JP3470393B2 - Method for producing ethylene / α-olefin copolymer - Google Patents

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a method for producing an ethylene / α-olefin copolymer for copolymerizing ethylene and an α-olefin having 3 or more carbon atoms, in which the reaction vessel is divided into at least three chambers for reaction. An ethylene / α-olefin characterized in that the productivity of the ethylene / α-olefin copolymer is improved by supplying a metallocene catalyst to the upper chamber of the reactor and a Ziegler-type catalyst to the lower chamber of the reactor. The present invention relates to a method for producing a copolymer.

[0002]

2. Description of the Related Art In a method for producing an ethylene / α-olefin copolymer, the productivity of the ethylene / α-olefin copolymer is determined by the product of the feed rate of the raw material gas to the reactor and the conversion rate. The feed rate of the feed gas is determined by the capacity of the compressor, and the conversion rate is determined by the difference between the reactor outlet temperature and the feed gas temperature.

Therefore, in order to improve the productivity of the ethylene / α-olefin copolymer, usually, a method of improving the conversion rate, that is, raising the reactor outlet temperature is adopted. But,
Since the metallocene catalyst is more expensive than the Ziegler type catalyst, the above method is not preferable in terms of cost. Therefore, it is possible to raise the reactor outlet temperature by using a Ziegler type catalyst in the lower part of the reactor.
When using a Ziegler type catalyst and a metallocene catalyst at the same temperature, copolymers with completely different molecular weights are obtained, and the characteristics of the ethylene / α-olefin copolymer that should be obtained by the metallocene catalyst are impaired. Get lost.

[0004]

The object of the present invention is to improve the productivity of ethylene / α-olefin copolymers while maintaining the characteristics of ethylene / α-olefin copolymers obtained by metallocene catalysts. It is in.

[0005]

Means for Solving the Problems As a result of intensive studies for solving the above-mentioned problems, the present inventors have found that ethylene / α which copolymerizes ethylene and α-olefins having 3 or more carbon atoms.
In the method for producing an olefin copolymer, the inside of the reactor is divided into at least three chambers, the metallocene catalyst is supplied to one chamber at the upper part of the reactor, and the Ziegler-type catalyst is supplied to one chamber at the lower part of the reactor to obtain a metallocene catalyst Ethylene obtained by
The inventors have found that the productivity of the ethylene / α-olefin copolymer can be improved while maintaining the characteristics of the α-olefin copolymer, and completed the present invention. Hereinafter, the present invention will be described in detail.

In order to solve the problems in using a metallocene catalyst and a Ziegler type catalyst together and to improve productivity, the inside of the reactor is divided into small chambers and the metallocene catalyst is kept at a low temperature in the small chamber above the reactor. It is essential that the reaction is performed and the Ziegler type catalyst is reacted at a high temperature in a small chamber at the bottom of the reactor. As a result, since the temperature in each small chamber can be controlled individually, the metallocene catalyst is reacted at a low temperature in the small chamber at the upper part of the reactor, and the ethylene / α-olefin copolymer having a high degree of polymerization is supplied to the small chamber at the lower part of the reactor. Ethylene obtained by a metallocene catalyst by reacting a Ziegler-type catalyst at high temperature to obtain an ethylene / α-olefin copolymer having a degree of polymerization equivalent to that of the ethylene / α-olefin copolymer obtained by the metallocene catalyst. An ethylene / α-olefin copolymer having the characteristics of the / α-olefin copolymer is obtained.

The number of divisions in the reactor must be at least 3 or more, preferably 5. This is determined in consideration of the effect of reducing the mixing ratio of the catalysts by increasing the number of divisions and the complication of the device shape. The dividing method may be either a method of providing a baffle plate on the reactor body as shown in FIG. 1 or a method of providing a baffle plate on the stirrer, or a method of using at least two or more reactors arranged in series. Good.

The reaction temperature is 120 ° C. or higher and 300 ° C. because the metallocene catalyst is supplied in the upper part of the reactor.
The temperature is preferably 120 ° C. or higher and 250 ° C. or lower. Further, since the Ziegler type catalyst is supplied in the lower part of the reactor, the temperature thereof is 150 ° C. or higher and 300 ° C. or lower, preferably 200 ° C. or higher and 300 ° C. or lower.

The reaction pressure is 400 kg / cm ² or more 400
It is 0 kg / cm ² or less, preferably 500 kg / cm ² or more and 2000 kg / cm ² or less.

As a component of the metallocene catalyst used in the present invention, a) a metallocene compound is represented by the following general formula (1)

[0011]

[Chemical 1]

(Wherein Cp ¹ and Cp ² are each independently a substituted or unsubstituted cyclopentadienyl group, an indenyl group or a fluorenyl group, and R ¹ is a hydrogen atom, a substituted or unsubstituted alkylene group, A dialkylsilanediyl group, a dialkylgermandiyl group, an alkylphosphinediyl group or an alkylimino group, wherein R ² and R ³ are each independently a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 12 carbon atoms, an alkoxy group or Is an aryloxy group, and M ¹ is titanium, zirconium or hafnium), and is preferably a compound represented by the general formula (2), (3) or (4)

[0013]

[Chemical 2]

[0014]

[Chemical 3]

[0015]

[Chemical 4]

(In the formulas (2) and (3), Cp ³ and Cp ⁴ are each independently a substituted or unsubstituted cyclopentadienyl group, and R ⁴ is a substituted or unsubstituted alkylene group, dialkyl A silanediyl group, a dialkylgermandiyl group, an alkylphosphinediyl group or an alkylimino group, R ⁴ acts so as to bridge Cp ³ and Cp ⁴ , and R ² and R ³ are each independently a hydrogen atom. , A halogen atom, a hydrocarbon group having 1 to 12 carbon atoms, an alkoxy group or an aryloxy group, and in the formula (4), Cp ⁵ , Cp ⁶
Are each independently a substituted or unsubstituted cyclopentadienyl group, an indenyl group or a fluorenyl group,
R ² and R ³ are each independently a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 12 carbon atoms, an alkoxy group or an aryloxy group, and R ⁵ and R ⁶ are each independently a hydrogen atom, a substituted or unsubstituted atom. A substituted alkyl group, an alkoxy group or an aryl group, and M ² is titanium or zirconium)
Is a compound represented by.

As the hafnium compound of the formula (2) or (3), for example, bis (cyclopentadienyl) hafnium dichloride, bis (methylcyclopentadienyl) hafnium dichloride, bis (butylcyclopentadienyl) hafnium dichloride, Ethylenebis (indenyl) hafnium dichloride, dimethylsilylbis (2,4,5-trimethylcyclopentadienyl) hafnium dichloride, dimethylsilylbis (3
-Methylcyclopentadienyl) hafnium dichloride, dimethylsilylbis (4-t-butyl-2-methylcyclopentadienyl) hafnium dichloride, diethylsilylbis (2,4,5-trimethylcyclopentadienyl) hafnium dichloride, Diethylsilylbis (2,4-dimethylcyclopentadienyl) hafnium dichloride, diethylsilylbis (3-methylcyclopentadienyl) hafnium dichloride, diethylsilylbis (4-t-butyl-2-methylcyclopentadienyl) Hafnium dichloride, isopropyl (cyclopentadienyl) (fluorenyl) hafnium dichloride, diphenylmethylene (cyclopentadienyl) (fluorenyl) hafnium dichloride, methylphenylmethylene ( Clopentadienyl) (fluorenyl) hafnium dichloride, isopropyl (cyclopentadienyl) (2,7-di-t-butylfluorenyl) hafnium dichloride, diphenylmethylene (cyclopentadienyl) (2,7-di- t-Butylfluorenyl) hafnium dichloride, methylphenylmethylene (cyclopentadienyl) (2,7-di-t-butylfluorenyl) hafnium dichloride, isopropylidenebis (cyclopentadienyl) hafnium dichloride, diphenylmethylene Bis (cyclopentadienyl) hafnium dichloride, methylphenylmethylene bis (cyclopentadienyl) hafnium dichloride, isopropylidene (cyclopentadienyl) (tetramethylcyclopentadienyl) hafni Mujikuroraido, diphenylmethylene (cyclopentadienyl) (tetramethylcyclopentadienyl) hafnium dichloride, isopropylidene-bis (indenyl) hafnium dichloride, diphenylmethylene (indenyl)
Examples thereof include hafnium dichloride and methylphenylmethylene bis (indenyl) hafnium dichloride, but are not limited thereto.

Examples of the compound of the formula (4) include isopropylidene (cyclopentadienyl) (fluorenyl).
Titanium dichloride, isopropylidene (cyclopentadienyl) (fluorenyl) zirconium dichloride, diphenylmethylene (cyclopentadienyl)
(Fluorenyl) titanium dichloride, diphenylmethylene (cyclopentadienyl) (fluorenyl) zirconium dichloride, methylphenylmethylene (cyclopentadienyl) (fluorenyl) titanium dichloride, methylphenylmethylene (cyclopentadienyl) (fluorenyl) zirconium dichloride, Isopropylidene (cyclopentadienyl) (2,7-di-t-butylfluorenyl) titanium dichloride,
Isopropylidene (2,7-di-t-butylfluorenyl) zirconium dichloride, diphenylmethylene (cyclopentadienyl) (2,7-di-t-butylfluorenyl) titanium dichloride, diphenylmethylene (cyclopentadiene) Enyl) (2,7-di-t-butylfluorenyl) zirconium dichloride, methylphenylmethylene (cyclopentadienyl) (2,7-di-t-butylfluorenyl) titanium dichloride,
Methylphenylmethylene (cyclopentadienyl)
(2,7-Di-t-butylfluorenyl) zirconium dichloride, isopropylidene (cyclopentadienyl) (2,7-dimethylfluorenyl) titanium dichloride, isopropylidene (cyclopentadienyl)
(2,7-Dimethylfluorenyl) zirconium dichloride, diphenylmethylene (cyclopentadienyl)
(2,7-Dimethylfluorenyl) titanium dichloride, diphenylmethylene (cyclopentadienyl)
(2,7-Dimethylfluorenyl) zirconium dichloride, methylphenylmethylene (cyclopentadienyl) (2,7-dimethylfluorenyl) titanium dichloride, methylphenylmethylene (cyclopentadienyl) (2,7-dimethyl Fluorenyl) zirconium dichloride, isopropylidene (cyclopentadienyl) (2,7-diphenylfluorenyl) titanium dichloride, isopropylidene (cyclopentadienyl) (2,7-diphenylfluorenyl) zirconium dichloride, diphenyl Methylene (cyclopentadienyl) (2,7-diphenylfluorenyl) titanium dichloride, diphenylmethylene (cyclopentadienyl) (2,7-diphenylfluorenyl) zirconium dichloride, Le phenylmethylene (cyclopentadienyl) (2,7-diphenyl fluorenyl) titanium dichloride, methylphenylmethylene (cyclopentadienyl) (2,7-diphenyl fluorenyl)
Zirconium dichloride, isopropylidene (cyclopentadienyl) (a, i-dibenzofluorenyl) titanium dichloride, isopropylidene (cyclopentadienyl) (a, i-dibenzofluorenyl) zirconium dichloride, diphenylmethylene (cyclopentadiene) Dienyl) (a, i-dibenzofluorenyl) titanium dichloride, diphenylmethylene (cyclopentadienyl) (a, i-dibenzofluorenyl) zirconium dichloride, methylphenylmethylene (cyclopentadienyl) (a, i -Dibenzofluorenyl) titanium dichloride, methylphenylmethylene (cyclopentadienyl) (a, i-dibenzofluorenyl) zirconium dichloride, isopropylidene (cyclopentadienyl) ( , H-Dibenzofluorenyl) titanium dichloride, isopropylidene (cyclopentadienyl) (b, h-dibenzofluorenyl) zirconium dichloride, diphenylmethylene (cyclopentadienyl) (b, h-dibenzofluorenyl) Titanium dichloride, diphenylmethylene (cyclopentadienyl) (b, h-dibenzofluorenyl) zirconium dichloride, methylphenylmethylene (cyclopentadienyl) (b, h-dibenzofluorenyl) titanium dichloride, methylphenylmethylene ( Cyclopentadienyl) (b, h-dibenzofluorenyl) zirconium dichloride, bis (4-methylphenyl) methylene (cyclopentadienyl) (fluorenyl) titanium dichloride, bis (4-me) Ruphenyl) methylene (cyclopentadienyl) (fluorenyl) zirconium dichloride, bis (4-phenylphenyl) methylene (cyclopentadienyl) (fluorenyl) titanium dichloride, bis (4-phenylphenyl) methylene (cyclopentadienyl) ( Fluorenyl) zirconium dichloride, isopropylidenebis (cyclopentadienyl) titanium dichloride, isopropylidenebis (cyclopentadienyl) zirconium dichloride, diphenylmethylenebis (cyclopentadienyl) titanium dichloride, diphenylmethylenebis (cyclopentadienyl) Zirconium dichloride, methylphenylmethylenebis (cyclopentadienyl) titanium dichloride, methylphenylmethylenebi Sus (cyclopentadienyl) zirconium dichloride, isopropylidene (cyclopentadienyl) (tetramethylcyclopentadienyl) titanium dichloride, isopropylidene (cyclopentadienyl) (tetramethylcyclopentadienyl) zirconium dichloride, diphenylmethylene (Cyclopentadienyl)
(Tetramethylcyclopentadienyl) titanium dichloride, diphenylmethylene (cyclopentadienyl) (tetramethylcyclopentadienyl) zirconium dichloride, isopropylidene bis (indenyl)
Titanium dichloride, isopropylidene bis (indenyl) zirconium dichloride, diphenylmethylenebis (indenyl) titanium dichloride, diphenylmethylenebis (indenyl) zirconium dichloride, methylphenylmethylenebis (indenyl) titanium dichloride, methylphenylmethylenebis (indenyl) zirconium dichloride, etc. Is mentioned.

Of these, the substituent Cp ⁶ in the general formula (4) is a substituted or unsubstituted fluorenyl group and / or
Alternatively, a metallocene compound in which at least one of the substituents R ⁵ and R ⁶ is a substituted or unsubstituted aryl group is preferable because efficient copolymerization can be performed.

The b) ionized ionic compound used in the present invention is a compound capable of converting the a) metallocene compound into a cationic metallocene compound and is a compound which does not react with the produced cationic metallocene compound. , Specifically, tri-n-butylammonium tetrakis (p-tolyl) borate, tri-n-butylammonium tetrakis (m-tolyl) borate, tri-
n-butylammonium tetrakis (2,4-dimethylphenyl) borate, tri-n-butylammonium tetrakis (3,5-dimethylphenyl) borate, tri-n-butylammonium tetrakis (pentafluorophenyl) borate, N, N- Dimethylanilinium tetrakis (p-tolyl) borate, N, N-Dimethylanilinium tetrakis (m-tolyl) borate, N, N
-Dimethylanilinium tetrakis (2,4-dimethylphenyl) borate, N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate, triphenylcarbenium tetrakis (p-tolyl) borate, triphenylcarbenium tetrakis (m-) Tolyl) borate, triphenylcarbenium tetrakis (2,4-dimethylphenyl) borate, triphenylcarbenium tetrakis (3,5-dimethylphenyl)
Borate, triphenylcarbenium tetrakis (pentafluorophenyl) borate, tropylium tetrakis (p-tolyl) borate, tropylium tetrakis (m-tolyl) borate, tropylium tetrakis (2,4-dimethylphenyl) borate, tropylium tetrakis (3,5-dimethylphenyl) borate, tropylium tetrakis (pentafluorophenyl) borate, lithium tetrakis (pentafluorophenyl)
Borate, lithium tetrakis (phenyl) borate,
Lithium tetrakis (p-tolyl) borate, lithium tetrakis (m-tolyl) borate, lithium tetrakis (2,4-dimethylphenyl) borate, lithium tetrakis (3,5-dimethylphenyl) borate, lithium tetrafluoroborate, sodium tetrakis ( Pentafluorophenyl) borate, sodium tetrakis (phenyl) borate, sodium tetrakis (p-tolyl) borate, sodium tetrakis (m-)
Tolyl) borate, sodium tetrakis (2,4-dimethylphenyl) borate, sodium tetrakis (3,5-dimethylphenyl) borate, sodium tetrafluoroborate, potassium tetrakis (pentafluorophenyl) borate, potassium tetrakis (phenyl) borate, potassium Tetrakis (p-tolyl) borate, potassium tetrakis (m-tolyl) borate,
Boron compounds such as potassium tetrakis (2,4-dimethylphenyl) borate, potassium tetrakis (3,5-dimethylphenyl) borate, potassium tetrafluoroborate, tri-n-butylammonium tetrakis (p-tolyl) aluminate, tri- n-butylammonium tetrakis (m-tolyl) aluminate, tri-n-butylammonium tetrakis (2,4-dimethylphenyl) aluminate, tri-n-butylammonium tetrakis (3,5-dimethylphenyl) aluminate, tri -N-butylammonium tetrakis (pentafluorophenyl) aluminate, N, N-dimethylanilinium tetrakis (p-tolyl) aluminate,
N, N-dimethylanilinium tetrakis (m-tolyl) aluminate, N, N-dimethylanilinium tetrakis (2,4-dimethylphenyl) aluminate,
N, N-dimethylanilinium tetrakis (pentafluorophenyl) aluminate, triphenylcarbenium tetrakis (p-tolyl) aluminate, triphenylcarbenium tetrakis (m-tolyl) aluminate, triphenylcarbenium tetrakis (2,2) 4-dimethylphenyl) aluminate, triphenylcarbenium tetrakis (3,5-dimethylphenyl) aluminate, triphenylcarbenium tetrakis (pentafluorophenyl) aluminate, tropylium tetrakis (p-tolyl) aluminate, tropylium Tetrakis (m-tolyl) aluminate, Tropylium tetrakis (2,4-dimethylphenyl) aluminate, Tropylium tetrakis (3,5-dimethylphenyl) aluminate, Tropiliu Tetrakis (pentafluorophenyl) aluminate, lithium tetrakis (pentafluorophenyl) aluminate, lithium tetrakis (phenyl) aluminate, lithium tetrakis (p- tolyl) aluminate, lithium tetrakis (m-tolyl)
Aluminate, lithium tetrakis (2,4-dimethylphenyl) aluminate, lithium tetrakis (3,5
-Dimethylphenyl) aluminate, lithium tetrafluoroaluminate, sodium tetrakis (pentafluorophenyl) aluminate, sodium tetrakis (phenyl) aluminate, sodium tetrakis (p)
-Tolyl) aluminate, sodium tetrakis (m-
Trily) aluminate, sodium tetrakis (2,4
-Dimethylphenyl) aluminate, sodium tetrakis (3,5-dimethylphenyl) aluminate, sodium tetrafluoroaluminate, potassium tetrakis (pentafluorophenyl) aluminate, potassium tetrakis (phenyl) aluminate, potassium tetrakis (p-tolyl) ) Aluminum compounds such as aluminate, potassium tetrakis (m-tolyl) aluminate, potassium tetrakis (2,4-dimethylphenyl) aluminate, potassium tetrakis (3,5-dimethylphenyl) aluminate, potassium tetrafluoroaluminate, etc. However, the present invention is not limited to these.

Further, the c) organoaluminum compound used in the present invention is represented by the following general formula (5):

[0022]

[Chemical 5]

(In the formula, R ⁶ , R ^{6 ′} and R ^{6 ″} are each independently a hydrogen atom, a halogen atom, an amido group, an alkyl group, an alkoxy group or an aryl group, and at least one is an alkyl group. A), specifically, trimethyl aluminum, trimethyl aluminum, triisopropyl aluminum, diisopropyl aluminum chloride, isopropyl aluminum dichloride, tributyl aluminum, triisobutyl aluminum, diisobutyl aluminum chloride, isobutyl aluminum dichloride, tri-t- Butyl aluminum, di-t-butyl aluminum chloride, t-butyl aluminum dichloride, triamyl aluminum, diamyl aluminum chloride, amyl aluminum dichloride Ride and the like are mentioned, but the present invention is not limited to these.

In the present invention, a method for preparing a catalyst from the above a) metallocene compound, b) ionized ionic compound and c) organoaluminum compound is, for example, a method of mixing these compounds in an inert solvent. However, the present invention is not limited to these.

The amount of the b) ionized ionic compound used in the present invention is 0.1 with respect to the a) metallocene compound.
˜100 times mol, particularly preferably 0.5 to 30 times mol.

Further, the amount of c) the organoaluminum compound is not particularly limited, but it is preferably 1 to 10000 mol per mol of the a) metallocene compound.

The Ziegler type catalyst is disclosed in JP-B-62-322.
No. 04, Japanese Patent Publication No. 2-31085, and JP-A-61
No. 123605, and the like. Specifically, [A] (a) Titanium trichloride or a composite component of titanium trichloride and magnesium chloride, (b) vanadium trichloride and general formula B (OR ⁷ ) described in JP-A-61-123605. ) in _{^{m X 1 3-m · Y}} n ( wherein, R ⁷ is a hydrocarbon group having 1 to 20 carbon atoms, X ¹ is a halogen atom, Y represents an electron-donating compound, m is 0 ≦ m
≦ 3, n is a number of 0 or 1), and a catalyst system comprising a solid catalyst component obtained by co-milling a boron compound and [B] an organoaluminum compound. Also, (A) (i) at least one member selected from the group consisting of (A) (i) metal magnesium and an organic compound containing hydroxide, an oxygen-containing organic compound of magnesium and a halogen-containing compound described in JP-A-5-287021; and (ii)
A reaction product obtained by reacting titanium with an oxygen-containing organic compound, (iii) a solid catalyst component obtained by reacting an organoaluminum halide compound, and (B) at least one selected from organoaluminum compounds In such a catalyst system, a Ziegler type catalyst in which the organoaluminum compound in the component (B) is 20 times or less mol per 1 gram atom of titanium contained in the component (A) is also included. The Ziegler type catalyst is not limited to the above.

As the α-olefin having 3 or more carbon atoms, propylene, 1-butene, 4-methyl-1-pentene, 1
-Hexene, 1-octene, styrene, etc. can be mentioned, and these 1 type may be used or 2 or more types may be mixed and used. The α-olefin is not limited to the above.

[0029]

EXAMPLES The present invention will be described in detail with reference to Examples and Comparative Examples, but the present invention is not limited to these Examples. Table 1 shows reaction conditions and the like of each example and comparative example.

Example 1 In a process for producing an ethylene / α-olefin copolymer, a reactor divided into 5 chambers by a stirrer with a baffle plate was used, and a metallocene catalyst was placed in one chamber above the reactor. While supplying the Ziegler-type catalyst to the lower chamber, the reaction pressure was 900 kg / cm ² , and the temperature in the upper part of the reactor was 150.
℃, the temperature of the bottom of the reactor is 250 ℃, 1500 rpm
Continuous operation was carried out with stirring. The metallocene catalyst is diphenylmethylene (cyclopentadienyl).
(Fluorenyl) zirconium dichloride, N, N-
Dimethylanilinium tetrakis (pentafluorophenyl) borate and triisobutylaluminum were used at a molar ratio of boron / zirconium = 1/1, aluminum / zirconium = 250/1, and a zirconium concentration of 650 μm.
A toluene solution adjusted to ol / l was used. As a Ziegler type catalyst, the main catalyst was titanium trichloride (TiCl ₃ .1 / 3AlCl ₃ ) obtained by reducing titanium tetrachloride with metallic aluminum and magnesium dichloride co-milled at a molar ratio of 1: 2.5. As a cocatalyst, triethylaluminum was prepared so that the molar ratio of titanium / aluminum was 1/3, and a slurry liquid obtained by diluting this with normal heptane to a titanium concentration of 75 mmol / l was used.

Example 2 The procedure of Example 1 was repeated, except that the reactor main body was provided with a baffle plate instead of the stirrer with a baffle plate.

Example 3 Example 3 was repeated except that the number of divisions was changed from 5 to 3.

Comparative Example 1 The procedure of Example 1 was repeated except that a stirrer without a baffle plate was used in place of the stirrer with a baffle plate.

Comparative Example 2 The procedure of Example 1 was repeated, except that a stirrer without a baffle plate was used in place of the stirrer with a baffle plate, and the temperature of the reactor was raised to 150 ° C. while supplying only the metallocene catalyst.

EXAMPLE 4 The metallocene-catalyzed diphenylmethylene (cyclopentadienyl) (fluorenyl) zirconium dichloride was replaced by diphenylmethylene (dicyclopentadienyl) (2,7-dimethylfluorenyl) zirconium dichloride, Zirconium concentration 300 μmol
/ L, the reaction pressure was 500 kg / cm ² , and the temperature above the reaction temperature was 180 ° C.

Comparative Example 3 The procedure of Example 4 was repeated except that a stirrer without a baffle plate was used instead of the stirrer with a baffle plate.

Comparative Example 4 The procedure of Example 4 was repeated, except that the stirrer without a baffle plate was used instead of the stirrer with a baffle plate, and the temperature of the reactor was set to 180 ° C. while supplying only the metallocene catalyst.

[0038]

[Table 1]

[0039]

As described above, by using the method of the present invention, the characteristics of the ethylene / α-olefin copolymer obtained by the metallocene catalyst can be maintained while maintaining the characteristics of the ethylene / α-olefin copolymer. Productivity can be improved.

[Brief description of drawings]

FIG. 1 is a diagram showing a structure of a reactor main body.

Claims (3)

(57) [Claims] 1. In a method for producing an ethylene / α-olefin copolymer for copolymerizing ethylene and an α-olefin having 3 or more carbon atoms, the reactor is divided into at least three chambers,
A metallocene catalyst was placed in one chamber at the top of the reactor,
A method for producing an ethylene / α-olefin copolymer, which comprises supplying a Ziegler type catalyst to the chamber. 2. The temperature of the upper part of the reactor is 120 ° C. or higher and 300 ° C.
Below the temperature of the lower part of the reactor 150 ℃ 300 ℃
The method for producing an ethylene / α-olefin copolymer according to claim 1, wherein the reaction is carried out below. 3. A reaction pressure of 400 kg / cm ² or more 400
The method for producing an ethylene / α-olefin copolymer according to claim 1 or 2, wherein the reaction is carried out at 0 kg / cm ² or less.