JPS6410528B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a novel method for producing polyolefins. More specifically, the present invention provides a product obtained by reacting (1) a solid inorganic oxide and (2) a carboxylic acid halide, and (3) a substance obtained by reacting with an organomagnesium compound on a solid carrier. year,
A method for producing a polyolefin by polymerizing or copolymerizing an olefin using a catalyst system obtained by combining a solid component obtained by supporting a titanium compound or a titanium compound and a vanadium compound on the solid carrier and an organoaluminum compound. . According to the method of the present invention, the polymer yield per solid and the polymer yield per transition metal are significantly increased, thereby eliminating the need for the step of removing catalyst residues in the polymer, and at the same time reducing the amount of polymer produced. It is possible to increase the bulk specific gravity of the polyolefin and reduce the fine powder portion of the produced polymer, thereby making it possible to suitably produce a polyolefin. Conventionally, in this type of technical field, many catalysts are known in which compounds of transition metals such as titanium or vanadium are supported on inorganic magnesium solids such as magnesium halides, magnesium oxides, and magnesium hydroxides. . However, in these known techniques, the particle shape of the obtained polymer is amorphous;
Since the bulk specific gravity is generally small and the particle size distribution is generally wide, there is a large proportion of fine particles, and improvements have been strongly desired from the viewpoint of productivity and slurry handling. Furthermore, when molding these polymers, problems such as generation of dust and reduction in efficiency during molding occur, so it has been strongly desired to increase the bulk specific gravity and reduce the particulate powder portion as described above. The present invention has been made through intensive research aimed at improving the above-mentioned drawbacks and obtaining a polymer with good polymer particle shape, high bulk specific gravity, narrow particle size distribution, and significantly less fine particulate portions. As a result,
This has led to the present invention. That is, the present invention provides a method for polymerizing or copolymerizing olefin using a component in which a titanium compound or a titanium compound and a vanadium compound are supported on a solid carrier and an organometallic compound as a catalyst, wherein the solid carrier is (1) a solid inorganic oxide; and (2) a carboxylic acid halide, and (3) a substance obtained by further reacting with an organomagnesium compound. By using the method of the present invention, it is possible to obtain a highly active polyolefin in which the shape of the polymer particles is extremely good, the particle size distribution is narrow, and there are few fine particulate parts, and the bulk specific gravity of the produced polyolefin is high. This is extremely advantageous, and there are also fewer troubles during molding, making it possible to produce polyolefins extremely advantageously. Here, the term "polymer particles having good shape" means that the polymer particles have a spherical or nearly spherical shape and have a smooth particle surface. The solid inorganic oxide used in the present invention is an oxide of aluminum, magnesium, silicon, or calcium, or a complex oxide containing at least one type of oxide of aluminum, magnesium, silicon, or calcium, and specifically, Al ₂ O ₃ , MgO,
SiO ₂ , CaO, Al ₂ O ₃・MgO, Al ₂ O ₃・CaO,
Al ₂ O ₃・SiO ₂ , Al ₂ O ₃・MgO・CaO, Al ₂ O ₃・
MgO・SiO ₂ , Al ₂ O ₃・CaO, Al ₂ O ₃・Fe ₂ O ₃ ,
_Al2O3・_NiO , _SiO2・MgO, _SiO2・CaO,
Examples include various natural or synthetic oxides or multiple oxides such as SiO ₂ ·CaO · MgO and SiO ₂ ·ZrO ₂ . Here, the above formula represents only the composition, not the molecular formula, and the structure and component ratio of the multiple oxide used in the present invention are not particularly limited. It goes without saying that the solid inorganic oxide used in the present invention may adsorb a small amount of water without any problem, and can be used without any problem even if it contains a small amount of impurities. The carboxylic acid halide used in the present invention has the general formula

It is a compound represented by the formula (where R is a hydrocarbon residue such as an alkyl group, aryl group, or aralkyl group having 1 to 20 carbon atoms, and X is a halogen atom), and a specific example is acetyl chloride. , acetyl bromide, acetyl iodide,
propionyl chloride, propionyl bromide,
n-butyryl chloride, sec-butyryl chloride,
t-butyryl chloride, n-valeryl chloride,
Isovaleryl chloride, n-caproyl chloride, caprylic chloride, stearoyl chloride,
Examples include benzoyl chloride, benzoyl fluoride, benzoyl bromide, benzoyl iodide, toluoyl chloride, toluoyl fluoride, toluoyl bromide, naphthoyl chloride, and the like. Examples of the organomagnesium compound used in the present invention include organomagnesium complexes soluble in inert hydrocarbons and Grignard compounds soluble in ether compounds. Typical organomagnesium complexes soluble in inert hydrocarbons include dialkylmagnesium represented by the general formula R ₂ Mg (where R represents an alkyl group having 1 to 24 carbon atoms) and general formula AlR ₃ (where R represents an alkyl group having 1 to 24 carbon atoms). and R represents an alkyl group having 1 to 24 carbon atoms. An example of dialkylmagnesium is
(n-C ₄ H ₉ ) ₂ Mg, (sec-C ₄ H ₉ ) ₂ Mg, (tert-
C ₄ H ₉ ) ₂ Mg, (n-C ₄ H ₉ ) (C ₂ H ₅ ) Mg, (n-
C ₄ H ₉ ) (sec-C ₄ H ₉ )Mg, (n-C ₄ H ₉ ) (tert-
C ₄ H ₉ ) Mg, (n-C ₆ H ₁₃ ) ₂ Mg, (n-C ₆ H ₁₃ )
Examples include (C ₂ H ₅ )Mg, and a preferred example of the trialkylaluminum is triethylaluminum. Here, the molar ratio of dialkylmagnesium:trialkylaluminium in the complex of dialkylmagnesium and trialkylaluminium is
A range of 100:1 to 1:10 is preferred. Grignard compounds that are soluble in ether compounds have the general formula RMgX (where R represents a hydrocarbon group,
X represents a halogen atom), specifically R is an alkyl group, aryl group or aralkyl group having 1 to 20 carbon atoms, particularly methyl, ethyl, propyl, butyl, acyl,
Preferred are alkyl groups such as hexyl, aryl groups such as phenyl, and aralkyl groups such as benzyl. Examples of the halogen include chlorine, bromine, and iodine. In the present invention, the method of reaction between the solid inorganic oxide and the carboxylic acid halide is not particularly limited, and a preferred example is a method in which the solid inorganic oxide and the carboxylic acid halide are reacted under reflux, and then unreacted carboxylic acid halide is removed. It can be mentioned as follows. Alternatively, the same method can be used by diluting the carboxylic acid halide with an inert hydrocarbon solvent. The reaction is carried out using 0.1 to 100 g of carboxylic acid halide per 1 g of solid inorganic oxide, preferably 0.5 to 50 g of carboxylic acid halide.
It is better to allow g reaction. Temperature is usually 20-300℃
It can be carried out at a temperature of 40 to 200°C, and preferably 40 to 200°C. In the present invention, a reaction product of a solid inorganic oxide and a carboxylic acid halide is further reacted with an organomagnesium compound, but the reaction method at this time is not particularly limited either. For example, a method may be mentioned in which an organomagnesium compound is solubilized in an inert hydrocarbon, and then a reaction product of a solid inorganic oxide and a carboxylic acid halide is brought into contact. The amount of the organomagnesium compound at this time is preferably in the range of 10 ^-4 to ^{10 -2} gram atoms of magnesium per 1 g of solid inorganic oxide, and the reaction temperature is preferably 5 to 200°C. In the present invention, the method for supporting the titanium compound or the titanium compound and vanadium compound on the solid carrier is not particularly limited, and any known method can be selected. This can be carried out by contacting a solid support with an excess of a titanium compound or a titanium compound and a vanadium compound under heating, preferably in the presence or absence of an inert solvent, and preferably,
This is conveniently carried out by heating both to 50-300°C, preferably 100-150°C in the absence of a solvent. Although the reaction time is not particularly limited, it is usually 5 minutes or more, and long-term contact may be allowed, although it is not necessary. For example, 5 minutes to 10 minutes
The processing time can be increased. Of course, this treatment should be carried out under an inert gas atmosphere free of oxygen and moisture. After the completion of the reaction, the method for removing unreacted titanium compounds or titanium compounds and vanadium compounds is not particularly limited, and the Ziegler catalyst may be washed several times with an inert solvent and the washing liquid may be evaporated under reduced pressure to obtain a solid powder. Obtainable. The amount of titanium compound or titanium compound and vanadium compound to be supported is 0.5 to 20% by weight of titanium or titanium and vanadium contained in the produced solid.
It is most preferable to adjust the amount within the range of 1 to 10% by weight in order to obtain a well-balanced activity per titanium or titanium and vanadium, and activity per solid. Examples of the titanium compound or the titanium compound and vanadium compound used in the present invention include halides, alkoxy halides, alkoxides, and halogenated oxides of titanium or titanium and vanadium. As the titanium compound, a tetravalent titanium compound is particularly suitable, and specifically, it has the general formula Ti(OR) _o X _4-o (where R is a carbon number of 1 to
20 alkyl, aryl or aralkyl groups, and X represents a halogen atom. n is 0≦n≦
It is 4. ) are preferred, and titanium tetrachloride, titanium tetrabromide, titanium tetraiodide, monomethoxytrichlorotitanium, dimethoxydichlorotitanium, trimethoxymonochlorotitanium, tetramethoxytitanium, monoethoxytrichlorotitanium,
Diethoxydichlorotitanium, triethoxymonochlorotitanium, tetraethoxytitanium, monoisopropoxytrichlorotitanium, diisopropoxymonochlorotitanium, triisopropoxymonochlorotitanium, tetraisopropoxytitanium, monobutoxytrichlorotitanium, dibutoxydichlorotitanium, monopentoxy Examples include trichlorotitanium, monophenoxytrichlorotitanium, diphenoxydichlorotitanium, triphenoxymonochlorotitanium, and tetraphenoxytitanium. Examples of vanadium compounds include tetravalent vanadium compounds such as vanadium tetrachloride, vanadium tetrabromide, vanadium tetraiodide, and tetraethoxyvanadium; Examples include vanadium compounds of valence. In the present invention, a combination system of a titanium compound and a vanadium compound often gives more preferable results than a titanium compound alone, but in this case, the V/Ti molar ratio is 2/1.
A range of 0.01/1 is preferable. Examples of organoaluminum compounds used in the present invention include general formulas R ₃ Al, R ₂ AlX, RAlX ₂ , R ₂ AlOR,
Organoaluminum compounds of RAl( _{OR)X and R 3 Al 2} Specific examples include triethylaluminum, triisopropylaluminum, triisobutylaluminum, trisec-butylaluminum, tritert-
Examples include butylaluminum, trihexylaluminum, trioctylaluminum, diethylaluminum chloride, diisopropylaluminum chloride, ethylaluminum sesquichloride, and mixtures thereof. In the present invention, the amount of the organoaluminum compound used is not particularly limited, but is usually compared to the titanium compound or the titanium compound and the vanadium compound.
It can be used in amounts of 0.1 to 1000 moles. Olefin polymerization using the catalyst of the present invention can be carried out by slurry polymerization, solution polymerization or gas phase polymerization, and the polymerization reaction is carried out in the same manner as the olefin polymerization reaction using a conventional Ziegler type catalyst. That is, all reactions are carried out in the presence or absence of inert hydrocarbons, substantially deprived of oxygen, water, and the like. The polymerization conditions for olefin are at a temperature of 20 to 120°C. Preferably 50 to 100
℃, and the pressure is normal pressure to 70 kg/cm ² , preferably 2 to 60 kg/cm ² . The molecular weight can be controlled to some extent by changing polymerization conditions such as polymerization temperature and catalyst molar ratio, but it is effectively carried out by adding hydrogen to the polymerization system. Of course, using the catalyst of the present invention, a two-step or more multi-step polymerization reaction with different polymerization conditions such as hydrogen concentration and polymerization temperature can be carried out without any problem. The method of the present invention is applicable to the polymerization of all olefins that can be polymerized with Ziegler's catalyst, and α-olefins having 2 to 12 carbon atoms are particularly preferred, such as ethylene, propylene, 1-butene, hexene-1,4-methyl Homopolymerization of α-olefins such as pentene-1, ethylene and propylene,
It is suitably used for copolymerization of ethylene and 1-butene, propylene and 1-butene, etc. Copolymerization with dienes is also preferably carried out for the purpose of modifying polyolefins. Examples of these include copolymerization of ethylene and butadiene, ethylene and 1,4-hexadiene, and the like. Examples will be described below, but these are for illustrative purposes to carry out the present invention, and the present invention is not limited thereto. Example 1 (a) Production of catalyst component Silica (manufactured by Fuji Davison, DA-VISON) was placed in a 300 c.
Add 5g of SILICAGEL #951) and heat at 150°C.
After vacuum drying for an hour, 20 c.c. of benzoyl chloride was added and reacted at 120°C for 1 hour.
After the reaction is complete, unreacted benzoyl chloride is converted into n-
After washing and removing with hexane, a heptane solution of a complex of di-n-butylmagnesium and triethylaluminum containing 2.2wt% magnesium (manufactured by Texas Alkyl, MAGALA
BEM/HEPT-205) 5 c.c. was added together with 50 c.c. of hexane and reacted at 70°C for 1 hour. After the reaction was completed, the liquid components were washed away with n-hexane, and then 50 c.c. of n-hexane and 5 c.c. of titanium tetrachloride were added, and the mixture was reacted for 1 hour under n-hexane reflux. After the reaction was completed, the liquid component was removed by washing with n-hexane to obtain a black-purple solid powder. 60 mg of titanium was contained in 1 g of this solid powder. (b) Polymerization The stainless steel autoclave equipped with an induction stirrer from step 2 was purged with nitrogen, 1000 ml of hexane was added thereto, 3 mmol of triethylaluminum and 50 mg of the above solid powder were added, and the temperature was heated at 90°C with stirring.
The temperature rose to . At the vapor pressure of hexane, the system is 2Kg/
cm ²・G, but hydrogen was added until the total pressure reached 6 kg/cm ²・G, and then ethylene was added until the total pressure reached 10 kg/cm 2 ・G.
The polymerization was started by charging the mixture to kg/cm ² ·G. Ethylene was continuously introduced so that the total pressure was 10 Kg/cm ² ·G, and polymerization was carried out for 1 hour. After polymerization, the polymer slurry was transferred to a beaker, hexane was removed under reduced pressure, and the melt index was 6.2.
220 g of white polyethylene with a bulk specific gravity of 0.35 was obtained.
Catalytic activity is 18300g polyethylene/gTi・hr・
C ₂ H ₄ pressure, 1100g polyethylene/g solids・hr・
Polyethylene with high bulk specific gravity and C ₂ H ₄ pressure was obtained with extremely high activity. The average particle size of the obtained polyethylene was 50μ, and the proportion of fine particles of 100μ or less was 0.03%. Comparative Example 1 A catalyst component was synthesized in the same manner as in Example 1 except that benzoyl chloride was not used, and a solid powder containing 80 mg of titanium per gram was obtained. Using 50 mg of the above solid powder, polymerization was carried out for 1 hour in the same manner as in Example 1 to obtain a melt index.
1.3, and 82 g of white polyethylene with a bulk specific gravity of 0.21 was obtained. Catalytic activity is 5130g polyethylene/gTi・hr・
C ₂ H ₄ pressure, 410g polyethylene/g solids・hr・
It was at C ₂ H ₄ pressure. The average particle size of the obtained polyethylene was 360μ, and 5.1% of the particles were 100μ or less. Comparative Example 2 A catalyst component was synthesized in the same manner as in Example 1 except that the organomagnesium compound was not used in Example 1, and a solid powder containing 85 mg of titanium per gram was obtained. Using 50 mg of the above solid powder, polymerization was carried out for 1 hour in the same manner as in Example 1 to obtain a melt index.
15 g of polyethylene with a bulk specific gravity of 3.1 and 0.18 was obtained.
Catalytic activity is 880g polyethylene/gTi・hr・C ₂ H ₄
The pressure was 75 g polyethylene/g solids/hr/C ₂ H ₄ pressure. The average particle size of the obtained polyethylene is
The particle diameter was 380μ, and the proportion of particles smaller than 100μ was 4.8%. Example 2 Example 1 except that acetyl chloride was used instead of benzoyl chloride in Example 1.
The catalyst component was synthesized in the same manner as 68 mg/g.
A solid powder containing titanium was obtained. Using 50 mg of the above solid powder, polymerization was carried out for 1 hour in the same manner as in Example 1 to obtain a melt index.
5.7, and 235 g of white polyethylene with a bulk specific gravity of 0.32 was obtained. Catalytic activity is 17300g polyethylene/gTi・
hr・C ₂ H ₄ pressure, 1180g polyethylene/g solid・
The pressure was hr・C ₂ H ₄ pressure. The average particle size of the obtained polyethylene was 460μ, and particles smaller than 100μ accounted for 0.07%.
It was hot. Example 3 A catalyst component was synthesized in the same manner as in Example 1, except that 5.8 cc of monobutoxytrichlorotitanium was used instead of 5 c.c. of titanium tetrachloride, and 1 g of solid powder was synthesized. A solid powder containing 60 mg of titanium was obtained. Using 50 mg of the above solid powder, polymerization was carried out for 1 hour in the same manner as in Example 1, and the melt index was
6.5, and 200 g of white polyethylene with a bulk specific gravity of 0.37 was obtained. Catalytic activity is 16,700g polyethylene/gTi・
hr・C ₂ H ₄ pressure, 1000g polyethylene/g solid・
hr・C ₂ H ₄ pressure, and polyethylene with high bulk specific gravity was obtained with extremely high activity. The average particle size of the obtained polyethylene was 480μ, and the proportion of fine particles of 100μ or less was 0.02%. Example 4 The same procedure as in Example 1 was carried out except that titanium tetrachloride 5c.c. and triethoxyvanadyl 2c.c. were used in place of titanium tetrachloride 5c.c. 55 per gram of solid powder by synthesizing catalyst components
A solid powder containing mg of titanium and 5 mg of vanadium was obtained. Using 50 mg of the above solid powder, polymerization was carried out for 1 hour in the same manner as in Example 1, and the melt index was
6.3, and 170 g of white polyethylene having a bulk specific gravity of 0.38 was obtained. Catalytic activity is 15500g polyethylene/gTi・
V・hr・C ₂ H ₄ pressure, 850g polyethylene/g solid・
hr・C ₂ H ₄ pressure, and polyethylene with high bulk specific gravity was obtained with extremely high activity. The average particle size of the obtained polyethylene was 470μ, and the proportion of fine particles of 100μ or less was 0.02%. The stainless steel autoclave equipped with an induction stirrer from Example 5 2 was purged with nitrogen, 1000 ml of hexane was added, 3 mmol of triethylaluminum and 30 mg of solid powder obtained in the same manner as in Example 1 were added, and the temperature was raised to 60°C with stirring. It was warm. Then, propylene was continuously introduced so that the total pressure was 5 kg/cm ² ·G, and polymerization was carried out for 1 hour. After the polymerization was completed, the polymer slurry was transferred to a beaker, and hexane was removed under reduced pressure to obtain 50 g of white polyprene with a bulk specific gravity of 0.40.

[Brief explanation of drawings]

FIG. 1 is a flowchart showing one example of the preparation of a catalyst for olefin polymerization of the present invention.

Claims (1)

[Claims] 1. A method of polymerizing or copolymerizing an olefin using a component in which a titanium compound or a titanium compound and a vanadium compound are supported on a solid carrier and an organic aluminum compound as a catalyst, in which the solid carrier contains (1) a solid inorganic oxide and (2) 1. A method for producing a polyolefin, characterized in that the product is a substance obtained by reacting a product obtained by reacting with a carboxylic acid halide and (3) an organomagnesium compound.