydrogen/butene molar ratio is low, the moldability is significantly reduced and the amount of residual halogen in the polymer increases, causing corrosion in the molding machine. .

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 singly 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 specific solid catalyst component (A);
Butene-1 in the presence of a catalyst comprising the organoaluminum compound (B) and the specific heterocyclic compound (C).
Alternatively, butene-1 and other α-olefins are polymerized under gas phase polymerization conditions.

As the composition of the catalyst, the organoaluminum compound (B)
is 0.1 to 1000 times the molar amount of the tetravalent titanium halogen compound having the width of the solid catalyst component (A).

The amount of the heterocyclic compound (G) is preferably 1 to 500 times the mole of the solid catalyst component (A).
) 0.1 to 500 times the mole, preferably 0.5 to 500 times the titanium atom in the halogen compound of tetravalent titanium in
It is desirable that the amount is 200 times the molar amount.

Interest rate as a gas phase polymerization condition! ! It is desirable that the temperature is 45-70°C, preferably 50-65°C.

When the polymerization temperature is lower than 45°C, liquefaction is prevented (l-
However, since the partial pressure of butene-1 cannot be made too high, it may not be possible to increase the polymerization rate sufficiently, and it may be difficult to remove the polymerization heat on an industrial scale. Moreover, if the polymerization temperature is higher than 70°C,
The polymer particles produced may aggregate or adhere to walls, making the polymerization operation difficult, and the catalyst activity may also decrease, making it impossible to carry out the polymerization operation smoothly.

The partial pressure of butene-1 varies depending on the degree of polymerization, 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 1.5 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 above-mentioned specific range, the catalyst activity will be lowered or the amount of residual l\\rogene in the polymer will increase. Further, in some cases, it may become difficult to control the molecular H,+ of the polymer.

In the method of the present invention, it is possible to adjust the molecular weight i+1 of the polymer to a suitable range by using hydrogen, but if necessary, molecular weight adjusting agents other than hydrogen may be appropriately used.

Furthermore, an inert gas having a boiling point lower than that of butene-1, 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 the heat of polymerization. The effective use of inert gas is
The amount is 0.2 times or more by mole relative to butene-1.

Gas phase polymerization can be carried out using a fluidized bed or a stirred fluidized bed at a ratio of 1/1. 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 monomer.
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 monomers, and the butene-1 content in the copolymer is 60 to 98.5 mol%, preferably 70 to 98 mol%. % together with hydrogen etc. to a polymerization vessel and copolymerize.

When producing a so-called block copolymer, the first stage [-1
After the polymerization treatment of 1, the second stage [as the polymerization treatment of 1,
In the presence of the α-olefin homopolymer obtained in the first stage, butene-1 according to the present invention or butene-1 and other α-olefins are copolymerized.

Here, α-olefins other than butene-1 include, for example, propylene, ethylene, linear monoolefins such as hexene-11-1, branched heptan-olefins such as 4-methyl-pentene-1, and butadiene. Dienes such as can be used.

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

When gas phase polymerization D: is employed, the step of recovering the polymerization solvent can be omitted, and the step of drying the produced polymer can be greatly simplified by IPI.

In the method of this invention, post-treatment after polymerization can be carried out in the usual manner. That is, in the polymer powder extracted from the polymerization vessel after gas phase polymerization.

In order to remove olefins and the like contained therein, a nitrogen stream or the like may be passed through, if desired.

It may be pelletized using an extruder, and in this case, a small amount of water, alcohol, etc. may be added to completely deactivate the catalyst.

As described in 1- below, the butyl/
-1 polymer usually has an intrinsic viscosity [η] (decalin solution, 135°C) of 2.0 to 7.0 dl/g, and 1.1. (insoluble matter after 6 hours of Tuxlet extraction with boiling diethyl ether) is 95% or more, and the bulk density is 0.28 H/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) Catalytic activity is extremely high and catalyst residue Wrj remaining in the polymerization product can be reduced, so that catalyst residue from the obtained butene-1 polymer can be reduced. (2) It is possible to omit the step of removing polymers, and since there is almost no harmful residual liquid, it is possible to solve the problem of corrosion during molding. It is convenient for transportation, and (3) [η] is 2,
0-7. A method for producing a butene-1 polymer, which has advantages such as Od crossing/g and excellent stereoregularity (I-1,) and creep resistance, so it can be suitably used for pipes, for example. can be provided.

[Example] Next, examples of the present invention and comparative examples will be shown.
1 will be explained more specifically.

(Example 1) (1) Preparation of solid catalyst component In a well-dried 10M four-eye flask, 75 g of de-icing and purified ■-hexa and 500 g of magnesium jetoxide were added.
g (4,4 m o) and 153 g (0,55 m o n) of jubutylphthalate were added and the reaction was carried out under reflux for 1 hour.Then, the temperature was raised to 90 °C, and 2.5 kg of titanium tetrachloride was added. (132 m on)
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 removed, and butane 71 was added to n~ and stirred. After that, the supernatant liquid was removed after being allowed to stand still, and this operation was repeated twice to wash. I did it. After that, add 5 new n-hebutanes,
The temperature was set to 70°C, and 2.5 kg of titanium tetrachloride (13
2 m on) was added dropwise and the reaction was carried out at 90°C for 2 hours.Then, the temperature was raised to 80°C, the supernatant liquid was extracted, and the
- Washing was carried out by adding 7 grams of hebutane. 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 35 m, and the geometric standard deviation (σg) of particle size IIi was 1.3. Furthermore, when titanium JIU114 was measured by a colorimetric method, it was found to contain 2.8 tons of titanium.

(2) Preparation of Catalyst The solid catalyst component obtained in the above (1) was diluted to 2 mmouTiZ and placed in the catalyst tank W1. This catalyst 31
In the manufacturing tank, 30mmol of triisobutylaluminum
n/l, and 1,8-cineole 12 m m
o 41/view was provided. After that, titanium l m m
Propylene was fed at a rate of 50 g/on. The inside of the catalyst preparation tank was heated to 40° C.), and a reaction for catalyst preparation was carried out.

■ Production of butene-1 polymer A fluidized bed polymerization vessel with a diameter of 300 m5+ and a capacity of 100 was used.
The T1 catalyst slurry prepared in 11 batches was transferred from the catalyst preparation tank to the polymerization vessel for 0.15 hours/hr. 5, and triimbutylaluminum at 80 m m o n /
hr, Q:,'<, 1.8 cinere 24mm
on/hr.

They were each supplied to the polymerization vessel at an IQ jl' of .

The partial pressure of butene-1 and nitrogen were adjusted to 3 kg/crn' and 4 kg/crn', respectively, and the butene-1, N2
Gas and H2 gas were supplied. The discharge of the polymer was adjusted so that the amount of polymer in the 5 polymerization vessel was constant.

The drawing temperature was 55°C.

Intrinsic viscosity [η] of the obtained polymer, 1. r,, bulk density, residual titanium (analysis method: fluorescent X-ray method), residual! 1.1
111 Rik: (Analysis method: fluorescent X-ray method), creep resistance (evaluated in accordance with ASTM D2990), etc. are shown in Table 1.

(Example 2.3) The same procedure as in Actual Mph Example 1 was carried out except that H2/butene-1 (molar ratio) was changed to I shown in Table 1.

The results are shown in Table 1.

(Comparative Example 1) In Example 1 (3), methyl toluate was replaced with 3.8 mm 0/cross instead of 1,8-cineole, and Example 1 (3)
Example 1 was repeated, except that 1,8-cineole was replaced by a stream of 7.5 m m o i/br of methyl toluate.

The results are shown in Table 1.

(Comparative Example 2) In Example 1■, 1 mmon/l of diphenyldimethoxysilane was used instead of 1.8-cineole.
The same procedure as in Example 1 was conducted except that diphenyldimethoxysilane was supplied at a flow rate of 3 mmoi/hr in place of 1,8-cineole.

The results are shown in Table 1.

(Comparative Example 3.4) In Example 1, 5H2/butene-1 (molar ratio) was
The same procedure was carried out except that the procedure was changed to A11 shown in the table.

The results are shown in Table 1.

(Comparative Example 5) In Example 1■, di-n-butyl phthalate (7)
Addition 1.1- from 153 g (0.55 mol) of 7.
The same procedure as in Example 1 was carried out except that the amount was changed to 6 g (0,028 mol). In addition, in the solid catalyst component, 3-Off<
% of titanium.

The results are shown in Table 1.

(Example 4) In Example 1■, butene-1, propylene, N2 gas and N2 gas were supplied in the 11 combinations shown in Table 1, and a butene-1/propylene copolymer was produced. The same procedure as in Example 1 was carried out.

The results are shown in Table 1.

(Example 5) (1) Preparation of solid catalyst components 288.8 g of anhydrous Mg Cu, 33.2 g of diisobutyl phthalate and 13.2 g of vinyltriethoxysilane.
9g was placed in a vibrating mill with an internal volume of 1mm, and heated under a nitrogen atmosphere for 6 hours.
Co-milled for 0 hours.

25g of co-milled product was crushed at 500c under nitrogen atmosphere.
210 cc of T i Cl 4
brought into contact with.

Treatment with TiCua was carried out for 2 hours at 80°C with stirring at 100 rpm, after which excess TiCJL* and the product dissolved therein were removed by siphoning at 80°C.

This operation was followed by 200 ml of 65°C ethane per wash.
Washed 5 times using cc.

(2) 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 ton Dokton combination The same procedure as in Example 1 (2) was carried out except that the conditions shown in Table 2 were used.

Mu fruits are shown in Table 2.

(Example 6. Comparative Example 6) The same procedure as in Example 5 was carried out except that H2butene-1 (molar ratio) was changed to the value shown in Table 2.

The results are shown in Table 2.

(Example 7) (+) Preparation of solid catalyst component A calcined silicon oxide (manufactured by Futo-Davison Co., Ltd., grade 852, specific surface gl.
; 350 m'/g, f-average particle size; 54-85 gm
) and 1.51 g of trimethylchlorosilane were added, and after reacting for 12 hours with stirring in a reflux oven, n
- Decantation with hebutane was repeated 5 times and drying.

1! 2. An n-hebutane solution containing jetoxymagnesium (2500 mmol) and tetra-n-butoxytitanium (+500 mmol) in 500 g of the separated solids.
5 sentences were added and the mixture was left in contact for 1 hour at room temperature. After that, 1250 mjL of Improper Tool was added dropwise, stirred at 80°C for 1 hour, and then decanted with 5 parts of n-hebutane for 3 times.
The mixture was repeated several times and dried under reduced pressure at 80° C. for 1 hour to obtain a white catalyst carrier. In this catalyst carrier, 3.3 m; I'y'%
contained magnesium atoms.

375 g of the catalyst support obtained in this way was placed in a 52 glass container, and mixed with 2.5 g of n-hebutane, 95 mm of diisopropylphthalate, and 2250 g of titanium tetrachloride.
I put in. This mixture was stirred at 90° C. for 2 hours. Thereafter, the supernatant liquid was removed by decantation, and the obtained solid portion was washed with hot n-hebutane for -1 min to obtain a solid catalyst component. This catalyst contains 3.2. [
(Contains 1% Ti.

(2) Preparation of catalyst: The same procedure as in Example 1 (2) was carried out except for the conditions shown in Table jS2.

(2) Production of butene-1 homopolymer 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. Explanation of Figures The first is a flowchart showing catalyst preparation and polymerization.

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 (σg) 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 ▲ Numerical formula, chemical formula, table, etc. ▼ (1) (However, in the formula, R^1 and R^4 are hydrocarbon groups,
R^2, R^3 and R^5 each represent hydrogen or a hydrocarbon group. ) is a heterocyclic compound represented by
is 0.001 to 0.1.
1 Polymer manufacturing method.