JPH0651751B2 - 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 Ziegley-Natsuta type catalyst, the 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 made 5 times or more higher 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 the damage of damage.

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 Problems As a result of earnest research, the present inventors have found that magnesium,
By using a catalyst component containing titanium and halogen as essential components, the polymerization temperature is gradually raised from the initial polymerization temperature of 0 ° C. or less to 15 to 40 ° C., and the polymerization is further continued at that temperature. The present invention has been achieved by finding that the above object can be achieved.

SUMMARY OF THE INVENTION That is, the gist of the present invention is 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. It is a process for polymerizing 1-butene which comprises gradually increasing from an initial temperature to a final temperature of 15-40 ° C, preferably 20-40 ° 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 a magnesium metal or magnesium compound into contact with a titanium halide compound, and preferably an activator such as an electron-donating compound, a halogen element, a halogen-containing compound, an organoaluminum compound during preparation. It was obtained by contacting with.

The magnesium compound is represented by the general formula MgR ¹ nR ² _2-n . In the formula, R ¹ and R ² are the same or different hydrocarbon groups,
OR ³ group (R ³ is a hydrocarbon group which is the same as or different from R ¹ and R ² ), OH
A group and a halogen atom, and 0 ≦ n ≦ 2.

These magnesium compounds include MgCl ₂ , MgBr ₂ , Mg
Magnesium halides such as I ₂ , Mg (CH ₃ ) ₂ , Mg (C
₂ H ₅ ) ₂ , Mg (C ₃ H ₇ ) ₂ , Mg (C ₄ H ₉ ) ₂ , MgC ₂ H ₅ · C ₄ H ₉ , Mg (C
_{6 H 13) 2, Mg (} C 8 H 17) 2, Mg (C 6 H 5) dihydrocarbyl magnesium such as _{2, Mg (OCH 3) 2} , Mg (OC 2 H 5) 2, Mg (OC 3 H ₇ ) ₂ , Mg
Examples thereof include dialkoxy magnesium such as (OC ₄ H ₉ ) ₂ , Mg (OC ₆ H ₁₃ ) ₂ , Mg (OC ₃ H ₁₇ ) ₂ , Mg (OC ₆ H ₅ ) ₂ and Mg (OH) Cl.
As the magnesium compound, a mixture with an organic compound of aluminum, boron, beryllium or zinc, or a complex with a metal or compound of aluminum, boron, beryllium or zinc may be used.

Titanium halide compounds include TiCl ₄ , TiCl ₃ , Ti (O
_{C 2 H 5) Cl 3,} Ti (OC 4 H 9) Cl 3, Ti (OC 2 H 5) 2 Cl 2, Ti (OC 6 H 5) 2 Cl 2 , and the like.

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 alcohols 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, butyl butyrate, propyl bivalate, 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 such as acetic acid amide. Amides, benzoic acid amide, toluic acid amide, etc., nitriles such as acetonitrile, benzonitrile, tolunitrile, etc., ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, benzophenone, acetophenone, etc., and aldehydes such as acetaldehyde, propione. Aldehydes, hexyl aldehydes, benzaldehydes, naphthaldehydes and the like are organic phosphorus-containing compounds such as trimethyl phosphite, triphenyl phosphite, diphenyl ethyl phosphonate, diethyl benzene. Ruhosuhoneito, tributyl phosphine, triphenylphosphine or the like, as a thioether, diethyl thioether, dibutyl ether,
Examples include diphenyl thioether and ethyl phenyl thioether.

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

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 , PC
Examples thereof include halogen compounds of metal or non-metal elements such as l ₅ and HSiCl ₃ , and oxyhalides of non-metal elements such as SO ₂ Cl ₂ , SOCl ₂ , NOCl and POCl ₃ .

Examples of the organic aluminum compound include diethyl aluminum chloride, dibutyl aluminum chloride, diethyl aluminum bromide, dibutyl aluminum bromide, dihexyl aluminum chloride, diphenyl aluminum chloride and other dihydrocarbyl aluminum halides, methyl aluminum dichloride, ethyl aluminum dichloride, propyl aluminum dichloride,
Examples thereof include hydrocarbyl aluminum dihalides such as butyl aluminum dichloride, phenyl aluminum dichloride, ethyl aluminum dipromide, and butyl aluminum dibromide.

Two or more kinds of these activators can be used, and when two or more kinds are used, they may be used simultaneously or may be used sequentially. The contact between the magnesium metal or the magnesium compound and the titanium halide compound and the above-mentioned activator is carried out in the presence or absence of an inert medium, for example, a hydrocarbon such as hexane, heptane, octane, cyclohexane, benzene, toluene and xylene. The bottom is mechanically pulverized or mixed and stirred. The contact order and contact method of the activator with the magnesium metal or the magnesium compound and the titanium halide compound are arbitrary, but will be described in more detail. For example, the magnesium compound is contacted with the electron-donating compound, and then the titanium halide is used. Method of contacting with compound, Method of contacting magnesium compound with halogen-containing compound and contacting with electron donating compound, or contacting with titanium halide compound without contacting, After contacting magnesium compound and electron donating compound A method of contacting an organoaluminum compound, a halogen element or a halogen-containing compound, and then contacting a titanium halide compound, or a method of contacting the catalyst component obtained by the method with a halogen-containing compound or an organoaluminum compound, and halogenating magnesium metal. element After contacting with the halogen-containing compound and / or an electron-donating compound, or contacting the electron-donating compound, a method of contacting with titanium halide compounds not touch, and the like.

Organoaluminum Compound In the present invention, the organoaluminum compound that can be used 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 aluminium dichloride, ethyl aluminum sesquichloride, diethyl aluminum methoxide, diethyl aluminum phenoxide, diethyl aluminum hydride, diisobutyl aluminum hydride Etc. 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, hebutane, 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 0 ° C. or lower, and gradually increase the polymerization temperature from this initial temperature to keep the final polymerization temperature within the range of 15 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 0 ° C., the polymerization rapidly progresses and the bulk density of the obtained poly-1-butene decreases, so it is necessary to set the temperature to 0 ° C. or lower. Since the growth of 1-butene is delayed and the polymerization time is wasted, the initial temperature is from −50 ° C.
It is desirable to set the temperature in the range of 0 ° C. The final polymerization temperature is 15
If it is less than ℃, it takes a long time to produce a sufficient polymer,
Above 40 ° C, the polymer begins to swell, neither of which is 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 amount of the organoaluminum compound used with respect to the catalyst component in the polymerization reaction is 1 to 1,000 g atom, preferably 10 to 200 g atom, as aluminum per 1 g atom of titanium in the catalyst component.
In addition to these polymerization catalysts, an electron donating compound can be used if necessary. The electron-donating compound may be the same as the electron-donating compound as an activator that may be used during the preparation of the catalyst component, but other than those, an electron-donating compound composed of an organosilicon compound, nitrogen, An electron-donating compound containing a hetero atom such as sulfur or oxygen can also be used.

Specific examples of the organic silicon compound include tetraethoxysilane, tetrabutoxysilane, tetraphenoxysilane,
Electron donors containing heteroatoms such as ethyltriethoxysilane, butyltriethoxysilane, phenyltriethoxysilane, butyltributoxysilane, ethyltriphenoxysilane, dimethyldiethoxysilane, diethyldiisobutylsilane, and dibutyldiphenoxysilane Specific examples of the organic compound include 2,2,6,6-tetramethylpiperidine, 2,6-dimethylpiperidine, 2,2,2.
5,5-tetramethylpyrrolidine, 2,5-diisopropylpyrrolidine, 2-methylpyridine, 2,6-diisobutylpyridine, nicotinamide, dibutylamine,
Thiofenol, 2-methylthiophene, diphenylthioether, tetrahydrofuran, 2,2,5,5-tetraethylterolahydrofuran, o-tolyl-t-butylketone, methyl-2,6-dit-butylphenylketone, etc. Can be mentioned. When an electron-donating compound is used, the amount used is usually 1 per mol of the organoaluminum compound.
It is less than or equal to mol.

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 Adjustment of Catalyst Components A 200 ml flask purged with nitrogen gas was charged with 8.0 g of magnesium diethoxide and 45 ml of n-heptane, to which a mixture consisting of 28 g of olichlorosilane and 17 ml of n-heptane was added. Added under stirring for 45 minutes. 70
After stirring at 6 ° C for 6 hours, the obtained solid was washed with n-hexane at 65 ° C. Next, after adding 30 ml of toluene and 20 g of di-n-butyl phthalate and heating to 50 ° C, 60 ml of titanium tetrasalt was added and stirred at 120 ° C for 2 hours. 90
After cooling to ° C, the solid was washed with toluene, 30 ml of toluene and 60 ml of titanium tetrachloride were further added, and the mixture was stirred at 120 ° C for 2 hours. The obtained solid was washed with hexane and then vacuum dried to obtain 8.5 g of a powdery catalyst component. This catalyst component contains 1.7% titanium, 16.9% magnesium,
It contained 49.5% chlorine.

Polymerization of 1-butene In a 1.5 autoclave equipped with a stirrer, under a nitrogen atmosphere, 44.4 mg of the catalyst component obtained above was enclosed in a glass amble, 3.15 mmol of triethylaluminum, and 0.16 mmol of Phenyltriethoxysilane, 800 mg of liquefied 1-butene and 400 ml of hydrogen gas were added, and the mixture was cooled to -50 ° C. The amble was broken by rotating 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 further continued for 3 hours and 20 minutes. The unreacted 1-butene was barged and the resulting polymer was vacuum dried (65 ° C., 7 hours) to give a bulk density of 0.36.
Poly 1-butene 10 g / cm ³ , MI 2.2 g / 10 min
7.3 g was obtained. Catalyst specific activity Ec (catalyst component 1 g, polymer production amount per hour) = 604, Et (titanium in catalyst component 1 g, polymer production kg amount per hour) = 3
It was 3.6.

Example 2 In the autoclave used in Example 1, 27.9 mg of the catalyst component used in Example 1, 400 ml of 1-butene, and 4 of isobutane.
Then, 00 ml and 200 ml of hydrogen gas were added, and polymerization of 1-butene was started at -10 ° C in the same manner as in Example 1. Simultaneously with the start of polymerization, the polymerization temperature was raised to 33 ° C. 30 minutes later, and 1-butene polymerization was continued at the same temperature for 3.5 hours.

The results are shown in the table.

Examples 3 and 4 1-butene was polymerized in the same manner as in Example 1 except that the initial temperature, the final temperature, and the temperature rising time were as shown in the table.
The results are shown in the table.

Example 5 In the autoclave used in Example 1, 37.9 mg of the catalyst component used in Example 1, 300 ml of 1-butene and 3 of isobutane were used.
00 ml and 200 ml of hydrogen gas were added, and the polymerization of 1-butene was started at -27 ° C in the same manner as in Example 1. Simultaneously with the start of the polymerization, the polymerization temperature was raised to 30 ° C. 30 minutes later, at which point 200 ml of 1-butene was injected, and the polymerization of 1-butene was continued at the same temperature for 3.5 hours. The results are shown in the table.

Example 6 In the autoclave used in Example 1, 23.9 mg of the catalyst component used in Example 1, 100 ml of 1-butene, and 3 of isobutane were used.
00 ml and 200 ml of hydrogen gas were added, and the polymerization of 1-butene was started at -5 ° C in the same manner as in Example 1. Simultaneously with the initiation of the polymerization, 400 ml of 1-butene was gradually injected over 40 minutes, and the polymerization temperature was raised at the same time as the initiation of the polymerization to 30 ° C. 30 minutes later, and 1-butene was polymerized at the same temperature for 3.
It lasted 5 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 changed as shown in the table, and the results are shown in the table.

Example 7 Preparation of Catalyst Components A vibration mill pot made of stainless steel (SUS316) was charged with 19.0 g of anhydrous magnesium chloride, 3.0 g of ethyl benzoate and 2.6 g of 1-hexene under a nitrogen gas atmosphere and shaken for 1 hour while cooling with water. Finally crushed. Next, 3.8 g of titanium tetrachloride was added to this pot, and the mixture was shaken for 24 hours while being cooled with water and pulverized to obtain 24.8 g of a catalyst component.

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.

Example 8 Preparation of catalyst components 20 g anhydrous magnesium chloride, 5.2 g ethyl benzoate
And 3.0 ml of methyl polysiloxane (particle size 100CS),
2.8kg stainless steel balls with a diameter of 15mm in a nitrogen atmosphere
The mixture was placed in a stainless steel vibrating mill pot having an internal volume of 800 ml and an inner diameter of 100 mm, and shaken for 24 hours for pulverization. 20.3 g of the obtained co-ground product was added to titanium tetrachloride 200
After suspending in ml and stirring at 80 ° C. for 2 hours, the solid component was immediately filtered with a glass filter, and washed with 200 ml of purified n-hexane at room temperature eight times. It was dried at room temperature under reduced pressure for 1 hour to prepare 20.8 g of a catalyst component. This catalyst component contained Ti2.1%, Mg22.5%, Cl66.0%.

Polymerization of 1-butene 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 In a 500 ml flask, which was thoroughly purged with nitrogen gas, 4.76 g of anhydrous magnesium chloride, 25 ml of n-decane and 2
25 ml of ethylhexanol were added. Reaction was carried out at 130 ° C. for 2 hours, and 1.11 g of phthalic anhydride was added. Titanium tetrachloride (200 ml) was added dropwise to the mixture at -20 ° C over 30 minutes, and the temperature was gradually raised. When the temperature reached 110 ° C, 2.68 ml of diisobutyl phthalate was added,
Stirring was continued for 2 hours at ° C. After the reaction was completed, the supernatant was removed,
It was washed twice with 100 ml of toluene at 110 ° C.
Titanium tetrachloride (200 ml) was added again, the mixture was reacted at 110 ° C. for 2 hours, and the obtained solid substance was washed with 100 ml of n-hexane at room temperature eight times. The catalyst component was prepared by drying under reduced pressure at room temperature for 1 hour.

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.

[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 catalyst component containing magnesium, titanium and halogen as essential components and a polymerization catalyst consisting of an organoaluminum compound, wherein the polymerization temperature is from 0 ° C. or lower to an initial temperature of 15 to 15.
Consisting of gradually increasing to a final temperature of 40 ° C 1-
Butene polymerization method. 2. The method according to claim 1, wherein the initial temperature is in the range of -50 ° C to 0 ° 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).