JPH07188336A - Production of ethylenic copolymer - Google Patents

Abstract

PURPOSE:To economically and advantageously obtain an ethylenic copolymer excellent in melt tension, having a narrow distribution of composition and useful as a blow molding, etc., by copolymerizing ethylene with an alpha-olefin using a specific catalyst. CONSTITUTION:The method for producing this copolymer is to copolymerize ethylene with a 4-20C alpha-olefin by using a catalyst composed of a product prepared by bringing (A) a compound expressed by formula I {(C5R<1>5) is cyclopentadienyl, etc.; R<1> is H, a halogen, etc.; M is a group IV to VI metal of the long-form Periodic Table; (p), (q) and (r) each is (p)>=1; (q)>=0, (r)>=0 and [(p)+(q)+(r)] is the valence of M} or formula II {R<3> is a neutral ligand of M; R<4> is a counter anion of M ion; (s), (u), (t), (x) and (y) each is (s)>=0; (u)>=1; [(t)-(x)] is the valence of M; (u)X(Y) is (x)} into contact with (B) a clay (mineral), etc., and (C) an organoaluminum compound. The resultant ethylenic copolymer has a relationship between the melt tension(MT) and the melt index(MI) satisfying formula III, and 2-5 of the ratio of the weight-average molecular weight to the number-average molecular weight.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a method for producing an ethylene copolymer. More specifically, it relates to a method for producing an ethylene-based copolymer having excellent melt tension and a narrow composition distribution under economically advantageous conditions.

[0002]

2. Description of the Related Art In producing an ethylene-based copolymer by copolymerizing ethylene and an α-olefin in the presence of a catalyst, (1) a metallocene compound is added to a transition metal component as a catalyst. Using (2)
A method using aluminoxane as an organic metal component is disclosed in Japanese Patent Laid-Open No.
It is proposed in Japanese Patent Laid-Open No. 8-19309. The polymerization method using this catalyst has a very high polymerization activity per transition metal and a polymer having a narrow molecular weight distribution as compared with the conventional method using a Ziegler-Natta catalyst. However, the above catalyst is a very economically disadvantageous production method because a large amount of expensive aluminoxane is used and the polymerization activity per aluminum is low, and it is necessary to remove the catalyst residue from the produced polymer. Further, when the polymer obtained by the same method is molded by various molding methods, there is a problem that it is difficult to mold because of a narrow molecular weight distribution and a low melt tension. Specifically, for example, when it is used for blow molding, drawdown occurs, and the thickness of the molded product becomes uneven, and in some cases, there is a problem of blowout or shake.

When an inflation film is formed at high speed, bubbles are torn or shake. Furthermore, the T-die molding has a problem in that rough skin is likely to occur and neck-in is likely to occur. On the other hand, in recent years,
Various methods for polymerizing olefins have been proposed for the purpose of improving the moldability. For example, JP-A-4-213306
In the publication, (1) a transition metal compound having, as a ligand, a compound having a structure in which at least two groups having a cyclopentadienyl skeleton are crosslinked with a carbon and / or a silicon-containing group is used as a transition metal component, (2) A method of polymerizing ethylene and α-olefin using a catalyst system that requires aluminoxane as an organic metal component has been proposed. However, the copolymer obtained by the above production method has a relatively narrow composition distribution, and although a certain improvement effect can be obtained with respect to the above-mentioned molding problems, it is economical because an expensive transition metal compound or aluminoxane is used. In terms of aspect, it cannot be said that this is an excellent manufacturing method.

[0004]

In order to solve the above problems, the inventors of the present invention have earnestly studied a method for producing an ethylene copolymer having excellent moldability and a narrow composition distribution by an economically inexpensive method. As a result, by using a specific metallocene compound and clay, a clay mineral or an ion-exchange layered compound and an organoaluminum compound as an essential catalyst component and copolymerizing ethylene and an α-olefin having 4 to 20 carbon atoms, the melt tension can be increased. It has been found that an ethylene-based copolymer which is excellent and has a narrow composition distribution can be obtained, and the present invention has been accomplished.

That is, the present invention relates to [A] one or more metallocene compounds represented by the following general formula [1] or [2]:

[0006]

## STR3 ## ^{_{(C 5 R 1 5) p}} (C 5 R 1 5) q MR 2 r [1] or

[0007]

Embedded image ^{_{[(C 5 R 1 5) p}} (C 5 R 1 5) q MR 2 r R 3 s ] ^x + uR ^{4 y-} [2]

(However, in the formulas [1] and [2], each (C ₅ R
¹ ₅ ) is a cyclopentadienyl group which may be the same or different, or a cyclopentadienyl group having a substituent, each R ¹ may be the same or different, hydrogen, halogen, a silicon-containing group, a halogen-substituted group A hydrocarbon group having 1 to 20 carbon atoms which may have a group, an alkoxy group or an aryloxy group, and two R ^{1 s} are present at two adjacent carbon atoms of the cyclopentadienyl ring. May be bonded to each other to form a C _{4 to} C ₆ ring, and R ² has the same or different hydrogen, halogen, silicon-containing group, and the number of carbon atoms which may have a halogen substituent. 1 to 20 hydrocarbon groups, alkoxy groups, aryloxy groups, SO ₁ R ⁵ groups, NR ⁶ _m groups or PO _n R ⁷ ₃ groups, wherein R ⁵ , R ⁶ and R ⁷ are hydrogen, halogen, Silicon-containing group or halogen substitution A hydrocarbon group having 1 to 20 carbon atoms which may have, l is 0, 1, 2 or 3, m is 0, 1, 2 or 3, and n is 0, 1, 2 or 3, and p, q, r, s,
t, u, x, and y are integers that satisfy the following equation.

[0009]

## EQU00002 ## p.gtoreq.1, q.gtoreq.0, r.gtoreq.0, s.gtoreq.0, u.gtoreq.1 p≥q + r = t in the case of the formula [1] and p in the case of the formula [2].
+ Q + r = t−x, x = u × y, and t is the valence of the metal M. M is a metal of Groups 4, 5 and 6 of the long periodic table, R ³ is a neutral ligand coordinating to M, and R ^{4 y-} can stabilize the above metal cation. Indicates a counter anion)

A product obtained by contacting [B] clay, a clay mineral or an ion-exchange layered compound and [C] an organoaluminum compound, and, if necessary,

[D] In the presence of a catalyst composed of an organoaluminum compound, ethylene and α having 4 or more and 20 or less carbon atoms are used.
-Copolymerization with olefin, a) Melt index (MI) at 190 ° C under a load of 2.16 kg is 0.001 g / 10 min to 100 g.
/ 10 min range, b) density in the range of 0.86 to 0.97 g / cm ³ , c) 10.2 kg and 1.02 kg at 190 ° C.
Outflow ratio (FR) under load condition is 13 to 50
D) the relationship between melt tension (MT) at 190 ° C. and MI satisfies the relationship of logMT> −0.46logMI + 0.5, and e) the relationship of Mw / Mn measured by GPC in the range of 2 to 5 And a method for producing an ethylene-based copolymer, characterized in that an ethylene-based copolymer satisfying the requirements is obtained.

The method for producing the ethylene copolymer of the present invention will be described in detail below. The ethylene-based copolymer produced by the present invention comprises ethylene and 4 to 20 carbon atoms.
Is a random copolymer with α-olefin. Examples of the α-olefin having 4 to 20 carbon atoms include butene-1, pentene-1, 3-methylbutene-1, hexene-1, 4
-Methylpentene-1, 3-methylpentene-1, octene-1, decene-1, tetradecene-1, hexadecene-1, octadecene-1, eicosene-1 and the like are used. Further, vinyl compounds such as vinylcyclohexane or styrene and its derivatives can also be used. Further, it may be a ternary random copolymer of ethylene, α-olefin and a small amount of non-conjugated polyene, if necessary. The ethylene copolymer thus copolymerized has a density of 0.86 g / cm ³ to 0.97 g / c.
m ³ , preferably 0.87 g / cm ³ to 0.94 g
/ Cm ³ . The density was measured by the density gradient tube method after heat-treating the strand obtained at the time of measuring the melt index at 100 ° C. for 1 hour and allowing it to cool at room temperature for 1 hour.

Such an ethylene copolymer has an ethylene unit content of 55.0 to 99.9% by weight, preferably 65%.
To 98% by weight, and 0.01 to 45% by weight, preferably 2 to 35% by weight of an α-olefin unit having 4 to 20 carbon atoms. Next, the melt index (MI) of the ethylene-based copolymer is 0.001 to 10
0 g / 10 minutes, preferably 0.01 to 50 g / 10
It is in the range of minutes. If the MI is less than 0.001, it is difficult to mold and it is not preferable. If MI is 100 or more, the mechanical strength is poor. In addition, MI is based on ASTM D1238,
It was measured at 190 ° C. under a load of 2.16 kg. The ethylene-based copolymer produced by the present invention was measured at 190 ° C. under the conditions of 10.2 kg load and 1.02 kg load using the same apparatus as the above-mentioned MI measurement, that is, the outflow rate (FR), that is,

[0014]

[Equation 3] Is in the range of 13 to 50, preferably 14 to 45. When FR is less than 13, moldability such as extrudability, drawdown resistance, bubble stability, and uniform stretchability is poor, which is not preferable.

Further, the ethylene copolymer produced according to the present invention has a relationship between melt tension (MT) and MI of logMT> -0.46logMI + 0.5, preferably logMT> -0.46log.
Satisfies the relationship represented by MI + 0.65. In the relationship between MT and MI, M
When T is less than or equal to the above formula, the molding characteristics such as bubble stability, drawdown resistance, and uniform stretchability are inferior, which is not preferable.

The MT was measured using a melt tension tester manufactured by Itesco Co., Ltd., and the nozzle diameter was 2.095.
mmφ, nozzle length = 8 mm, inflow angle = 90 °, 190 ° C.
At an extrusion speed of 0.716 cc / min, a take-up speed of 10 m / min, and an air gap of 40 cm. In addition, when measuring the above-mentioned MI, FR and MT, the ethylene-based copolymer was previously
0.1 parts by weight of 6-di-t-butylparacresol was added.

The molecular weight distribution of the ethylene copolymer produced according to the present invention is such that the Mw / Mn measured by GPC is in the range of 2 to 5, preferably 2.5 to 5. G
The measurement of PC uses a 150C type device manufactured by Millipore, and ortho-dichlorobenzene as a solvent.
It was measured at 5 ° C.

The ethylene-based copolymer produced according to the present invention is measured by the cross fractionation method. The relation between the temperature (T _max ) at the maximum peak position of the elution curve and the density (d) is T _max <800d-658. It is preferable to satisfy the relationship shown by. As described above, the ethylene-based copolymer produced by the present invention has a narrow composition distribution according to the above formula, and thus is excellent in transparency, heat sealing property, hot tack property and the like.

In the measurement by the cross fractionation method, CFC T-102L manufactured by Mitsubishi Petrochemical was used, ortho-dichlorobenzene was used as a solvent, and the flow rate was 1 ml / min and the temperature decreasing rate was 1
° C / min, temperature rising rate; 1 ° C / min, column size; 0.46
cmφ × 15 cm, packing material; glass beads, detector; infrared detector, measurement wave number; 3.42 μm, sample concentration; 1 mg
/ Ml, injection amount; under the condition of 500 μl, specifically, the sample solution was introduced into the column at 135 ° C., and 1 ° C./min was 40 ° C.
After cooling to 50% to adsorb the polymer on the packing material, the concentration of the polymer eluted at each temperature was detected with an infrared detector while the column temperature was raised. Here, the temperature of the main elution peak is T
defined as _(max) .

Next, an ethyle having the characteristics described above
The method for producing the copolymer will be described. Touch of the invention
Of the metallocene compound used as the medium, that is, the component [A]
Examples are compounds represented by the above general formula [1] or [2].
It is a thing. In the above general formula [1] or [2], each C_FiveR¹
_FiveMay be the same or different cyclopentadienyl
Or a substituted cyclopentadienyl group. Where R
¹May be the same or different, hydrogen, fluorine, salt
Halogen such as elemental, bromine, iodine, trimethylsilyl, tri
Silicon-containing groups such as ethylsilyl and triphenylsilyl groups,
Methyl, ethyl, propyl, butyl, isobutyl, pen
Chill, isopentyl, hexyl, heptyl, octyl,
Nonyl, decyl, phenyl, chloromethyl, chloroethy
1 to 1 carbon atoms which may have a halogen group such as
20 hydrocarbon groups, methoxy, ethoxy, propoxy,
Alkoxy group such as butoxy group, phenoxy, methylphen
Aryloxy such as noxy and pentamethylphenoxy groups
Group, 2 R¹Are adjacent to each other on the cyclopentadienyl ring
Present on 3 carbon atoms and bound to each other by C_Four~ C₆A ring
Forming, indenyl, tetrahydroindenyl, fluor
Even if it becomes a renyl, octahydrofluorenyl group, etc.
Yes. Of these, hydrogen, a methyl group, and two R¹But
Combined with each other, indenyl, tetrahydroindenyl,
Fluorenyl, octahydrofluorenyl group formed
Hydrocarbon groups are preferred. Especially, hydrogen and methyl groups are preferred.
Yes. R²Are hydrogen, which may be the same or different,
Halogen such as elemental, chlorine, bromine and iodine, trimethylsilyl
Silicon such as chloro, triethylsilyl and triphenylsilyl groups
Containing groups, methyl, ethyl, propyl, butyl, isobutyl
Le, pentyl, isopentyl, hexyl, heptyl, o
Cutyl, nonyl, decyl, phenyl, chloromethyl, cu
Charcoal optionally having a halogen substituent such as a loroethyl group
Hydrocarbon groups having a prime number of 1 to 20, methoxy, ethoxy,
Alkoxy groups such as propoxy and butoxy groups, phenoxy
Ci, methylphenoxy, pentamethylphenoxy groups, etc.
Aryloxy group, SO_lR^FiveGroup, NR⁶ _mGroup or P
O _nR⁷ ₃Group, where R^Five, R⁶, R⁷Are the same
Or may be different hydrogen, fluorine, chlorine, bromine, iodine
Elemental halogen, trimethylsilyl, triethylsilyl
Group, a silicon-containing group such as triphenylsilyl group, methyl,
Chill, propyl, butyl, isobutyl, pentyl, iso
Pentyl, hexyl, heptyl, octyl, nonyl, de
Ha, such as silyl, phenyl, chloromethyl, and chloroethyl groups.
C1 to C20 optionally having a rogen substituent
Hydrocarbon group, especially hydrogen, chlorine and methyl groups are preferred.
Yes. Also, l is 0, 1, 2 or 3, and m is 0, 1,
2 or 3, n is 0, 1, 2 or 3, S
O_lR^FiveExamples of the group include a methylmercapto group and ethyl group.
Rumercapto group, thiophenyl group, methyl sulfone group,
Methyl sulfoxide group, methanesulfonato group, p-tolu
Ensulphonato group, benzenesulphonato group, trifluor
Rmethanesulfonato group, pentafluorobenzenesulfo
Is a nato group, etc.³Is methoxy, ethoxy, pro
NR, such as poxy and phenoxy groups⁶ _mAs an example
For example, a dimethylamide group, a diethylamide group, etc.,
PO_nR⁷ ₃As the group, a trimethylphosphine group,
And a triphenylphosphine group.

In the general formulas [1] and [2],
p, q, r, s, t, u, x, y are integers that satisfy the following equation.

## EQU00004 ## p.gtoreq.1, q.gtoreq.0, r.gtoreq.0, s.gtoreq.0, u.gtoreq.1 p≥q + r = t in the case of the formula [1] and p in the case of the formula [2].
+ Q + r = t−x, x = u × y, and t is the valence of the metal M.

In particular, p = 1, q = 1, r = 2, t = 4
It is preferable that u = 1, x = 1 and y = 1. M is titanium,
Zirconium, hafnium, vanadium, niobium, tantalum, chromium, molybdenum, and tungsten are metals of Groups 4, 5, and 6 of the long periodic table, and titanium, zirconium, and hafnium are particularly preferable. R ³ is a neutral ligand that coordinates with M such as tetrahydrofuran, and R ^4- is the above-mentioned general formula such as tetraphenylborate, tetra (p-tolyl) borate, carbadodecaborate, dicarbaundecaborate. The counter anion capable of stabilizing the metal cation in 2] is shown.

The metallocene-based transition metal compound compound is specifically represented by the formula [1] when zirconium is taken as an example.
Examples of bis (methylcyclopentadienyl) zirconium dichloride, bis (ethylcyclopentadienyl) zirconium dichloride, bis (methylcyclopentadienyl) zirconium dimethyl, bis (ethylcyclopentadienyl) zirconium dimethyl , Bis (methylcyclopentadienyl) zirconium dihydride, bis (ethylcyclopentadienyl) zirconium dihydride, bis (dimethylcyclopentadienyl) zirconium dichloride, bis (trimethylcyclopentadienyl) zirconium dichloride, bis (Tetramethylcyclopentadienyl) zirconium dichloride, bis (ethyltetramethylcyclopentadienyl) zirconium dichloride, bis (indenyl) zirconium Chloride, bis (dimethylcyclopentadienyl) zirconium dimethyl, bis (trimethylcyclopentadienyl) zirconium dimethyl, bis (tetramethylcyclopentadienyl) zirconium dimethyl, bis (ethyltetramethylcyclopentadienyl) zirconium dimethyl, bis (Indenyl) zirconium dimethyl, bis (dimethylcyclopentadienyl) zirconium dihydride, bis (trimethylcyclopentadienyl) zirconium dihydride, bis (ethyltetramethylcyclopentadienyl) zirconium dihydride, bis (trimethylsilyl) Cyclopentadienyl) zirconium dimethyl, bis (trimethylsilylcyclopentadienyl) zirconium dihydride, bis (trifluoromethylcyclopentadiene Nil)
Zirconium dichloride, bis (trifluoromethylcyclopentadienyl) zirconium dimethyl, bis (trifluoromethylcyclopentadienyl) zirconium dihydride, pentamethylcyclopentadienyl (cyclopentadienyl) zirconium dichloride,
Pentamethylcyclopentadienyl (cyclopentadienyl) zirconium dimethyl, pentamethylcyclopentadienyl (cyclopentadienyl) zirconium dihydride, ethyl tetramethylcyclopentadienyl (cyclopentadienyl) zirconium dihydride, Bis (cyclopentadienyl) zirconium dichloride,
Bis (cyclopentadienyl) zirconium dimethyl,
Bis (cyclopentadienyl) zirconium diethyl,
Bis (cyclopentadienyl) zirconium dipropyl, bis (cyclopentadienyl) zirconium diphenyl, methylcyclopentadienyl (cyclopentadienyl) zirconium dichloride, ethylcyclopentadienyl (cyclopentadienyl)

Zirconium dichloride, methylcyclopentadienyl (cyclopentadienyl) zirconium dimethyl, ethylcyclopentadienyl (cyclopentadienyl) zirconium dimethyl, methylcyclopentadienyl (cyclopentadienyl) zirconium dihydride, Ethylcyclopentadienyl (cyclopentadienyl) zirconium dihydride, dimethylcyclopentadienyl (cyclopentadienyl) zirconium dichloride, trimethylcyclopentadienyl (cyclopentadienyl) zirconium dichloride, tetramethylcyclopentadienyl (Cyclopentadienyl) zirconium dichloride, bis (pentamethylcyclopentadienyl) zirconium dichloride, tetramethylcyclopentadienyl (Cyclopentadienyl) zirconium dichloride, indenyl (cyclopentadienyl) zirconium dichloride, dimethylcyclopentadienyl (cyclopentadienyl) zirconium dimethyl, trimethylcyclopentadienyl (cyclopentadienyl) zirconium dimethyl, tetramethylcyclo Pentadienyl (cyclopentadienyl) zirconium dimethyl, bis (pentamethylcyclopentadienyl) zirconium dimethyl, ethyltetramethylcyclopentadienyl (cyclopentadienyl) zirconium dimethyl, indenyl (cyclopentadienyl) zirconium dimethyl, Dimethylcyclopentadienyl (cyclopentadienyl) zirconium dihydride, trimethylcyclopentadienyl (cyclopentadienyl) Z) zirconium dihydride, bis (pentamethylcyclopentadienyl) zirconium dihydride, indenyl (cyclopentadienyl) zirconium dihydride, trimethylsilylcyclopentadienyl (cyclopentadienyl) zirconium dimethyl, trimethylsilylcyclopenta Dienyl (cyclopentadienyl) zirconium dihydride, trifluoromethylcyclopentadienyl (cyclopentadienyl) zirconium dichloride, trifluoromethylcyclopentadienyl (cyclopentadienyl) zirconium dimethyl, trifluoromethylcyclopenta Dienyl (cyclopentadienyl)

Zirconium dihydride, bis (cyclopentadienyl) (trimethylsilyl) (methyl) zirconium, bis (cyclopentadienyl) (triphenylsilyl) (methyl) zirconium, bis (cyclopentadienyl) [tris ( (Trimethylsilyl) silyl] (methyl) zirconium, bis (cyclopentadienyl)
[Bis (methylsilyl) silyl] zirconium, bis (cyclopentadienyl) (trimethylsilyl) (trimethylsilylmethyl) zirconium, bis (cyclopentadienyl) (trimethylsilyl) (benzyl) zirconium, cyclopentadienylzirconium trichloride, bis ( Cyclopentadienyl) zirconium bis (methanesulfonato), bis (cyclopentadienyl)
Zirconium bis (p-toluenesulfonato), bis (cyclopentadienyl) zirconium bis (trifluoromethanesulfonato), bis (cyclopentadienyl) zirconium trifluoromethanesulfonato chloride, bis (cyclopentadienyl)

Zirconium bis (benzenesulfonato), bis (cyclopentadienyl) zirconium bis (pentafluorobenzenesulfonato), bis (cyclopentadienyl) zirconium benzenesulfonato chloride, bis (cyclopentadienyl) zirconium ( Ethoxy) trifluoromethanesulfonato, bis (tetramethylcyclopentadienyl) zirconium bis (trifluoromethanesulfonato), bis (indenyl) zirconium bis (trifluoromethanesulfonato) and the like.

The compounds corresponding to the general formula [2] include bis (methylcyclopentadienyl) zirconium (chloride) (tetraphenylborate) tetrahydrofuran complex, bis (ethylcyclopentadienyl) zirconium (chloride) ( Tetraphenylborate)
Tetrahydrofuran complex, bis (methylcyclopentadienyl) zirconium (methyl) (tetraphenylborate) tetrahydrofuran complex, bis (ethylcyclopentadienyl) zirconium (methyl) (tetraphenylborate) tetrahydrofuran complex, bis (methylcyclopentadienyl) ) Zirconium (hydrido) (tetraphenylborate) tetrahydrofuran complex, bis (ethylcyclopentadienyl) zirconium (hydrido) (tetraphenylborate) tetrahydrofuran complex ,, bis (dimethylcyclopentadienyl) zirconium (chloride) (tetraphenylborate) ) Tetrahydrofuran complex, bis (trimethylcyclopentadienyl) zirconium (chloride) (tetraphenylborate) tetrahydr Furan complex, bis (tetramethylcyclopentadienyl) zirconium (chloride)
(Tetraphenylborate) tetrahydrofuran complex,
Bis (ethyltetramethylcyclopentadienyl) zirconium (chloride) (tetraphenylborate) tetrahydrofuran complex, bis (indenyl) zirconium (chloride) (tetraphenylborate) tetrahydrofuran complex, bis (dimethylcyclopentadienyl) zirconium (methyl) (Tetraphenylborate) tetrahydrofuran complex, bis (trimethylcyclopentadienyl) zirconium (methyl) (tetraphenylborate) tetrahydrofuran complex, bis (tetramethylcyclopentadienyl) zirconium (methyl)
(Tetraphenylborate) tetrahydrofuran complex,
Bis (ethyltetramethylcyclopentadienyl) zirconium (methyl) (tetraphenylborate) tetrahydrofuran complex, bis (indenyl) zirconium (methyl) (tetraphenylborate) tetrahydrofuran complex, bis (dimethylcyclopentadienyl) zirconium (hydride) (Tetraphenylborate) tetrahydrofuran complex, bis (trimethylcyclopentadienyl) zirconium (hydride) (tetraphenylborate) tetrahydrofuran complex, bis (ethyltetramethylcyclopentadienyl) zirconium (hydride) (tetraphenylborate) tetrahydrofuran complex, Bis (trimethylsilylcyclopentadienyl) zirconium (methyl) (tetraphenylborate) tetrahydrofuran complex, Sus (trimethylsilylcyclopentadienyl) zirconium (hydride) (tetraphenylborate) tetrahydrofuran complex, bis (trifluoromethylcyclopentadienyl) zirconium (methyl) (tetraphenylborate) tetrahydrofuran complex, bis (trifluoromethylcyclopentadi) (Enyl) zirconium (hydride) (tetraphenylborate) tetrahydrofuran complex, pentamethylcyclopentadienyl (cyclopentadienyl) zirconium (chloride) (tetraphenylborate) tetrahydrofuran complex, ethyltetramethylcyclopentadienyl (cyclopentadienyl) ) Zirconium (chloride)
(Tetraphenylborate) tetrahydrofuran complex,
Pentamethyl cyclopentadienyl (cyclopentadienyl) zirconium (methyl)

(Tetraphenylborate) tetrahydrofuran complex, ethyltetramethylcyclopentadienyl (cyclopentadienyl) zirconium (methyl) (tetraphenylborate) tetrahydrofuran complex, pentamethylcyclopentadienyl (cyclopentadienyl) zirconium ( Hydride) (tetraphenylborate) tetrahydrofuran complex, ethyltetramethylcyclopentadienyl (cyclopentadienyl) zirconium (hydrido) (tetraphenylborate) tetrahydrofuran complex, bis (cyclopentadienyl) zirconium (chloride) (tetraphenylborate) ) Tetrahydrofuran complex, bis (cyclopentadienyl) (methyl) zirconium (tetraphenylborate) tetrahydrofuran complex, Scan (cyclopentadienyl) (ethyl) zirconium (tetraphenylborate) tetrahydrofuran complex, bis (cyclopentadienyl) (propyl) zirconium (tetraphenylborate) tetrahydrofuran complex, bis (cyclopentadienyl)
(Phenyl) zirconium (tetraphenylborate)
Tetrahydrofuran complex, methylcyclopentadienyl (cyclopentadienyl)

Zirconium (chloride) (tetraphenylborate) tetrahydrofuran complex, ethylcyclopentadienyl (cyclopentadienyl) zirconium (chloride) (tetraphenylborate) tetrahydrofuran complex, bis (ethylcyclopentadienyl) zirconium (chloride) (Tetraphenyl borate)
Tetrahydrofuran complex, methylcyclopentadienyl (cyclopentadienyl) zirconium (methyl) (tetraphenylborate) tetrahydrofuran complex, ethylcyclopentadienyl (cyclopentadienyl) zirconium (methyl) (tetraphenylborate) tetrahydrofuran complex, methyl Cyclopentadienyl (cyclopentadienyl) zirconium (hydrido) (tetraphenylborate) tetrahydrofuran complex, ethylcyclopentadienyl (cyclopentadienyl) zirconium (hydrido) (tetraphenylborate) tetrahydrofuran complex, dimethylcyclopentadienyl (Cyclopentadienyl) zirconium (chloride) (tetraphenylborate) tetrahydrofuran complex, trimethylcyclopenta Enyl (cyclopentadienyl) zirconium (chloride) (tetraphenylborate)
Tetrahydrofuran complex, tetramethylcyclopentadienyl (cyclopentadienyl) zirconium (chloride) (tetraphenylborate) tetrahydrofuran complex, bis (pentamethylcyclopentadienyl) zirconium (chloride) (tetraphenylborate) tetrahydrofuran complex, indenyl ( Cyclopentadienyl) zirconium (chloride) (tetraphenylborate) tetrahydrofuran complex, dimethylcyclopentadienyl (cyclopentadienyl) zirconium (methyl) (tetraphenylborate) tetrahydrofuran complex, trimethylcyclopentadienyl (cyclopentadienyl) ) Zirconium (methyl) (tetraphenylborate) tetrahydrofuran complex, tetramethylcyclopentadienyl ( Cyclopentadienyl) zirconium (methyl) (tetraphenylborate) tetrahydrofuran complex, bis (pentamethylcyclopentadienyl)
Zirconium (methyl) (tetraphenylborate) tetrahydrofuran complex, cyclopentadienyl (indenyl)

Zirconium (methyl) (tetraphenylborate) tetrahydrofuran complex, dimethylcyclopentadienyl (cyclopentadienyl) zirconium (hydride) (tetraphenylborate) tetrahydrofuran complex, trimethylcyclopentadienyl (cyclopentadienyl) zirconium (Hydride) (tetraphenylborate) tetrahydrofuran complex, bis (pentamethylcyclopentadienyl) zirconium (hydrido) (tetraphenylborate) tetrahydrofuran complex, indenyl (cyclopentadienyl) zirconium (hydride) (tetraphenylborate) tetrahydrofuran complex , Trimethylsilyl cyclopentadienyl (cyclopentadienyl) zirconium (methyl) (tetraphenylborate Tetrahydrofuran complex, trimethylsilylcyclopentadienyl (cyclopentadienyl) zirconium (hydride) (tetraphenylborate) tetrahydrofuran complex, trifluoromethylcyclopentadienyl (cyclopentadienyl) zirconium (hydrido) (tetraphenylborate) tetrahydrofuran complex , Bis (cyclopentadienyl) (trimethylsilyl) zirconium (tetraphenylborate) tetrahydrofuran complex, bis (cyclopentadienyl) (triphenylsilyl) zirconium (tetraphenylborate) tetrahydrofuran complex, bis (cyclopentadienyl) [tris (Trimethylsilyl) silyl] zirconium (tetraphenylborate) tetrahydrofuran complex, bis (cyclopentadiene) Ru) (trimethylsilylmethyl) zirconium (tetraphenylborate) tetrahydrofuran complex, bis (cyclopentadienyl) (benzyl) zirconium (tetraphenylborate) tetrahydrofuran complex, bis (cyclopentadienyl) zirconium (methanesulfonato) (tetraphenyl Borate) tetrahydrofuran complex, bis (cyclopentadienyl) zirconium (p-toluenesulfonato) (tetraphenylborate) tetrahydrofuran complex, bis (cyclopentadienyl) zirconium (trifluoromethanesulfonato) (tetraphenylborate) tetrahydrofuran complex, Bis (cyclopentadienyl) zirconium (benzenesulfonato) (tetraphenylborate) tetrahydrofuran complex, bis (cyclo Pentadienyl) zirconium (pentafluorobenzenesulfonato) (tetraphenylborate) tetrahydrofuran complex, bis (tetramethylcyclopentadienyl) zirconium (trifluoromethanesulfonato) (tetraphenylborate) tetrahydrofuran complex, bis (indenyl) zirconium (trifluoromethane) Sulfonato) (tetraphenylborate) tetrahydrofuran complex and the like.

Further, as the other Group 4, 5, and 6 metal compounds such as titanium compounds and hafnium compounds, the same compounds as mentioned above can be mentioned. Further, a mixture of these compounds may be used. In the present invention, clay, clay mineral or ion-exchangeable layered compound is used as the component (B). Clay is usually composed mainly of clay minerals. The ion-exchangeable layered compound is a compound having a crystal structure in which planes formed by ionic bonds and the like are stacked in parallel with each other with weak bonding forces, and the ions contained therein are exchangeable. Most clay minerals are ion-exchangeable layered compounds. Moreover, examples of these clays, clay minerals, and ion-exchange layered compounds are not limited to naturally occurring ones, and artificially synthesized products can also be preferably used. As the component [B], clay, clay minerals, hexagonal close packing type, antimony type,
Examples thereof include ionic crystalline compounds having a layered crystal structure such as CdCl ₂ type and CdI ₂ type.

Specific examples of the component [B] include clays and clay minerals such as kaolin, bentonite, kibushi clay, gyrome clay, allophane, hissingelite, pyrophyllite, ummo group, montmorillonite group, vermiculite and ryokdeite. Group, palygorskite, kaolinite, nacrite, dickite, halloysite and the like. Specific examples of the ion-exchange layered compound include α-Zr (HAsO ₄ ) ₂ · H ₂ O and α-Zr (H
_{PO 4) 2, α-Zr} (KPO 4) 2 · 3H 2 O, α-
Ti (HPO ₄ ) ₂ , α-Ti (HAsO ₄ ) ₂ · H ₂
O, α-Sn (HPO ₄ ) ₂ · H ₂ O, γ-Zr (HP
O ₄ ) ₂ , γ-Ti (HPO ₄ ) ₂ , γ-Ti (NH ₄
Examples thereof include crystalline acidic salts of polyvalent metals such as PO ₄ ) ₂ · H ₂ O.

As the component [B], those having a pore volume of 20 cc or more in radius measured by mercury porosimetry of 0.1 cc / g or more, particularly 0.3 to 5 cc / g are preferable. here,
The pore volume is measured by the mercury porosimetry using a mercury porosimeter in the pore radius range of 20 to 30000Å. In this embodiment, “Aut” manufactured by Shimadzu Corporation is used.
o Pore 9200 ". In addition,
As the component [B], the pore volume with a radius of 20 Å or more is 0.1
When a compound having a cc / g or less is used, it tends to be difficult to obtain high polymerizability.

Further, it is also preferable to chemically treat the clay and clay mineral as the component [B]. Here, as the chemical treatment, both surface treatment for removing impurities adhering to the surface and treatment for affecting the crystal structure of clay can be used. Specific examples thereof include acid treatment, alkali treatment, salt treatment, and organic substance treatment. The acid treatment removes impurities on the surface and increases the surface area by eluting cations such as Al, Fe and Mg in the crystal structure. Alkali treatment destroys the crystal structure of clay, resulting in a change in clay structure. Further, in the salt treatment and the organic substance treatment, an ionic complex, a molecular complex, an organic derivative and the like can be formed to change the surface area and the interlayer distance.

Utilizing the ion-exchange property, the exchangeable ion between the layers is exchanged.
Layer by replacing the ion with another large, bulky ion.
It is also possible to obtain a layered material in a state where the space is enlarged. sand
That is, bulky ions play the role of pillars that support the layered structure.
It is carried and is called a pillar. Also, between layered materials
Introducing another substance into the material is called intercalation.
U As the guest compound to be intercalated,
TiCl_Four, ZrCl _FourInorganic compounds such as T, T
i (OR)_Four, Zr (OR)_Four, PO (OR) ₃, B
(OR)₃Metal alcohol such as [R is a hydrocarbon group]
G, [Al₁₃O_Four(OH)_{twenty four}]⁷⁺, [Zr_Four(O
H)₁₄]²⁺, [Fe₃O (OCOCH₃)₆]⁺Etc gold
Examples thereof include a hydroxide ion of the genus. These compounds are
Can be used alone or in combination of two or more.
Yes. It also intercalates these compounds
When Si (OR)_Four, Al (OR)₃, Ge (OR)
_FourA polymer obtained by hydrolyzing a metal alcoholate or the like,
SiO₂Coexistence of colloidal inorganic compounds such as
You can also Further, as an example of the pillar, the above-mentioned hydroxide ion is used.
Is intercalated between layers and then heated and dehydrated
Oxides and the like generated by the above are included.

The component [B] may be used as it is, or may be used after treatment such as ball milling and sieving. Further, it may be used after newly adsorbing and adsorbing water, or after heat dehydration treatment. Furthermore, they may be used alone or in combination of two or more of the above solids. As the component [B], preferred is clay or clay mineral, and most preferred is montmorillonite.

Examples of the organoaluminum compound used as the component [C] in the present invention include trialkylaluminum such as trimethylaluminum, triethylaluminum, tripropylaluminum, triisobutylaluminum, diethylaluminum monochloride, diethylaluminum methoxide. And the like, halogen- or alkoxy-containing alkylaluminum, aluminoxane such as methylaluminoxane, and the like, among which trialkylaluminum is particularly preferable.

Regarding the contact method for obtaining the polymerization catalyst from the components [A], [B] and [C], when the component [B] is clay or clay mineral, the transition in the component [A] The molar ratio of metal to hydroxyl group in clay or clay mineral and aluminum in the [C] component organoaluminum compound is 1: 0.1 to 100000: 0.1 to 1000.
0000, especially from 1: 0.5 to 10000:
The catalytic reaction is preferably carried out at 0.5 to 1,000,000.

When the component [B] is other than clay or clay mineral, the weight ratio of the transition metal in the component [A] to aluminum in the component [C] is 1 g of the component [B]. 0.00001-1 (g): 0.001-100
It is preferable to bring them into contact so as to give (g). Contact with pentane, hexane, heptane, in an inert gas such as nitrogen,
It may be carried out in an inert hydrocarbon solvent such as toluene or xylene. The contact temperature is between -20 ° C and the boiling point of the solvent, preferably room temperature to the boiling point of the solvent.

Further, in the present invention, as the organoaluminum compound [D] used as necessary, [C]
The same compounds as the components can be mentioned. The amount of the organoaluminum compound used at this time is such that the molar ratio of the transition metal in the catalyst component [A] to the aluminum in the component [D] is 1: 0.
Selected to be ~ 10,000. The order of contacting the catalyst components is not particularly limited, but they can be contacted in the following contacting order.

After the components [A] and [B] are contacted with each other, the component [C] is added. The component [A] and the component [C] are brought into contact with each other, and then the component [B] is added. After the component [B] and the component [C] are contacted with each other, the component [A] is added. In addition, the three components may be simultaneously added by contact. During or after the contact of each component of the catalyst, a polymer such as polyethylene or polypropylene, or a solid of an inorganic oxide such as silica or alumina may coexist or contact.

The olefin may be prepolymerized in the presence of the above-mentioned components [A], [B] and [C] and optionally [D]. The prepolymerization temperature is −50 to 100 ° C., and the prepolymerization time is 0.1 to 100 hours, preferably 0.1.
It is about 1 to 50 hours. Examples of the organoaluminum compound used as necessary during this prepolymerization include the same compounds as the component [C]. The amount of the organoaluminum compound used at this time is such that the molar ratio of the transition metal in the catalyst component [A] to the aluminum in the component [D] is 1: 0.
Selected to be 10,000.

The olefin used in the prepolymerization is preferably the olefin used in the polymerization, but other olefins may be used. Also, olefins can be mixed and used. The amount of polymer produced by prepolymerization is
The component (B) is in the range of 0.001 to 1000 g, preferably 0.1 to 300 g per 1 g.

The solvent used in the prepolymerization is butane, pentane, hexane, heptane, octane, cyclohexane, toluene, xylene, etc., or a mixture thereof. The catalyst thus obtained may be used without washing or may be used after washing.

When the olefin polymerization is carried out using the olefin polymerization catalyst in which the olefin is prepolymerized as described above, the organoaluminum compound optionally used includes the same compounds as the component [C]. . The amount of the organoaluminum compound used at this time is selected so that the molar ratio of the transition metal in the catalyst component [A] to the aluminum in the organoaluminum compound is 1: 0 to 10,000.

The polymerization reaction is carried out in the presence or absence of a solvent such as an inert hydrocarbon such as butane, pentane, hexane, heptane, toluene, cyclohexane or a liquefied α-olefin. The temperature is −50 ° C. to 250 ° C., preferably 30 ° C. to 250 ° C., and the pressure is not particularly limited, but preferably atmospheric pressure to about 2000 kg · f.
The range is / cm ² .

Further, hydrogen may be present as a molecular weight modifier in the polymerization system. Further, the polymerization temperature and the concentration of the molecular weight modifier may be changed to carry out the polymerization in multiple stages. As described above, according to the method for producing an ethylene-based copolymer of the present invention, it is not necessary to use a transition metal compound having a compound having an expensive crosslinked structure as a ligand as a transition metal component, Also in the organometallic component, since it is not necessary to use expensive aluminoxane, the ethylene copolymer can be produced by an economically inexpensive method.

[0048]

EXAMPLES Next, the present invention will be described in more detail by way of examples, but the present invention is not limited by these examples without departing from the gist thereof. Further, FIG. 1 is a flow chart for facilitating the understanding of the technical contents included in the present invention, and the present invention is not restricted by the flow chart unless it deviates from the gist thereof.

(Example-1) (1) Preparation of catalyst component A commercially available montmorillonite (Montmorillonite manufactured by Aldrich) was placed in a 300 ml round bottom flask.
(K10; the same applies below) 4.0 g was sampled, the inside of the flask was thoroughly replaced with nitrogen, and 40 ml of toluene was added to form a slurry. Separately, in a 300 ml round bottom flask, 36.25 mmol of triethylaluminum was added to 36.3 m of toluene.
It was dissolved in 1. Next, the whole amount of the montmorillonite slurry prepared before stirring was added at 40 ° C. for 10 minutes. Furthermore, it stirred at 40 degreeC for 1 hour. Then 20 μmol / ml
16 ml of a toluene solution of biscyclopentadienyl zirconium chloride of was added and stirred at 25 ° C. for 1 hour to obtain a catalyst component slurry.

(2) Polymerization A predetermined amount of normal hexane was introduced into an autoclave having an internal volume of 2 l, which was sufficiently dried and purged with nitrogen, and then 2.5 μmol of the catalyst component prepared in (1) in terms of Zr atom was charged. Next, a predetermined amount of butene-1 was introduced and then the temperature was raised to 70 ° C. After the temperature was raised to 70 ° C., a slight amount of a mixed gas of hydrogen and ethylene was introduced, and the total pressure was 25.5 kg / cm ² . After that, replenish the mixed gas to keep the total pressure at 25.5 kg / cm ² ,
Copolymerization was carried out at 0 ° C. for 2 hours.

The polymerization was stopped by pressing in 20 ml of ethanol and then the copolymer slurry was dried. The obtained results are shown in Table 1. Figure 2 shows the relationship between MT and MI.
The condition d) was satisfied. Furthermore, T _max is T
The relationship of _max <800d-658 was satisfied.

(Examples 2 and 3) The polymerization was carried out in the same manner as in Example 1 except that the amount of hydrogen added was changed. The polymerization conditions and results are shown in Table 1. In addition,
The condition d) is satisfied as shown in the relationship between MT and MI. Furthermore, T _max satisfied the relationship of T _max <800d-658.

(Examples 4 to 5) The polymerization was carried out in the same manner as in Example 1 except that the concentration of butene-1 was changed. The polymerization conditions and results are shown in Table 1. In addition,
The condition d) is satisfied as shown in the relationship between MT and MI. Furthermore, T _max satisfied the relationship of T _max <800d-658.

Comparative Example 1 (1) Preparation of Catalyst 0.2 μmol of bis (cyclopentadienyl) zirconium dichloride was dissolved in 15 ml of toluene at room temperature, and methylaluminoxane (molecular weight 1
232; Tosoh Akzo) 2 mmol in terms of Al atom
It was pre-contacted with the toluene solution of 30 minutes.

(2) Ethylene-butene-1 copolymerization In a 2 liter induction-stirring autoclave sufficiently replaced with purified nitrogen, 740 m of normal hexane at room temperature under a nitrogen stream.
1, the total amount of the catalyst prepared in (1) was added. Next 70 ℃
Then, the total pressure was 25 kg / cm ² , the gas phase butene-1 / ethylene was 8.3 mol% and the H ₂ / ethylene was 0.028 mol% so that ethylene and butene-
1, hydrogen was introduced and polymerization was carried out for 2 hours. Thereafter, the supply of ethylene, butene-1, and hydrogen was stopped, ethanol was introduced to stop the polymerization, and the gas inside the autoclave was purged to obtain 110 g of a powdery copolymer. This copolymer had MI of 0.15 g / 10 min, FR of 13, and density of 0.1.
It was 913 g / cm ³ . Further, MT was 6.9 g and did not satisfy the condition d) as shown in FIG. 2, and T _max was 7
T _max > 800d-658 at 8 ° C.

Comparative Example 2 (1) Preparation of Catalyst Silica (Fuji Davison MSID 951; 700 ° C. under nitrogen stream, 6 ° C.)
(Hour firing) 1.3 g, and add 20 ml of toluene, and stir. There triisobutylaluminum 4.5mmo
1 of toluene solution was added, and the mixture was stirred at room temperature for 30 minutes. Next, methylaluminoxane (molecular weight 1232; manufactured by Tosoh Akzo) was added with a 7.8 mmol toluene solution in terms of Al atoms, and the mixture was stirred at room temperature for 30 minutes, and then bis (cyclopentadienyl) zirconium dichloride 0.21 mmo
1 of toluene solution was added and stirred for 30 minutes at room temperature.
Further, 50 ml of normal hexane was added, ethylene gas at a normal pressure was continuously supplied, and prepolymerization was carried out at 30 ° C. for 4 hours. After the completion of the prepolymerization, the supernatant was removed, and heat washing (60 ° C.) with 200 ml of normal hexane was performed 3 times, and further 200 ml of normal hexane was washed (room temperature) 3 times. As a result, 17 g polyethylene per 1 g silica
A prepolymerization catalyst containing was obtained.

(2) Ethylene-butene-1 copolymerization In Comparative Example 1 (2), 0.05 g of the prepolymerization catalyst prepared in the above (1) in terms of silica and 0.7 mmol of triisobutylaluminum were used as catalyst components. as used, butene-1 / ethylene 19.8mol%, H ₂ / ethylene was replaced with 0.042 mol% of in the same manner as in Comparative example 1 (2) ethylene - result of performing butene-1 copolymer 227 g of copolymer was obtained. MI of this thing
Is 0.87 g / 10 minutes, FR is 13, density is 0.911
It was g / cm ³ . Further, MT was 3.3 g and did not satisfy the condition of d) as shown in FIG. 2, and T _max was 72 ° C.
In was a T _{ma x>} 800d-658.

[0058]

[Table 1]

[0059]

Industrial Applicability According to the method of the present invention, an ethylene-based copolymer having an excellent melt tension and a narrow composition distribution can be produced economically, and is industrially very useful.

[Procedure amendment]

[Submission date] June 27, 1994

[Procedure Amendment 1]

[Document name to be amended] Statement

[Name of item to be corrected] Brief description of the drawing

[Correction method] Added

[Correction content]

[Brief description of drawings]

FIG. 1 is a flow chart of a catalyst used in the method of the present invention.

FIG. 2 is a diagram showing the relationship between MI and MT of ethylene-based copolymers in Examples and Comparative Examples of the present application.

[Explanation of Reference Signs] The data positions of the embodiment shown in FIG. 2 are represented, and the numeral therein indicates the embodiment number. (Triangle | delta) represents the data position of the comparative example in FIG. 2, and the number in the inside represents the comparative example number.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Eiji Isobe 1000, Kamoshida-cho, Midori-ku, Yokohama-shi, Kanagawa Sanryo Kasei Co., Ltd.

Claims (1)

[Claims] 1. [A] The following general formula [1] or [2]
In one or more metallocene compounds embedded image represented ^{_{(C 5 R 1 5) p}} (C 5 R 1 5) q MR 2 r [1] or [Formula 2] [(C ₅ R ¹ _{5) p ^{(C 5 R 1 5) q}} MR 2 r R 3 s ] ^x + uR ^{4 y-} [2] (where, [1], in [2] wherein each (C ₅ R ¹ ₅₎ is be the same or different A cyclopentadienyl group or a cyclopentadienyl group having a substituent, each R ¹
Are hydrogen, halogen, a silicon-containing group which may be the same or different, a hydrocarbon group having 1 to 20 carbon atoms which may have a halogen substituent, an alkoxy group or an aryloxy group, and two R ¹ Are present on two adjacent carbon atoms of the cyclopentadienyl ring, they may combine with each other to form a C ₄ -C ₆ ring, and R ² may be the same or different hydrogen, halogen. , A silicon-containing group, a hydrocarbon group having 1 to 20 carbon atoms which may have a halogen substituent, an alkoxy group, an aryloxy group, SO _l R
⁵ groups, NR ⁶ _m groups or PO _n R ⁷ ₃ groups, wherein R ⁵ , R ⁶ and R ⁷ have a carbon number which may have hydrogen, halogen, a silicon-containing group or a halogen substituent. Or 2
A hydrocarbon group of 0, 1 is 0, 1, 2, or 3, m is 0, 1, 2, or 3, n is 0, 1, 2, or 3, and p, q, r, s, t, u, x, y
Is an integer that satisfies the following formula. ## EQU1 ## p ≧ 1, q ≧ 0, r ≧ 0, s ≧ 0, u ≧ 1 p + q + r = t in the case of the formula [1], and p in the case of the formula [2].
+ Q + r = t−x, x = u × y, and t is the valence of the metal M. M is a metal of Groups 4, 5 and 6 of the long periodic table, R ³ is a neutral ligand coordinating to M, and R ^{4 y-} can stabilize the above metal cation. A counter anion) [B] Clay, clay mineral or a product obtained by contacting an ion-exchange layered compound and [C] organoaluminum compound, and, if necessary, a catalyst comprising [D] organoaluminum compound In existence,
Copolymerization of ethylene and α-olefin having 4 or more and 20 or less carbon atoms, a) Melt index (MI) at 190 ° C. under 2.16 kg load is 0.001 g / 10 min to 100 g.
/ 10 min range, b) density in the range of 0.86 to 0.97 g / cm ³ , c) 10.2 kg and 1.02 kg at 190 ° C.
Outflow ratio (FR) under load condition is 13 to 50
D) the relationship between melt tension (MT) at 190 ° C. and MI satisfies the relationship of logMT> −0.46logMI + 0.5, and e) the relationship of Mw / Mn measured by GPC in the range of 2 to 5 A method for producing an ethylene-based copolymer, characterized in that an ethylene-based copolymer satisfying the requirements is obtained.