JPS61204206A - Method of polymerizing 1-butene - Google Patents

Abstract

PURPOSE:In subjecting 1-butene to slurry polymerization in the presence of a polymerization catalyst consisting of a catalytic component comprising Mg, Ti, and a halogen as essential components, and an organo-aluminum compound, to obtain easily poly 1-butene having high bulk density, raising gradually the polymerization temperature. CONSTITUTION:In subjecting 1-butene to slurry polymerization in the presence of a polymerization catalyst consisting of a catalytic component (preferably one prepared by bringing Mg compound into contact with Ti halide compound) comprising Mg, Ti and a halogen as essential components and an organoalumi num compound (e.g., diethylaluminum chloride, butylaluminum dibromide, etc.), the polymerization temperature is gradually raised from >=0 deg.C initial temperature to 15-40 deg.C final temperature to complete the polymerization within preferably 10-60min. EFFECT:Main polymerization temperature can be reached in a shorter time that in a two-stage polymerization method accompanying a preliminary polymerization.

Description

[Detailed description of the invention] ＊Jh f) 4zeji54 The present invention relates to a method for polymerizing 1-butene.

Prior Art When 1-butene is slurry polymerized in a hydrocarbon medium in the presence of a Ziegler-Natsuta type catalyst, the resulting poly 1-
Butenes are easily swollen by hydrocarbons and therefore pose various problems in polymerization operations and are difficult to propagate into high bulk density polymers.

As a final measure, for example, a small amount of 1-butene is prepolymerized at a temperature of 20° C. or less at a concentration of titanium trihalide at least 5 times that in the main polymerization, and then 25 to 48
A method of main polymerization at a temperature of less than 50°C (Japanese Patent Publication No. 5B-461!!2) uses a titanium composite containing magnesium, titanium, halogen, and an electron donor as essential components.
Prepolymerize a small amount of 1-butene at jlK or at 80℃
A method in which a small amount of α-olefin is prepolymerized at a temperature of
JP-A-55-F23607 Bulletin J1 A method of polymerizing a small amount of α-olefin to give a highly crystalline polymer other than poly-1-butene in advance using trichloride (JP-A-55-F23607)
-127409] and the like have been proposed.

Although the bulk density of poly-1-butene is improved by these methods, it is difficult to control the prepolymerization of 1-butene and α-olefin, the prepolymerization takes a long time, and the main polymerization is difficult. Since the reaction temperature is relatively high, the amount of soluble polymer increases, and when it is removed by a t-7 lash using a reconstituted hydrogen medium after polymerization, there are problems such as adhesion of particles and formation of thin skin. Furthermore, in the case of prepolymerization with α-olefins other than 1-butene, if the prepolymerization i- is not strictly controlled, the content of polyα-olefin in poly-1-butene will increase and the original properties of poly-1-butene will be affected. There is a constant tendency to damage the

Problems to be Solved by the Invention It is an object of the present invention to provide a method for polymerizing 1-butene that can be easily developed into a poly-1-butene having a high bulk density.

Ninth Means to Solve the Problems As a result of intensive study, the inventors found that magnesium,
By using a catalyst component containing titanium and halogen as essential components, gradually increasing the polymerization temperature from an initial polymerization temperature of 0°C or less to 15 to 40°C, and continuing the polymerization at that temperature, The present invention was achieved by discovering that the object of the present invention can be achieved.

SUMMARY OF THE INVENTION That is, the gist of the present invention is to provide a method for slurry polymerizing 1-butene in the presence of a catalyst component containing magnesium, titanium, and halogen as essential components and a polymerization catalyst consisting of an organoaluminum compound. A process for polymerizing 1-butene which comprises gradually increasing the temperature from 15 to 40°C, preferably to a final temperature of 20 to 40°C.

Catalyst component The catalyst component used in the present invention contains magnesium, titanium, and halogen as essential components. The catalyst component is prepared by bringing magnesium metal or a magnesium compound into contact with a halogenated titanium compound, and desirably contains an electron-donating compound, a halogen element,
It is obtained by contacting with an activator such as a zero-gen-containing compound or an organic aluminum compound.

Magnesium compounds are represented by the general formula MgR"nR%-n. In the formula, R1 and R2 are the same or different hydrocarbon groups, OR3 group (R1 is the same or different hydrocarbon group as R1 and R1), OH group, halogen atom, 0≦n
≦2.

These magnesium compounds include Mg046MgB
Magnesium halides such as r1, Mgxl.

Mg(OHm)s * Mg(CxHg)s *”g(
'51hh a Mg(OaH,)s *MgO Goose Hs
-OaH Book 1 Mg (CsHtsha Mg (
OsHty)
OOtHs h # Mg (0℃sHy )se
Mg (0℃sHs)s, Mg (oc, a,)
s a'g(OOaHxy) * e Mg(0℃sHi
) m etc. dialkoxymagnesium, Mg (01)
) Oj etc. Also, magnesium compounds include aluminum and boron.

Perilicum, mixtures of zinc with organic compounds, aluminum, boron, beryllium, complexes of zinc with metals or compounds may also be used.

As a halogenated titanium compound, TiO4゜TiO4
, Ti (OOsH5) (/a , Ti (0℃s
Hi) CLs.

Ti (0℃sHs) sot*, Ti (00@
H@)10tt etc. are mentioned.

Examples of electron-donating compounds include alcohols, ethers, carboxylic acid esters, lactones, amines, and carboxylic acid esters.
Examples thereof include carbonaceous compounds, carboxylic acid anhydrides, carboxylic acid anhydrides, nitriles, ketones, aldehydes, thioethers, organic sulfur-containing compounds, and the like.

Alcohols include methanol, ethanol, globanol, butanol, and hexanol.

Octatool, cyclohexanol, phenol, cresol, catechol, ethylene glycol, 2,2.2
-) Lichlorethanol, 3-liC1/I/-1-70
Panol, p-/lorphenol, etc., and diethyl ether as the ether.

Dipropyl ether, diisopropyl ether.

Dibutyl ether, diisobutyl ether, diisoamyl ether, dihexyl ether, di2-ethylhexyl ether, anisole, tetrahydrofuran, etc., and examples of carboxylic acid esters include ethyl acetate, butyl butyrate, propyl pivalate, ethyl acrylic powder, and methacrylic acid. Ethyl, diethyl succinate, butyl adipate.

Examples of lactones include diethyl maleate, ethyl benzoate, methyl p-toluate, ethyl p-anisate, phthal dispersion, diptyl phthalate, and triethyl trimellidate. Examples include methylamine, ethylamine,
Diethylamine, tributylamine, aniline.

Tetramethylenediamine, etc., and carboxylic acid halides include acetic acid chloride, butyric acid chloride, acrylic acid chloride, methacrylic acid chloride, cepakun ryobromide,
maleic chloride.

Benzoyl chloride, p-toluic acid chloride, p-anisyl chloride, phthalic acid chloride, methyl maleic acid chloride, butyl phthalic acid chloride, etc., and the carboxylic acid anhydrides include acetic anhydride, maleic anhydride, benzoic anhydride, etc. , phthalic anhydride, etc., carboxylic acid amides such as acetic acid amide, benzoic acid amide, toluic acid amide, etc., nitriles such as acetonitrile, benzonitrile, tolnitrile, etc., and ketones such as acetone, methyl ethyl ketone, methyl inbutyl. Examples of aldehydes include acetaldehyde, propionaldehyde, hexylaldehyde, benzaldehyde, naphthaldehyde, etc.; Tylpenzyl phosphonate, tributylphosphine,
Triphenylphosphine etc., but as a thioether,
Diethyl thioether, diptyl thioether.

Examples include diphenylthioether and ethylphenylthioether.

Examples of the halogen element include chlorine, iodine, and bromine.

Examples of hydrogen-containing compounds include hydrogen halides such as hydrogen chloride and hydrogen bromide, and monochloroethane.

Halogenated hydrocarbons such as dichloroethane, trichloroethane, tetrachloroethane, hexachloroethane, dichloropropane, tetrachloropropane, hexachloropropane, dichlorobutane, trichloropentane, dichlorobenzene, TiO20a 81CZ4, 8nO
Z4 a B'Zs # 'l'4 #8b'4 a
BIs.

pcz, , pct, Hslots, etc. CD Metal or nonmetal element nohalokene compound, 80. C4,
, 800t, , N0O4P00ts, and the like include oxyhalides of nonmetallic elements.

Examples of organoaluminum compounds include dihydrocarbyl aluminum halides such as diethylaluminum chloride, diptylaluminum chloride, diethylaluminum bromide, dibutylaluminum bumide, dihexylaluminum chloride, diphenylaluminum chloride, methylaluminum dichloride, ethylaluminum dichloride, propylaluminum dichloride, etc. aluminum dichloride, butylaluminum dichloride.

Examples include hydrocarbyl aluminum dihalides such as phenyl aluminum dichloride, ethyl aluminum bromide, butyl aluminum dichloride, and the like.

Two or more types of these activators can be used, and when two or more types are used, they may be used simultaneously or sequentially. Contacting the magnesium metal or magnesium compound and the halogenated titanium compound with the above-mentioned activators can be carried out in an inert medium such as hexane, heptane, octane, cyclohexane, benzene, toluene.

- Mechanical pulverization or mixing and stirring in the presence or absence of hydrocarbons such as xylene. The order and method of contacting the activator with the magnesium metal or the magnesium compound and the halogenated titanium compound are arbitrary, but to explain in more detail, for example: A method of bringing a magnesium compound into contact with a halogen-containing compound and then contacting an electron-donating compound, or a method of bringing a magnesium compound into contact with a halogenated titanium compound without contacting the compound, ■ A method of bringing a magnesium compound into contact with a halogen-containing compound and an electron-donating compound, or a method of bringing a magnesium compound and an electron-donating compound into contact After contacting, a method of contacting an organoaluminum compound, a halogen element, or a halogen-containing compound, and then contacting a halogenated titanium compound, ■ Contacting the catalyst component obtained in ■ or ■ with a halogen-containing compound or an organoaluminum compound (2) A method in which magnesium metal is brought into contact with a halogen element, a halogen-containing compound, and/or an electron-donating compound, and then brought into contact with a halogenated titanium compound, with or without contacting with an electron-donating compound. It will be done.

Organoaluminum Compound In the present invention, the organoaluminum compound that can be used has the general formula RnAjXs-n (where R [alkyl group or aryl group, X] represents 10 gene atoms, an alkoxy group, or a hydrogen atom, and 1≦ n≦5. ] For example, trimethylaluminum, triethylaluminum, triprobylaluminium, triimbutylaluminum, trihexylaluminum, dimethylaluminum chloride, diethylaluminum chloride, diethylaluminum bromide, diisobutylaluminum chloride, methylaluminum dichloride, Ethyl aluminum dichloride, ethyl aluminum dibromide, isobutyl aluminum dichloride,
Ethylaluminum sesquichloride, diethylaluminum methoxide, diethylaluminum phenoxide,
Examples include diethylaluminolhamnohydride, diisoptylaluminolhydride, and the like. Two or more kinds of organoaluminum compounds may be used.

Polymerization Process Slurry polymerization of 1-butene is carried out in an inert medium and/or in liquefied 1-butene. Inert media that can be used include saturated hydrocarbons such as isobutane, n+butane, pentane, hexane, heptane, octane, decane, Schiff's hexane, and aromatic hydrocarbons such as benzene, toluene, and xylene.

In the present invention, it is important to keep the initial polymerization temperature below t-0°C, and the polymerization temperature is gradually increased from this initial temperature to bring the final polymerization temperature within the range of 15 to 40°C. The polymerization is further continued while maintaining the following. It is desirable to raise the temperature from the initial temperature to the final temperature within 10 minutes to 60 minutes, particularly within 20 minutes to 50 minutes. The polymerization time that continues after the temperature reaches the final temperature is usually about 1 to 10 hours.

Furthermore, the present invention, in conjunction with the above-mentioned temperature programming, allows the concentration of 1-butene during polymerization to be adjusted to a low S! It is also possible to adopt a method in which the concentration is gradually increased from 30 to 50°C, and the maximum concentration is reached when the final polymerization temperature is reached. In that case, the initial Is degree of 1-butene in an inert medium is
It is preferable to use a method in which 50 to 5 tons of liquefied 1-butene is gradually added per liter when the final polymerization temperature is reached. Alternatively, instead of adding 1-butene gradually as the temperature rises, it may be added all at once when the final polymerization temperature is reached. According to the above method,
When polymerization is carried out in an inert medium, the initial polymerization temperature can be relatively high compared to when no inert medium is used, but the maximum temperature cannot exceed +5°C.

In the present invention, if the initial polymerization temperature exceeds 0°C, the polymerization will proceed rapidly and the bulk density of the resulting poly-1-butene will decrease, so it must be kept below 0°C, but it is much lower than that temperature. Since the length of poly-1-butene is delayed and the polymerization time is wasted, the initial temperature is t--5o℃.
It is desirable to set it as the range of -0 degreeC. Also, the final polymerization temperature is 1
Below 5°C it takes a long line time to produce sufficient polymer, and above 40°C the polymer begins to swell, both of which are undesirable.

Polymerization may be carried out in one stage or in multiple stages.

When performing the polymerization in multiple stages, the polymerization can be performed by changing the polymerization temperature of the polymerization tank in each stage from the initial temperature to the final temperature.

The amount of the organoaluminum compound to be used in the catalyst component in the polymerization reaction is 1 to 1 ODD gram atom, preferably 10 to 200 gram atom of aluminum per gram atom of titanium in the catalyst component.

In addition to these polymerization catalysts, electron-donating compounds can be used if necessary. As the electron-donating compound, l! of the catalyst component is used. The same electron-donating compound as the activator sometimes used for 1 g may be used, but in addition to these, electron-donating compounds made of organosilicon compounds,
Nitrogen, sulfur.

Electron-donating compounds containing heteroatoms, such as dust, can also be used.

Specific examples of organosilicon compounds include tetraethoxysilane, tetrabutoxysilane, tetraphenoxysilane,
Ethyltriethoxysilane.

Butyltriethoxysilane, phenyltriethoxysilane, butyltributoxysilane, ethertriphenoxysilane, dimethyljethoxysilane, diethyldiisoptersilane, dibutyldiphenoxysilane 7, etc. are examples of electron-donating compounds containing heteroatoms. For example, 2,2
, 6.6-tetramethylbiperidine, 2,6-dimethylbiperidine, 2,2,5,5-tetramethylpyrrolidine, 2.5-diisopropylpyrrolidine, 2-methylpyridine, 2,6-dimethylpyrrolidine yptylpyridine, nicotinamide, diptylamine, thiophenol, 2-methylthiophene, diphenylthioether, tetrahydrofuran, 2,2,5.5-tetraethyltetrahydrofuran,
O-) di-t-butyl ketone, methyl-2,6-di-t
-butylphenyl ketone and the like. When an electron-donating compound is used, the amount thereof is usually 1 mol or less per 1 mol of the organoaluminum compound.

In order to control the molecular weight of the polymer, the polymerization reaction can be carried out in the presence of a known molecular weight regulator such as hydrogen, or can be copolymerized with a small amount of α-olefin other than 1-butene.

Effects of the Invention Compared to the known two-stage polymerization method involving prepolymerization, the method of the present invention employs a simple polymerization process in which the polymerization temperature is raised continuously, thereby increasing the main polymerization temperature in a short time. can be reached, and the bulk density of the poly-1-butene obtained therein is extremely high.

Example Hereinafter, the present invention will be explained in detail with reference to Examples.

In addition, "excellent" in the examples is based on the maximum weight unless otherwise specified. The bulk density of poly-1-butene is 8'l'M DI+395
Measured according to the -69 method. Also, Mx is M8T
Measured according to MD1238.

Example 1 Magnesium jetoxide 1LOf and n-hegetane 4Sdlf were added to a 200-liter flask which had been replaced with m-nitrogen gas as a catalyst component.
Add 2BF trichlorosilane and 17d n-
A mixture consisting of hebutane was added over a period of 45 minutes with stirring. 7
After stirring for 6 hours at 0 °C, the obtained solid i n-
Washed with hexane. Then toluene 30- and di-n-butyl heptatalate 2. After adding Of and heating to 50℃,
Quaternary titanium 60- was added and stirred at 120°C for 2 hours.

qacrtc was cooled, the solid was washed with toluene, 50 wt of toluene and 60-1 of titanium tetrachloride were added, and 1
The mixture was stirred at 20°C for 2 hours. The obtained solid was washed with hexane and then vacuum dried to obtain &5F powdered catalyst component gold.

The catalyst components include 17% titanium, 1 & 9% magnesium
It contained 49.5 chlorine.

Polymerization of 1-Butene In a t5t autoclave equipped with a stirrer, under nitrogen atmosphere, 44.4 mW'tM of the catalyst components obtained above, 515 mmol of triethylaluminum, (1) 6 mmol of phenyl trifluoride were added. Ethoxysilane, 8GO-〇 liquefied 1-butene, and 400 d of hydrogen gas were added, and the mixture was cooled to -50°C. The F ampoule was broken by the rotation of the stirrer, and stirring and heating of the polymerization system were immediately started, the temperature was raised to 25° C. in 40 minutes, and the polymerization was continued for an additional 3 hours and 20 minutes. Unreacted 1-butene was purged, and the resulting polymer was vacuum dried (65°C, 7 hours) to a bulk density of 136
f/eyn”, M x 2.2 f/10 min poly 1
-butene 1o y, S f was obtained. Catalyst specific activity Ec
(catalyst component 1f, polymer production fil per hour) =
604. It (titanium 1f in the catalyst component, phosphorus produced per hour in the polymer) was 356.

Example 2 27.9 m of the catalyst component used in Example 1 was placed in the autoclave used in Example 1. , 400 mg of 1-butene, 400 mg of isobutane, and 200 dt of hydrogen gas were added, and the polymerization of 1-butene was started at -10° C. in the same manner as in Example 1. At the same time as the start of polymerization, the polymerization temperature was completely raised and 50 minutes later, 33
The polymerization of 1-butene was further continued at the same temperature for 55 hours.

The results are shown in the table.

Examples 5 and 4 1-Butene was polymerized in the same manner as in Example 1, except that the initial temperature, final temperature, and heating time were as shown in the table, and the results are shown in the table.

Example 5 In the autoclave used in Example 1, 57.9 mW of the catalyst components used in Example 1, 300 − of 1-butene, 500 − of isobutane, and 200 − of hydrogen gas were charged, and the The weight of 1-butene at °C! -t- started. Simultaneously with the start of polymerization, the polymerization temperature was raised to 30° C. after 30 minutes, and at that point, 20 (1d) of 1-butene was introduced under pressure, and the addition of 1-butene was continued for 55 hours at the same temperature.

The results are shown in the full table.

Example 6 The catalyst component 2i used in Example 1 was added to the autoclave used in Example 1. mf, 100 d of 1-butene, 500 d of isobutane, and 200 dt of hydrogen gas, and polymerization of 1-butene was started at -5°C in the same manner as in Example 1. At the same time as the polymerization started, 400 d of 1-butene was added over 40 minutes. While gradually press-fitting, the polymerization temperature was also raised at the same time as the start of polymerization.
After 0 minutes, the temperature was raised to 30°C, and at the same temperature, 1-butene was polymerized.
- Lasted for 15 hours. The results are shown in the table.

Comparative Examples 1 and 2 1-Butene was polymerized in the same manner as in Example 1, except that the polymerization conditions were as shown in the table, and the results were shown in t-scale.

Example 7 Anhydrous magnesium chloride 19, Of, ethyl benzoate 10F, and 1-hexene λ6ff were placed in a vibrating mill pot made of stainless steel (8085163) under a nitrogen gas atmosphere, and pulverized by shaking for 1 hour while cooling with water. Add 58% of titanium tetrachloride to this pot, and add 24% of titanium tetrachloride while cooling with water.
The mixture was shaken for hours and pulverized to obtain a catalyst component of 24.8 f'.

Polymerization of 1-butene 1-Butene was polymerized in the same manner as in Example 1, except that the catalyst component obtained above was used, and the results are shown in the table.

Preparation of catalyst components Anhydrous chlorination! Gnesicum 20f, benzoin ethyl a2f and methylpolysiloxane (particle size 100aS) 50-,
15 diameter stainless steel balls 2.8k in nitrogen atmosphere
The mixture was placed in a stainless steel vibrating mill pot with an inner volume of 800-1 and an inner diameter of 10G containing 1I, and pulverized by shaking for 24 hours. Obtained co-pulverized product 2 (L5fi titanium tetrachloride 20
The suspension was suspended in 200° C. and stirred for 2 hours at 80° C., immediately filtered through a glass filter containing solid components, and washed 8 times with purified n-hexane 200° C. at room temperature. Dry for 1 hour at room temperature under reduced pressure to remove 2α8f catalyst component'f:@
Manufactured. This catalyst component Kt! T12.1%, Mg22.
5%, 0161>04 was included.

1-Butene was polymerized in the same manner as in Example 1, except that the catalyst component prepared as described above was used, and the results are shown in the table.

Example 9 Preparation of catalyst components 4.76 tSn-f cans of anhydrous magnesium chloride were placed in a 500-liter flask that had been sufficiently purged with nitrogen gas.
-Ethylhexanol 25- was added. The reaction was carried out at 150°C for 2 hours, and 1.1 ft of phthalic anhydride was added. Titanium tetrachloride was added dropwise to this at 200 di-20°C over 50 minutes, and the temperature was gradually raised. 1) When it reached 0°C, 2.68 dt of diimbutyl phthalate was added.
Stirring was continued for 2 hours at 0°C. After the reaction, supernatant gt-
and washed twice with 100 °C of toluene at 1) 0°C. Add 200% of titanium tetrachloride again, 1) 2 at 0°C.
After reacting for a period of time, the obtained next product is converted into n-
Washed 8 times with hexanoate at room temperature. Drying was performed at room temperature for 1 hour under reduced pressure to prepare a catalyst component.

Synthesis of 1-Butene 1-Butene was polymerized in the same manner as in Example 1, except that the catalyst component obtained above was used, and the results are tabulated.

Claims (3)

[Claims] (1) In a method of slurry polymerizing 1-butene in the presence of a catalyst component containing magnesium, titanium, and halogen as essential components and a polymerization catalyst consisting of an organoaluminum compound, the polymerization temperature is changed from an initial temperature of 0°C or lower to 15 to 40°C.
A process for the polymerization of 1-butene, which comprises gradually increasing the temperature to a final temperature of . (2) The method according to claim (1), wherein the initial temperature is within the range of -50°C to 0°C. (3) Temperature rise from initial temperature to final temperature is 10 minutes to 6 minutes
Claim (1) that is completed within 0 minutes
The method described in paragraph or (2).