JPS6222808A - Production of ultrahigh-mw poly-alpha-olefin - Google Patents

Abstract

PURPOSE:To obtain a high-density spherical ultrahigh-MW poly-alpha-olefin in high yields, by (co)polymerizing an alpha-olefin by using a catalyst comprising a specified catalyst component and a dialkylaluminum halide. CONSTITUTION:A reduce solid containing titanium trichloride is prepared by reducing titanium tetrachloride with an organoaluminum compound (e.g., trimethylaluminum). This solid is treated with a complexing agent (e.g., triethylamine) and a halogen-containing compound (e.g., aluminum trichloride) to prepare a catalyst component. An alpha-olefin (e.g., propylene) is polymerized or copolymerized with other olefins (e.g., ethylene) by using a catalyst comprising the obtained catalyst component and a dialkylaluminum halide (e.g., diethylaluminum chloride) to obtain the purpose ultrahigh-MW polyolefin.

Description

DETAILED DESCRIPTION OF THE INVENTION Field of the Invention The present invention relates to a process for producing ultrahigh molecular weight polyalpha-olefins, especially polypropylene.

BACKGROUND OF THE INVENTION In recent years, attempts have been made to utilize the properties of ultra-high molecular weight polyethylene and polypropylene to develop their applications. For example, a gel of the ultra-high molecular weight polymer,
By super-stretching the solution, the mechanical strength is increased and the material is made into a film.

Techniques for creating mat-like materials are attracting attention.

In this case, although polypropylene is inferior to polyethylene in terms of strength, it is superior in terms of heat resistance. Further, in order to obtain a high stretching ratio, a higher molecular weight is desired.

Several methods have been attempted for producing ultra-high molecular weight polyolefins with a molecular weight of several hundred blades (viscosity method). However, most of them are related to polyethylene, and most of them are manufactured using solid catalyst components (magnesium-supported catalysts) containing magnesium, titanium, and halogen as main components from the viewpoint of catalytic activity.

When propylene is polymerized in the absence of hydrogen using this magnesium-supported catalyst, although it exhibits high catalytic activity, the molecular weight cannot be made sufficiently high, so it is not suitable.

High molecular weight isotactic polypropylene can be produced by polymerizing propylene in the absence of hydrogen using a catalyst system consisting of a titanium trichloride-aluminum trichloride eutectic (large titanium trichloride) and a dialkyl aluminum chloride. It is possible to manufacture the product to a certain extent.

However, its molecular weight is only about 1 million,
In order to increase the molecular weight, polymerization is carried out at low temperatures.
Catalytic activity decreases significantly, making it impractical.

Problems to be Solved by the Invention Purpose of the Invention The purpose of the present invention is to obtain ultra-high molecular weight polyα-olefin, particularly polypropylene, in high yield, and the inventor has conducted extensive research. As a result, in the presence of a catalyst consisting of a catalyst component obtained by treating a reduced solid obtained by reducing titanium tetrachloride with an organoaluminum compound and a specific organoaluminum compound,
The present invention was completed by discovering that the object of the present invention can be achieved by polymerizing α-olefin.

That is, the present invention provides (a) a catalyst component obtained by treating a reduced solid containing titanium trichloride obtained by reducing titanium tetrachloride with an organoaluminum compound with a complexing agent and a halogen-containing compound; (b) A method for producing an ultra-high molecular weight polyα-olefin, which comprises homopolymerizing an α-olefin or copolymerizing it with another olefin using a catalyst comprising a dialkyl aluminum halide.

Catalyst The catalyst used in the present invention consists of (a) a catalyst component and (b) an organoaluminum compound.

(a) The catalyst component is obtained by treating a reduced solid containing titanium trichloride obtained by reducing titanium tetrachloride with an organoaluminum compound with a complexing agent and a halogen-containing compound.

The organoaluminum compound used in the reduction has the general formula RnAl! X, -n (However, 几 represents an alkyl group or an aryl group,
Indicates an arbitrary number in the range n≦3. ) or a mixture thereof, and a complex compound having 1 to 18 carbon atoms, preferably 2 carbon atoms, such as trialkylaluminium, dialkylaluminum halide, monoalkylaluminum civalide, and alkylaluminum sesquichloride. Particularly preferred are 6 to 6 alkyl aluminum compounds or mixtures or complexes thereof. Specifically, examples of trialkylaluminum include trimethylaluminum, triethylaluminum, and tributylaluminum, and examples of dialkylaluminum hydride include dimethylaluminum chloride, diethylaluminum chloride, diptylaluminum chloride, diethylaluminum bromide,
Examples of diethylaluminum iodide include monoalkylaluminium civalide, examples of which include methylaluminum dichloride, ethylaluminum dichloride, butylaluminum dichloride, ethylaluminum dichloride, and ethylaluminum diiodide; examples of alkylaluminum sesquihalides include ethylaluminum sesquihalide; chloride, in particular triethylaluminum, diethylaluminium chloride, ethylaluminum dichloride, ethylaluminum sesquichloride or mixtures or complexes thereof,
For example, a mixture of diethylaluminum chloride and ethylaluminum dichloride is particularly desirable because it is industrially easily available and exhibits excellent effects.

Reduction of titanium tetrachloride is usually performed by adding 150% titanium tetrachloride to a solution of titanium tetrachloride dissolved in an aliphatic hydrocarbon having 5 to 12 carbon atoms.
This is carried out by dropping the organoaluminum compound or its liquid resistance over a period of 30 minutes to 3 hours at a temperature of 0° to +30°0, but the reverse method may also be used. The amount of organic aluminum compound used is usually 1 to 5 gram moles per gram atom of titanium. In addition, the contact material of titanium tetrachloride and an organoaluminum compound is further heated at 20 to 150°.
Aging or heat treatment may be performed at a temperature of CL5 to 5 hours. Further, the reduction of titanium tetrachloride can be carried out in the presence of an ether used as a complexing agent described later.

The reduced solid containing titanium 9trichloride obtained as described above is washed with the aliphatic hydrocarbon as necessary and brought into contact with a complexing agent and a halogen-containing compound either as is or after drying.

Examples of complexing agents that can be used include ethers, thioethers, thiols, organic sulfur-containing compounds, organic nitrogen-containing compounds, ketones, and carboxylic acid esters. Specifically, the ethers include diethyl ether, diisopropyl ether, sinormal phthyl ether, diisobutyl ether, diisoamyl ether, di-2-ethylhexyl ether, di-2-ethylhexyl ether, allyl ethyl ether, allyl butyl ether, diphenyl ether, Anisole, phenethole, chloranisole, bromanisole, dimethoxybenzene, etc., and thioethers include diethyl thioether, di-n-propyl thioether, dicyclohexyl thioether, diphenyl thioether, ditolyl thioether, ethylphenyl thioether, and furobylphenyl. Thioether, diallyl thioether, etc.
Examples of organic sulfur-containing compounds include tri-n-butylphosphine, triphenylphosphine, triethylphosphite, and tributylphosphite; examples of organic nitrogen-containing compounds include diethylamine, triethylamine, and
-propylamine, di-n-propylamine, tri-n
-propylamine, aniline, dimethylaniline, etc.
Carboxylic acid esters include butyl formate, ethyl acetate, butyl acetate, iso, isobutyl butyrate, propyl pivalate, inbutyl pivalate, ethyl acrylate, methyl methacrylate, ethyl methacrylate, isobutyl methacrylate, diethyl malonate, malonic acid. diisobutyl,
Diethyl succinate, diptyl succinate, diisobutyl succinate, diethyl glutarate, dibutyl glutarate, diisobutyl glutarate, diisobutyl adipate, dibutyl sebacate, diisobutyl sebacate, diethyl maleate, dibutyl maleate, diisobutyl maleate, fumaric acid Monomethyl, diethyl fumarate, diisobutyl hexamarate, diethyl tartrate, dibutyl tartrate, diynbutyl tartrate, ethyl cyclohexanecarboxylate, methyl benzoate, ethyl benzoate, methyl p-)ruylate, p-tertiary butyl ethyl benzoate, Ethyl p-anisate, ethyl α-naphthoate, isobutyl α-su7toate, ethyl cinnamate, monomethyl phthalate, monobutyl phthalate, dibutyl phthalate, diisobutyl phthalate, dihexyl phthalate, dioctyl phthalate, phthalate Acid di2
-Ethylhexyl, diallyl phthalate, diphenyl phthalate, diethyl hepthalate, diisobutyl inphthalate, diethyl terephthalate, dibutyl terephthalate, diethyl naphthalate, dibutyl naphthalate, triethyl trictate, tributyl trictate, pyromellit Tetramethyl acid, tetraethyl pyromellitate, tetrabutyl pyromellitate, etc. are used. Ethers are particularly preferred, and ethers having 4 to 16 carbon atoms are particularly preferred.

As the halogen-containing compound, in addition to halogenated hydrocarbons and halogenated metal compounds, halogen elements can also be used.

The halogenated hydrocarbons used are mono- and polyhalogen-substituted saturated or unsaturated aliphatic, alicyclic and aromatic hydrocarbons having 1 to 12 carbon atoms. Specific examples of these compounds include methyl chloride, methyl bromide, methyl iodide, methylene chloride,
Methylene bromide, methylene iodide, chloroform, bromoform, iodoform, carbon tetrachloride, carbon tetrabromide, quaternary carbon, ethyl chloride, ethyl bromide,
Ethyl iodide, 1. 2-dichloroethane, 1.
．． 2-dibromoethane, 1,2-short ethane, methylchloroform, methylbromoform, methyliodoform, 1,1.2-)dichloroethylene, 1°1.2-
Tribromoethylene, 1,1,2,2-tetrachloroethylene, pentachloroethane, hexachloroethane, hexabromoethane, n-propyl chloride, 1,2-dichloropropane, hexachloropropylene, heptachloropropane, octa Chlorpropane, decabromobutane, chlorinated paraffin, alicyclic compounds such as chlorocyclopropane, tetrachlorocyclopentane, hexachlorocyclopentadiene, hexachlorocyclohexane, aromatic compounds such as chlorobenzene, bromobenzene, 0-
Examples include dichlorobenzene, p-dichlorobenzene, hexachlorobenzene, hexachlorobenzene, benzotrichloride, p-chlorobenzotrichloride, etc.0 These compounds may be used not only one type but two or more types0 Halogenation Metal compounds are listed in the periodic table of elements in the first s Wa
, ■b and v! The halides of elements selected from the group of L group elements include B, Ga, In.

'r4 81. Go, 8n, Pb, Ti
, Mus, 8b, 131 chloride, fluoride,
Mention may be made of bromides and iodides, especially ll01! ,,
BBr,, III,, Mu1ots, AI
! Br5p Mu115GaO/a, GaBr,,
In04. T104. 810/4. 8nO
/4°T 104 s' bOII # I! l
b'1! Examples of the halogen elements for which s and the like are preferable include chlorine and iodine, with iodine being particularly preferable.

Additionally, alkyl aluminum cybarides such as ethyl aluminum dichloride, dialkyl aluminum halides such as diethylaluminum chloride may also be used. Treatment of the zero-reduced solid with a complexing agent and...
It is usually carried out in the presence of an inert medium, such as a hydrocarbon such as hexane, heptane, octane, decane, cyclohexane, benzene, toluene, xylene and the like. Complexing agent and...
The rogen-containing compounds may be used in that order or simultaneously.

Processing by one or both sequentially or simultaneously is usually 0~
It is carried out at a temperature of 200'O for 5 minutes to 20 hours. The amount of complexing agent and nologen-containing compound to be used is 0.0 to 1 g mole of titanium in the reduced solid, usually the complexing agent power iα is 01 to 10 g mole, and the amount of the norogen containing compound is 105 to 10 g mole. When treated with, the treated material can be washed with the above inert medium as necessary,
The reduced solid treated with a complexing agent and a halogen-containing compound can also be further treated with a complexing agent, if necessary.

A specific example of contacting the reduced solid with a complexing agent and a halogen-containing compound is shown below.

(2) A method in which the reduced solid is treated with the ether in the presence or absence of the halogen element and then treated with the metal halide compound; (2) The reduced solid is treated in the presence or absence of the halogen element. A method of treating the reduced solid with the metal halide compound in the presence of the metal halide compound and the metal halide compound in the presence of the ether compound, (1) treating the reduced solid with the metal halide compound and the ether compound; Method, (1) a method of treating the reduced solid with the ether and then the halogenated hydrocarbon, (2) a method of treating the reduced solid with the halogenated hydrocarbon in the presence of the ether, (2) the above method; Or the treated product of (1) is further added to the above
Methods of treatment with logogenized metal compounds, etc.

The catalyst component obtained as described above can be used after being washed with the above-mentioned inert medium if necessary and further dried if necessary. Examples of the dialkylaluminum halide (b) used as a catalyst include dimethylaluminum chloride, diethylaluminum chloride, dibutylaluminum chloride, diethylaluminum bromide, diethylaluminium iodide, and the like.

Among these, dialkyl aluminum chloride, particularly diethyl aluminum chloride, is preferred. Organoaluminum compounds other than dialkyl aluminum halides,
For example, when using a trialkylaluminum such as triethylaluminum, chain transfer due to the trialkylaluminium progresses, making it impossible to achieve a sufficient molecular weight, and stereoregularity is also low. The dialkyl aluminum halide is generally used in an amount of 1 to 1000 g mol, preferably 20 to 500 g mol, per 1 gram atom of titanium in the catalyst component.

Further, in addition to the catalyst component and the dialkyl aluminum halide, an electron-donating compound can be used in combination as a third component. As the electron-donating compound, any compound among the complexing agents used in preparing the catalyst component can be used.

Among them, carboxylic acid esters are particularly desirable. In addition, other than the above-mentioned complexing agents (alkoxysilanes such as tetraethoxysilane, butyltriethoxysilane, 2,2,6
．． Sterically hindered electron-donating compounds containing heteroatoms such as 6-tetramethylbiperidine, 2,2,5,5-tetramethylpyrrolidine, 2-ethyltetrahydrofuran can also be used.0 Electron-donating compounds is fi0.02 to 10 mole per mole of dialkyl aluminum halide, preferably 104 to
1 mole is used.

Polymerization of α-olefins In the present invention, α-olefins are homopolymerized or copolymerized with other olefins using the above-described catalyst.
-Methyl-1-pente/, 1-hexene, etc. with 3 or more carbon atoms
Ten α-olefins are mentioned. Among these, polymerization of propylene is particularly desirable in the present invention. Copolymerization includes random polymerization and block copolymerization of α-olefin and ethylene in addition to the above-mentioned α-olefins.

The polymerization reaction may be carried out in either a gas phase or a liquid phase, and in the case of liquid phase polymerization, it is carried out in the above-mentioned inert medium or in a liquid monomer. The lower the temperature, the higher the molecular weight can be, but if the catalytic activity is lost, there is a limit to lowering the temperature too much, which is usually 10". Polymerization is carried out with hydrogen, alkyl Zero copolymerization is carried out at normal pressure or under pressure up to about 50 atmospheres in the absence of molecular weight regulators such as halides and zinc dialkyl (in this case, the amount of other olefins to be copolymerized with α-olefin is , usually up to 30% by weight, especially cL 3 to 15% by weight, based on the α-olefin.The polymerization reaction may be either continuous or batchwise.The copolymerization may be carried out in one stage or in two stages. It may be carried out in stages or more.0 By the above method, the molecular weight by the viscosity method is 200.
In the case of polypropylene (r) = t 10 x 10-', the molecular weight according to the viscosity method is the value calculated from the following formula. sMv'' formula, [η)*135°0 intrinsic viscosity measured in decalin, MY S viscosity average molecular weight formula, [η)s
Intrinsic viscosity measured in decalin at 115°C, Mv + viscosity average molecular weight Effects of the invention ■In contrast to the Mumu type titanium trichloride catalyst or magnesium supported catalyst, a molecular weight of only 300,000 to 400,000 can be obtained. According to the method of the present invention, a polymer having an ultra-high molecular weight of 2 to 5 million or more can be obtained. ■
The obtained polymer particles are spherical and have a high bulk density.

Generally, ultra-high molecular weight polymers cannot be made into pellets, so the powdered polymer obtained is usually handled as is, but the polymer particles obtained by the present invention As mentioned above, since it has excellent particle properties, it is extremely easy to handle. ■The catalyst according to the present invention has a polymerization activity 4 to 5 times that of the Mumu type titanium trichloride catalyst, and has excellent activity sustainability, so the catalytic effect can be greatly increased by increasing the polymerization time. Therefore, it is possible to simplify or omit the step of removing the catalyst in the polymer.Examples The present invention will be explained in detail with reference to Examples and Comparative Examples.O Obtained Polymers The bulk density of is 8? I → 1895-6
9 method.

Example 1 Preparation of catalyst components Into a 21 flask equipped with a stirrer, 700 ml of purified hebutane and 250 mj' of titanium tetrachloride were charged.
It was cooled to ゛C. Next, 3157FII! A mixture of diethylaluminum chloride (1171r11), ethylaluminum dichloride (1171r11) and 400 ml of purified hebutane was added dropwise over 3 hours while maintaining the reaction system at 0°C. After the addition was completed, the contents were heated with stirring, brought to 65°C after 1 hour, and stirring was continued at that temperature for another 1 hour. The resulting reduced solid was separated, washed with purified hebutane, and then dried under reduced pressure.

Next, 25 g of this reduced solid was suspended in 100 ml of purified hebutane, and per gram atom of titanium in the reduced solid,
A hebutane solution of hexachloroethane in an amount corresponding to 1 gram mole as hexachloroethane and an amount of di-n-butyl ether corresponding to α log mol are added, and 8
Stirring was carried out for 5 hours at 0"0. The obtained solid material was washed with purified hemobutane and then dried under reduced pressure to prepare a catalyst component.

1, 51 with a propylene polymerization stirrer installed! Into a stainless steel autoclave under a nitrogen gas atmosphere, a n-hebutane solution of diethylaluminium chloride in an amount of 15.0 g mol per duram atom of titanium in the catalyst component obtained above (52.0 ml, 1%) was added. so a mz
of liquid propylene was added and heated to 50°C. Stirring was started and propylene was polymerized at 50°0 for 4 hours. As a result, 851 polypropylene powders with bulk density o, s s t /(7)3 were obtained (catalytic activity = 2,60
0 Pφpp/I? -Catalyst component) 0 The viscosity average molecular weight (Mv) of the obtained polymer was 5.8 million.

Examples 2 and 3 Propylene polymerization was carried out in the same manner as in Example 1, except that the polymerization temperature was 60°C or 70°C, and the results are shown in the table.

Example 4 Polymerization of propylene was carried out in the same manner as in Example 2, except that 0.1 mol of ethyl benzoate was used per 1 mol of diethylaluminum chloride in addition to the catalyst component and diethylaluminum chloride as a catalyst, and the results were as follows. are shown in the table.

Example 5 Preparation of Catalyst Components 7200 ml of n-hexane was placed in a nitrogen-substituted SO OMZ flask equipped with a stirrer. V! j Titanium chloride s
oml! After cooling for 1°, add n-
The dropwise addition of a solution consisting of 150 ml of hexane and diethylaluminum chloride s s mt was completed in 2 hours while the temperature was at 1°0. Further, stirring was continued for 15 minutes at 1°0, and then the temperature was raised to 65°0 over 1 hour.

The reaction medium was then kept under stirring for a further hour at 65°C. After standing still, the supernatant liquid was extracted and removed, and the solid was
Washed 5 times with 0 ml of n-hexane.

After adding n-hexane so that the reduced solid slug IJ-K obtained above reached 480771JP, 85 ml of diisoamyl ether was added and the mixture was treated at 35°0 for 1 hour with stirring. After treatment, 9200ml by decantation! 5 with n-hexane
Washed twice.

Titanium tetrachloride and n-hexane were added to the slurry of the treated solid obtained above so that titanium tetrachloride had a volume of 40 and 280 ml of a titanium solution, and the slurry was treated at 65°C for 2 hours with stirring. After treatment, room temperature n-
The catalyst component was prepared by washing four times with 200 ml of hexane and finally once with 65°0 n-hexane 2α;Q71/ and drying.

Polymerization of propylene Polymerization of propylene was carried out in the same manner as in Example 2, except that the catalyst component obtained above was used, and the results are shown in the table.

Example 6 Preparation of catalyst component Same as Example 1 except that carbon tetrachloride was used instead of hexachloroethane used in preparing the catalyst component in Example 1, and the contact temperature with the reduced solid was 45°C. A catalyst component was prepared.

Polymerization of propylene was carried out in the same manner as in Example 1, except that the catalyst component obtained above was used.

The results are shown in the table.

Example 7 Preparation of catalyst components Instead of hexachloroethane, silicon tetrachloride (slo
A catalyst component was prepared in the same manner as in Example 1 using za) except for the following.

Polymerization of propylene Propylene 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 Component A catalyst component was prepared in the same manner as in Example 1, except that heptachloropropane was used instead of hexachloroethane and the contact temperature with the reduced solid was 70°.

Polymerization of propylene Polymerization of propylene was carried out 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 9 1-butene was used instead of propylene, and the polymerization temperature was set to 4.
1-Butene was polymerized in the same manner as in Example 1 except that the temperature was 0°0, and the results are shown in the table.

Comparative Example 1 The propylene polymerization catalyst component was mixed with titanium trichloride-aluminum trichloride eutectic (
Manufactured by Toyo Stoffer Co., Ltd., Mum grade)
Polymerization of propylene was carried out in the same manner as in Example 2, and the results are shown in the table.

Comparative Example 2 Preparation of catalyst components Commercially available anhydrous magnesium chloride 20t and ethyl benzoate &
Om/ in a nitrogen atmosphere into a stainless steel container with an internal volume of 800 m/ and an internal diameter of 100 fins containing 100 stainless steel (stys-s O2) balls with a diameter of 15 cm, Co-pulverization was carried out for 50 hours using a Nocuff G vibration mill device.

The obtained solid treated product was suspended in titanium tetrachloride and
After reacting at 0° C. for 2 hours, the solid component was separated and purified with hexane to prepare a catalyst component having a titanium content of 2.1 weight t=n.

Polymerization of propylene Propylene was polymerized in the same manner as in Example 2, except that the catalyst components obtained above and a n-hexane solution of triethylaluminum and ethyl benzoate (molar ratio 1:(L3) were used as catalysts. , the results are shown in the table.

Comparative Example 3 Polymerization of propylene was carried out in the same manner as in Example 2 except that ethylaluminum was used instead of diethylaluminum chloride used in the polymerization of propylene in Example 2, and the results are shown in the table.

Comparative Example 4 Propylene was polymerized in the same manner as in Example 1, except that 15 mj of hydrogen was added, and the results are shown in the table.

Claims (1)

[Scope of Claims] (a) A catalyst component obtained by treating a reduced solid containing titanium trichloride obtained by reducing titanium tetrachloride with an organoaluminum compound with a complexing agent and a halogen-containing compound; b) A method for producing an ultra-high molecular weight polyα-olefin, which comprises homopolymerizing an α-olefin or copolymerizing it with another olefin using a catalyst comprising a dialkyl aluminum halide.