JPH0651750B2 - Polymerization of 1-butene - Google Patents

Description

TECHNICAL FIELD The present invention relates to a method for polymerizing 1-butene.

2. Description of the Related Art When 1-butene is slurry-polymerized in a hydrocarbon medium in the presence of a Ziegler-Natsuta type catalyst, the resulting poly 1-
Butene is liable to swell in hydrocarbons, which causes various problems in the polymerization operation and makes it difficult to produce a polymer having a high bulk density.

As a solution to this problem, for example, at a temperature of 20 ° C. or lower, the concentration of titanium trihalide is set to 5 times or more than that in the main polymerization, and a small amount of 1-butene is prepolymerized, and then 25 to 48
A method of main polymerization at ℃ (JP-A-58-46132), a titanium complex containing magnesium, titanium, halogen and an electron donor as an essential component is used to produce a small amount of 1-butene at a temperature of less than 30 ℃. A method of prepolymerizing or prepolymerizing a small amount of α-olefin at a temperature of 80 ° C or lower, and then polymerizing 1-butene at a temperature of 30 to 48 ° C (JP-A-55-123607), titanium trichloride. To give a highly crystalline polymer other than poly-1-butene in advance with a small amount of α-
Method for polymerizing olefin (JP-A-55-12740)
No. 9) are proposed.

Although the bulk density of poly-1-butene is improved by these methods, it is difficult to control the amount of prepolymerization of 1-butene and α-olefin, and it takes a long time to carry out the prepolymerization. Since the reaction temperature is relatively high, the amount of soluble polymer increases, and when the hydrocarbon medium is removed by flashing after polymerization, there are problems such as mutual adhesion of particles and generation of thin skin. Furthermore, in the case of prepolymerization with α-olefin other than 1-butene, if the amount of prepolymerization is not strictly controlled, the content of poly α-olefin in poly 1-butene will increase, and the original properties of poly 1-butene will be retained. There is a harmful effect of damaging it.

DISCLOSURE OF THE INVENTION Problems to be Solved by the Invention An object of the present invention is to provide a method for polymerizing 1-butene that can easily produce poly-1-butene having a high bulk density.

Means for Solving the Problems As a result of intensive studies, the present inventors have used a titanium trichloride component to gradually increase the polymerization temperature from an initial polymerization temperature of 5 ° C. or lower to 20 to 40 ° C. The present invention was completed by finding that the object of the present invention can be achieved by further continuing the polymerization at that polymerization temperature.

That is, the present invention is a method of slurry-polymerizing 1-butene in the presence of a titanium trichloride component and an organoaluminum compound, wherein the polymerization temperature is 20 to 40 from an initial temperature of 5 ° C or lower.
The gist is a method for polymerizing 1-butene, which comprises gradually increasing the temperature to a final temperature of ° C.

Titanium trichloride component The titanium trichloride component used in the present invention is typically titanium trichloride obtained by reducing titanium tetrachloride with hydrogen, aluminum, an organic aluminum compound or the like, and heating them. Those modified by treatment are also included. These titanium trichloride components may be used themselves, but those obtained by treating them with an activator such as an electron donating compound, a halogen element, a halogen-containing compound and the like are preferable.

Examples of the electron-donating compound include alcohols, ethers, carboxylic acid esters, lactones, amines, carboxylic acid halides, carboxylic acid anhydrides, carboxylic acid amides, nitriles, ketones, aldehydes, thioethers and organic phosphorus-containing compounds.

Examples of alcohol include methanol, ethanol, propanol, butanol, hexanol, octanol, cyclohexanol, phenol, cresol, catechol, ethylene glycol, 2,2,2-trichloroethanol, 3-chloro-1-propanol, p-chlorophenol and the like. However, as ether, diethyl ether,
Dipropyl ether, diisopropyl ether, dibutyl ether, diisobutyl ether, diisoamyl ether, dihexyl ether, di2-ethylhexyl ether, anisole, tetrahydrofuran, etc., and carboxylic acid esters include ethyl acetate, ethyl butyrate, propyl pivalate, acrylic acid. Ethyl, ethyl methacrylate, diethyl succinate, butyl adipate, diethyl maleate, ethyl benzoate, methyl p-toluate, p
-Ethyl anisate, monobutyl phthalate, dibutyl phthalate, triethyl trimellitate and the like, lactones such as γ-butyrolactone and δ-valerolactone, and amines such as methylamine, ethylamine, diethylamine, tributylamine, aniline, Examples of carboxylic acid halides such as tetramethylenediamine include acetic acid chloride, butyric acid chloride, acrylic acid bromide, methacrylic acid chloride, sebacic acid bromide, maleic acid chloride, benzoyl chloride, p-toluic acid chloride, p-
Anisic acid chloride, phthalic acid dichloride, maleic acid methyl chloride, phthalic acid butyl chloride and the like, carboxylic acid anhydrides such as acetic anhydride, maleic anhydride, benzoic acid and phthalic anhydride, and carboxylic acid amides, Acetamide, benzoic acid amide, toluic acid amide and the like, nitriles such as acetonitrile, benzonitrile and tolunitrile, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, benzophenone and acetophenone, and aldehydes such as acetaldehyde, Propionaldehyde, hexylaldehyde, benzaldehyde, naphthaldehyde and the like are organic phosphorus-containing compounds such as trimethylphosphite, triphenylphosphite, diphenylethylphosphonate and diethylben. Ruhosuhoneito, tributyl phosphine, triphenylphosphine or the like, as a thioether, diethyl thioether, dibutyl ether,
Examples thereof include diphenyl thioether and ethyl phenyl thioether.

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

Examples of halogen-containing compounds include hydrogen halides such as hydrogen chloride and hydrogen bromide, monochloroethane, dichloroethane,
Halogenated hydrocarbons such as trichloroethane, tetrachloroethane, hexachloroethane, dichloropropane, tetrachloropropane, hexachloropropane, dichlorobutane, trichloropentane and dichlorobenzene, TiCl
₄ , SiCl ₄ , SnCl ₄ , BCl ₃ , AlCl ₃ , SbCl ₃ , BI ₃ , PCl ₃ , PCl
₅ , halogen compounds of metal or non-metal elements such as HSiCl ₃ and oxyhalides of non-metal elements such as SO ₂ Cl ₂ , SOCl ₂ , NOCl, POCl _{3 and the} like.

These activators are not limited to one type, and two or more types can be used. When two or more types are used, they may be used simultaneously or sequentially. Treatment with the activator may be carried out in the presence of an inert medium. Examples of the inert medium include hydrocarbons such as hexane, heptane, octane, cyclohexane, benzene, toluene and xylene.

The activation treatment with these activators will be described in more detail. For example, titanium trichloride or a complex thereof is treated with an electron-donating compound in the presence or absence of a halogen element and then further treated with a metal or non-metal. A method of treating with a halogen compound of an element, a method of treating with a halogen compound of a metal or non-metal element in the presence or absence of a halogen element, a treatment with a halogen compound of a metal or non-metal element after treatment with an electron-donating compound A method of treating with a complex compound of an electron donating compound, a method of treating with an electron donating compound and then a halogenated hydrocarbon, a method of treating with a halogenated hydrocarbon in the presence of an electron donating compound, A method of further treating the treated material with a halogen compound of a metal or a non-metal element, and the like can be mentioned.

Organoaluminum Compound The organoaluminum compound that can be used in the present invention is represented by the general formula RnAlX _3-n (wherein R represents an alkyl group or an aryl group, X represents a halogen atom, an alkoxy group or a hydrogen atom, and 1 ≦ n ≦ 3). ), For example, trimethyl aluminum, triethyl aluminum, tripropyl aluminum, triisobutyl aluminum, trihexyl aluminum, dimethyl aluminum chloride, diethyl aluminum chloride, diethyl aluminum bromide, diisobutyl aluminum chloride, methyl aluminum dichloride. , Ethyl aluminum dichloride, ethyl aluminum dipromide, isobutyl aluminum dichloride, ethyl aluminum sesquichloride, diethyl aluminum meth Sid, diethylaluminum phenoxide, diethylaluminum hydride, and diisobutylaluminum hydride and the like. The organoaluminum compound is
You may use 2 or more types.

Polymerization Method Slurry polymerization of 1-butene is carried out in an inert medium and / or liquefied 1-butene. Examples of the inert medium that can be used include saturated hydrocarbons such as isobutane, n-butane, pentane, hexane, heptane, octane, decane and cyclohexane, and aromatic hydrocarbons such as benzene, toluene and xylene.

In the present invention, it is important to set the initial polymerization temperature to 5 ° C. or lower, and gradually increase the polymerization temperature from this initial temperature to bring the final polymerization temperature to within the range of 20 to 40 ° C. and maintain this temperature. However, the polymerization is further continued.
Then, it is desirable to raise the initial temperature to the final temperature within 10 minutes to 60 minutes, particularly within 20 minutes to 50 minutes. After the temperature rises to the final temperature, the continuous polymerization time is usually 1
It is about 10 hours.

Further, in the present invention, in combination with the above temperature programming, when the polymerization is carried out in an inert medium, the concentration of 1-butene during the polymerization is gradually increased from a low concentration at the beginning of the polymerization to achieve the final polymerization temperature. The method of maximizing the concentration can also be adopted. In that case, the initial concentration of 1-butene in the inert medium is 5 to 50.
It is desirable to use a method of gradually adding liquefied 1-butene (500 ml to 5) per inert medium until the final polymerization temperature is reached by volume. It is also possible to adopt a method in which 1-butene is not added gradually when the temperature rises but is added all at once when the final polymerization temperature is reached. When the polymerization is carried out in an inert medium by the above method, the initial polymerization temperature can be relatively increased as compared with the case where an inert medium is not used, but the maximum temperature cannot exceed + 5 ° C.

In the present invention, when the initial polymerization temperature exceeds 5 ° C, the polymerization rapidly progresses and the bulk density of the obtained poly 1-butene decreases, so it is necessary to set it to 5 ° C or less, but if it is much lower than that temperature, Since the growth of 1-butene is delayed and the polymerization time is wasted, the initial temperature is -10 ° C to
It is desirable that the temperature range is + 5 ° C. The final polymerization temperature is 2
If it is lower than 0 ° C, it takes a long time to produce a sufficient polymer, and if it exceeds 40 ° C, the polymer starts to swell, which is not desirable.

The polymerization may be carried out in one stage or in multiple stages. When carrying out in multiple stages, the polymerization temperature in each stage of the polymerization tank can be changed in multiple stages from the initial temperature to the final temperature.

The ratio of titanium trichloride component and organoaluminum compound used in the polymerization reaction is aluminum / titanium (atomic ratio)
Is 1 to 2,000, preferably 20 to 500. In addition to these two components, an electron donating compound can be used if necessary. The electron donating compound may be the same as that used as an activator for the titanium trichloride or the complex thereof. When the electron-donating compound is used, the amount thereof is usually 1 mol or less per 1 mol of the organoaluminum compound.

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

EFFECTS OF THE INVENTION According to the method of the present invention, the main polymerization temperature can be reached in a short time by adopting a simple polymerization process in which the polymerization temperature is continuously increased as compared with the known two-step polymerization method involving prepolymerization. There is an effect that the obtained poly (1-butene) has a very high bulk density.

Examples Hereinafter, the present invention will be described in detail with reference to Examples. In addition,% in the examples is based on weight unless otherwise specified. The bulk density of poly 1-butene was measured according to ASTM D1895-69 Method A.

Also, MI was measured according to ASTM D1238.

Example 1 Preparation of titanium trichloride component 700 ml of n-heptane and 250 ml of titanium tetrachloride were placed in a flask 2 equipped with a stirrer and cooled to 0 ° C. Then 315 ml of diethyl aluminum chloride, 117 ml of ethyl aluminum dichloride and 40
A mixed solution of 0 ml of n-heptane was added dropwise at 0 ° C. over 3 hours, heated to 65 ° C., and further stirred for 1 hour. 25 g of the obtained reduced solid was added to 100 ml of n-heptane.
And 1 gram mole of hexachloroethane n-heptane solution and 0.6 gram mole of dinormal butene ether per gram atom of titanium in the reduced solid,
After stirring at 80 ° C. for 5 hours, it was washed with n-heptane to prepare a titanium trichloride component having a titanium content of 31.0%.

Polymerization of 1-butene In a 1.5 autoclave equipped with a stirrer, a glass ampoule in which 800 ml of liquefied 1-butene under nitrogen atmosphere, 4.5 mmol of diethylaluminum chloride, and 46.1 mg of the titanium trichloride component prepared above were enclosed. And 600 ml of hydrogen gas were added and the polymerization system was cooled to -5 ° C. While breaking the glass ampoule by rotating the stirrer, immediately start stirring and heating the polymerization system and raise the temperature to 35 ° C in 35 minutes.
Polymerization was continued for another 3 hours and 25 minutes. The unreacted 1-butene was barged, and the resulting polymer was vacuum dried (65 ° C., 7 hours) to obtain 55.9 g of poly-1-butene having a bulk density of 0.49 g / cm ³ and MI of 0.20 g / 10 min. Obtained. Catalyst specific activity Ec (titanium trichloride component 1 g, amount of polymer formed per t time)
= 303, Et (1 g of titanium in titanium trichloride component, amount of polymer produced per hour) = 975.

Examples 2 to 4 1-butene was polymerized in the same manner as in Example 1 except that the polymerization conditions were as shown in the table. The results are shown in the table.

Example 5 The autoclave used in Example 1 was charged with the titanium trichloride component used in Example 1 (76.7 mg), 1-butene (200 ml), isobutane (200 ml) and hydrogen gas (300 ml).
The polymerization of 1-butene was started at 2 ° C in the same manner as in. After 20 minutes from the start of the polymerization, 400 ml of 1-butene was injected under pressure, the polymerization temperature was raised to 33 ° C. 20 minutes after the start of the polymerization, and the 1-butene polymerization was continued at the same temperature for 7 hours and 40 minutes. The results are shown in the table.

Example 6 The autoclave used in Example 1 was charged with 49.8 mg of the titanium trichloride component used in Example 1, 50 ml of 1-butene, 200 ml of isobutane and 400 ml of hydrogen gas, and the same procedure as in Example 1 was conducted at 4 ° C. -The polymerization of butene has started. Simultaneously with the start of the polymerization, 750 ml of 1-butene was injected under pressure for 30 minutes, the polymerization temperature was raised to 33 ° C. 35 minutes after the initiation of the polymerization, and the polymerization of 1-butene was continued at the same temperature for 3 hours and 25 minutes. The results are shown in the table.

Comparative Examples 1 to 3 1-butene was polymerized in the same manner as in Example 1 except that the polymerization conditions were changed as shown in the table, and the results are shown in the table.

Example 7 Preparation of titanium trichloride component In a steel ball mill whose inside was replaced with argon gas,
240 g of commercially available AA type titanium trichloride was added, and further, a reaction product of 12 g of diethyl ether and 2.5 g of titanium tetrachloride was added, followed by grinding for 10 hours to prepare a titanium trichloride component.

Polymerization of 1-butene 1-butene was polymerized in the same manner as in Example 1 except that the titanium trichloride component obtained above was used and the polymerization conditions were as shown in the table. The results are shown in the table.

Comparative Example 4 1-same as in Example 1 except that the titanium trichloride component used in Example 7 was used and the polymerization conditions were as shown in the table.
Butene was polymerized and the results are shown in the table.

[Brief description of drawings]

FIG. 1 is a flow chart showing the method of the present invention.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Chihiro Imai 5-4, 4-49, Migamioka, Midori-ku, Yokohama-shi, Kanagawa (56) References JP-A-55-123607 (JP, A) JP-A-55-127409 ( JP, A) JP 53-146045 (JP, A)

Claims (3)

[Claims] 1. A method of slurry-polymerizing 1-butene in the presence of a titanium trichloride component and an organoaluminum compound, wherein the polymerization temperature is gradually increased from an initial temperature of 5 ° C. or less to a final temperature of 20 to 40 ° C. A method of polymerizing 1-butene comprising 2. The method according to claim 1, wherein the initial temperature is within the range of -10 ° C to + 5 ° C. 3. The temperature rise from the initial temperature to the final temperature is 10
Claims to be completed within minutes to 60 minutes
The method according to item (1) or (2).