JP2006307176A - ETHYLENE-alpha-OLEFIN COPOLYMER - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an ethylene based polymer excellent in the balance of mechanical strength and moldability. <P>SOLUTION: The ethylene-α-olefin copolymer comprises a monomer unit based on ethylene and a monomer unit based on a 3-20C α-olefin, and has a melt flow rate (MFR) of 0.01-100 g/10 min, a density of 860-970 kg/m<SP>3</SP>, molecular wt, distribution (Mw/Mn) of 2-8, and a ratio between a dynamic complex viscosity (η<SP>*</SP><SB>0.1</SB>) at a temperature of 190°C and at an angular frequency of 0.1 rad/second and a dynamic complex viscosity (η<SP>*</SP><SB>100</SB>) at a temperature of 190°C and at the angular frequency of 100 rad/second (η<SP>*</SP><SB>0.1</SB>/η<SP>*</SP><SB>100</SB>) of 15-100. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to an ethylene-α-olefin copolymer. More specifically, the present invention relates to an ethylene-α-olefin copolymer having an excellent balance between mechanical strength and workability.

  Ethylene polymers are molded into films, sheets, bottles and the like by various molding methods such as inflation molding, T-die casting, blow molding, and injection molding, and are used for various applications. Such an ethylene-based polymer is required to have excellent moldability, such as a small motor load during melt extrusion by an extruder, stable bubbles during inflation molding, and no parison dripping during blow molding. Yes. For example, a polymer obtained by polymerizing ethylene with a polymerization catalyst composed of silica supporting methylalumoxane, a specific metallocene complex and triisobutylaluminum, and silica and triisobutylaluminum supporting a specific metallocene complex and methylalumoxane. A polymer obtained by polymerizing ethylene with a polymerization catalyst consisting of is proposed (for example, see Patent Documents 1 and 2). Further, after contacting pentafluorophenol with diethylzinc, contact with hexamethyldisilazane-treated silica, and then with water, a co-catalyst support, triisobutylaluminum, racemic-ethylenebis (1-indenyl) ) A polymer formed by copolymerizing ethylene and α-olefin using a catalyst formed from zirconium diphenoxide (see, for example, Patent Document 3), and diethylzinc on hexamethyldisilazane-treated silica. Using a catalyst formed from a co-catalyst support that is contacted with pentafluorophenol and then contacted with water, and triisobutylaluminum and racemic-ethylenebis (1-indenyl) zirconium diphenoxide. A polymer obtained by copolymerizing ethylene and an α-olefin (for example, Patent Documents 4 and 5) have been proposed.

Japanese Patent Application Laid-Open No. 8-59741 Japanese Patent Laid-Open No. 9-235312 Japanese Patent Laid-Open No. 2003-171212 JP 2004-149760 A JP 200597481 A

However, the ethylene-based polymer described above may not be sufficiently satisfactory in mechanical strength or workability.
Under such circumstances, the problem to be solved by the present invention is to provide an ethylene polymer having an excellent balance between mechanical strength and workability.

  According to the present invention, an ethylene polymer having an excellent balance between mechanical strength and processability can be provided.

That is, the present invention has a monomer unit based on ethylene and a monomer unit based on an α-olefin having 3 to 20 carbon atoms, and has a melt flow rate (MFR) of 0.01 to 100 g / 10 min. The density is 860 to 970 kg / m ³ , the molecular weight distribution (Mw / Mn) is 2 to 8, the dynamic complex viscosity (η ^* _0.1 ) and the temperature 190 at a temperature of 190 ° C. and an angular frequency of 0.1 rad / sec. It relates to an ethylene-α-olefin copolymer having a ratio (η ^* _0.1 / η ^* ₁₀₀ ) to dynamic complex viscosity (η ^* ₁₀₀ ) at 15 ° C. and an angular frequency of 100 rad / sec.

  The ethylene-α-olefin copolymer of the present invention is a copolymer having a monomer unit based on ethylene and a monomer unit based on an α-olefin having 3 to 20 carbon atoms. Examples of the α-olefin having 3 to 20 carbon atoms include propylene, 1-butene, 4-methyl-1-pentene, 1-hexene, 1-octene, 1-decene and the like. More preferred are 1-butene and 1-hexene. Moreover, said C3-C20 alpha olefin may be used independently and may use 2 or more types together.

  The content of the monomer unit based on ethylene in the ethylene-α-olefin copolymer of the present invention is usually 50% by weight or more with respect to the total weight (100% by weight) of the ethylene-α-olefin copolymer. It is. The content of the monomer unit based on the α-olefin having 3 to 20 carbon atoms is usually 50% by weight or less with respect to the total weight (100% by weight) of the ethylene-α-olefin copolymer.

  In addition to the monomer unit based on ethylene and the monomer unit based on an α-olefin having 3 to 20 carbon atoms, the ethylene-α-olefin copolymer of the present invention is within a range not impairing the effects of the present invention. May have a monomer unit based on a monomer other than ethylene and an α-olefin having 3 to 20 carbon atoms. Examples of the monomer include 1,3-butadiene, 2-methyl-1 Conjugated dienes such as 1,3-butadiene; non-conjugated dienes such as 1,4-pentadiene and 1,5-hexadiene; unsaturated carboxylic acids such as acrylic acid and methacrylic acid; methyl acrylate, ethyl acrylate, butyl acrylate, Examples thereof include unsaturated carboxylic acid esters such as methyl methacrylate and ethyl methacrylate; vinyl ester compounds such as vinyl acetate.

  Examples of the ethylene-α-olefin copolymer of the present invention include an ethylene-propylene copolymer, an ethylene-1-butene copolymer, an ethylene-1-hexene copolymer, and an ethylene-4-methyl-1-pentene copolymer. Polymer, ethylene-1-octene copolymer, ethylene-1-butene-1-hexene copolymer, ethylene-1-butene-4-methyl-1-pentene copolymer, ethylene-1-butene-1-octene Examples thereof include copolymers. Preferably, ethylene-1-butene copolymer, ethylene-1-hexene copolymer, ethylene-1-octene copolymer, ethylene-1-butene-1-hexene copolymer, ethylene-1-butene-1 -An octene copolymer, more preferably an ethylene-1-hexene copolymer.

  The melt flow rate (MFR) of the ethylene-α-olefin copolymer of the present invention is 0.01 to 100 g / 10 min. If the MFR is too large, the mechanical strength may decrease, and is preferably 20 g / 10 min or less, more preferably 5 g / 10 min or less, and even more preferably 1 g / 10 or less. Moreover, when MFR is too small, workability may fall, Preferably it is 0.05 g / 10min or more, More preferably, it is 0.1 g / 10min or more. The MFR is measured by the A method according to JIS K7210-1995 under conditions of a temperature of 190 ° C. and a load of 21.18N.

The density of the ethylene-α-olefin copolymer of the present invention is 860 to 970 kg / m ³ . The density is preferably 960 kg / m ³ or less from the viewpoint of increasing mechanical strength. Moreover, it said seal degree, in view of enhancing the rigidity, is preferably 920 kg / m ³ or more, more preferably 930 kg / m ³ or more. In addition, this density is measured according to the A method prescribed | regulated to JISK7112-1980 using the sample which annealed as described in JISK6760-1995.

  The molecular weight distribution (Mw / Mn) of the ethylene-α-olefin copolymer of the present invention is 2-8. If the molecular weight distribution is too large, the mechanical strength may decrease, preferably 7 or less, more preferably 6 or less. Moreover, when molecular weight distribution is too small, workability may fall, Preferably it is 3 or more, More preferably, it is 4 or more. The molecular weight distribution (Mw / Mn) was determined by gel permeation chromatography and calculating polystyrene-reduced weight average molecular weight (Mw) and number average molecular weight (Mn), and Mw divided by Mn (Mw / Mn).

The ethylene-α-olefin copolymer of the present invention is a polymer having a relatively narrow molecular weight distribution as described above, and a polymer having a small amount of molecules having many long chain branches in the high molecular weight component of the polymer. It is. Such an ethylene-α-olefin copolymer is a copolymer having a high molecular weight component having a lot of long-chain branches, so that it can operate at a temperature of 190 ° C. and an angular frequency of 0.1 rad / sec. Since the copolymer has such a large complex viscosity (η ^* _0.1 , unit: Pa · sec) and a small amount of the molecules having many long chain branches, the temperature is 190 ° C. and the angular frequency is 100 rad / sec. Since the dynamic complex viscosity (η ^* ₁₀₀ , unit: Pa · second) does not increase so much, the temperature is 190 ° C. compared to a conventionally known ethylene-α-olefin copolymer having a relatively narrow molecular weight distribution. Ratio (η ^* _0.1 / η) of dynamic complex viscosity (η ^* _0.1 ) at an angular frequency of _0.1 rad / sec to dynamic complex viscosity (η ^* ₁₀₀ ) at a temperature of 190 ° C. and an angular frequency of 100 rad / sec ^* ₁₀₀ ) becomes larger. A conventionally known ethylene-α-olefin copolymer having a relatively narrow molecular weight distribution has an η ^* _0.1 / η ^* ₁₀₀ of less than 15, and such a copolymer may be inferior in processability.

Η ^* _0.1 / η ^* ₁₀₀ of the ethylene-α-olefin copolymer of the present invention is 15-100. η ^* _0.1 / η ^* ₁₀₀ is preferably 16 or more, more preferably 18 or more, from the viewpoint of improving workability. Moreover, from a viewpoint of raising mechanical strength, Preferably it is 80 or less, More preferably, it is 60 or less. Η ^* _0.1 and η ^* ₁₀₀ are measured using a viscoelasticity measuring apparatus (for example, Rheometrics Mechanical Spectrometer RMS-800 manufactured by Rheometrics).

  Examples of the method for producing the ethylene-α-olefin copolymer of the present invention include solid particles obtained by supporting a promoter component such as an organoaluminum compound, an organoaluminum oxy compound, a boron compound, and an organozinc compound on a particulate carrier. -Like promoter support (hereinafter referred to as component (A)) and two ligands having a cyclopentadienyl skeleton, and the two ligands are cross-linking groups such as alkylene groups and silylene groups. In the presence of a polymerization catalyst comprising a metallocene complex (hereinafter referred to as “component (B)”) having a structure bonded together with an organoaluminum compound (hereinafter referred to as “component (C)”) as a catalyst component, ethylene and Examples thereof include a method of copolymerizing with an α-olefin.

As the solid particulate promoter support of the component (A), component (a): diethyl zinc, component (b): fluorinated phenol having 4 or less fluorine atoms, component (c): water, component ( d): inorganic compound particles and component (e): a carrier obtained by contacting 1,1,1,3,3,3-hexamethyldisilazane (((CH ₃ ) ₃ Si) ₂ NH) Can do.

  Examples of the fluorinated phenol having 4 or less fluorine atoms as component (b) include 3,4,5-trifluorophenol, 2,4,6-trifluorophenol, 3,5-difluorophenol, 3,4,5-trifluorophenol is most preferred. Moreover, it is preferable to use a fluorinated phenol having a small number of fluorines from the viewpoint of reducing the content of molecules having many long chain branches contained in the high molecular weight component or narrowing the molecular weight distribution (Mw / Mn).

  The inorganic compound particles of component (d) are preferably silica gel.

The amount of component (a), component (b) and component (c) used is the molar ratio of the amount of each component used: component (a): component (b): component (c) = 1: y: z Then, it is preferable that y and z satisfy the following formula.
| 2-y-2z | <1
Y in the above formula is preferably 0.3 or more, more preferably 0.4 or more, and further preferably 0.45 or more. Moreover, as y, Preferably it is 0.55 or less. From the viewpoint of increasing η ^* _0.1 / η ^* ₁₀₀ , it is preferable to increase y, and from the viewpoint of decreasing η ^* _0.1 / η ^* ₁₀₀ , it is preferable to decrease y. Further, from the viewpoint of increasing the molecular weight distribution (Mw / Mn), it is preferable to increase y, and from the viewpoint of decreasing the molecular weight distribution (Mw / Mn), it is preferable to decrease y.

  The amount of the component (d) used relative to the component (a) is such that the number of moles of zinc atoms contained in the particles obtained by contacting the component (a) and the component (d) is 0.00 per gram of the particles. The amount is preferably 1 mmol or more, and more preferably 0.5 to 20 mmol. The amount of the component (e) to be used with respect to the component (d) is preferably an amount that makes the component (e) 0.1 mmol or more per 1 g of the component (d), and an amount that becomes 0.5 to 20 mmol. More preferably.

Examples of the order in which the component (a), the component (b), the component (c), the component (d), and the component (e) are brought into contact include the following orders.
<1> Component (d) and component (e) are contacted, then component (a) is contacted, then component (b) is contacted, and then component (c) is contacted.
<2> Component (d) and component (e) are contacted, then component (b) is contacted, then component (a) is contacted, and then component (c) is contacted.
The contact order is preferably <1>.

  The contact treatment of component (a), component (b), component (c), component (d) and component (e) is preferably carried out in an inert gas atmosphere. The treatment temperature is usually −100 to 300 ° C., preferably −80 to 200 ° C. The treatment time is usually 1 minute to 200 hours, preferably 10 minutes to 100 hours.

  The contact treatment of component (a), component (b), component (c), component (d) and component (e) preferably uses a solvent. Usually, as the solvent, those that do not react with each of the components to be contacted when the solvent is used or with the contact product obtained by contact are used. Examples of the solvent include aliphatic hydrocarbon solvents such as butane, pentane, hexane, heptane, octane, 2,2,4-trimethylpentane and cyclohexane; aromatic hydrocarbon solvents such as benzene, toluene and xylene, preferably Toluene.

  The metal atom of the metallocene complex of component (B) is preferably a group IV atom of the periodic table, more preferably zirconium or hafnium. The ligand having a cyclopentadienyl skeleton is preferably an indenyl group, a methyl indenyl group, a methyl cyclopentadienyl group, or a dimethylcyclopentadienyl group, and the crosslinking group is an ethylene group or a dimethylmethylene group. A dimethylsilylene group is preferred. Furthermore, as a remaining substituent which a metal atom has, a diphenoxy group and a dialkoxy group are preferable. Preferred examples of the metallocene complex include ethylene bis (1-indenyl) zirconium diphenoxide.

  The organoaluminum compound of component (C) is preferably triisobutylaluminum or trinormal octylaluminum.

The amount of the metallocene complex used as the component (B) is preferably 5 × 10 ^{−6 to} 5 × 10 ⁻⁴ mol with respect to 1 g of the promoter support of the component (A). The amount of the organoaluminum compound used as the component (C) is preferably a ratio of the number of moles of aluminum atoms in the organoaluminum compound as the component (C) to the number of moles of metal atoms in the metallocene complex as the component (B) (Al / M ) And 1 to 2000.

  The polymerization method is preferably a continuous polymerization method involving the formation of ethylene-α-olefin copolymer particles, such as a continuous gas phase polymerization method, a continuous slurry polymerization method, and a continuous bulk polymerization method, preferably It is a continuous gas phase polymerization method. The gas phase polymerization reaction apparatus used in the polymerization method is usually an apparatus having a fluidized bed type reaction tank, and preferably an apparatus having a fluidized bed type reaction tank having an enlarged portion. A stirring blade may be installed in the reaction vessel.

  As a method of supplying each component of the polymerization catalyst used in the production of the ethylene-α-olefin copolymer of the present invention to the reaction vessel, usually, using an inert gas such as nitrogen or argon, hydrogen, ethylene or the like, A method of supplying in a state free from moisture and a method of supplying each component in a solution or slurry after dissolving or diluting each component in a solvent are used. Each component of the catalyst may be supplied individually, or arbitrary components may be supplied in contact in advance in an arbitrary order.

  Further, before carrying out the main polymerization, prepolymerization may be carried out, and the prepolymerized prepolymerized catalyst component may be used as a catalyst component or catalyst for the main polymerization.

  The polymerization temperature is usually lower than the temperature at which the ethylene-α-olefin copolymer melts, preferably 0 to 150 ° C, more preferably 30 to 100 ° C. From the viewpoint of reducing the content of molecules having many long chain branches contained in the high molecular weight component or narrowing the molecular weight distribution, it is preferably 60 to 100 ° C, more preferably 70 to 100 ° C. .

In order to adjust the melt fluidity of the ethylene-α-olefin copolymer, hydrogen may be added as a molecular weight regulator in the polymerization reactor. Further, an inert gas may be added in the polymerization reactor. As the hydrogen concentration, from the viewpoint of increasing the η ^* _0.1 / η ^* _100, it is preferable to lower the hydrogen concentration, from the viewpoint of reducing the η ^* _0.1 / η ^* _100, it is preferable to increase the hydrogen concentration . Further, from the viewpoint of widening the molecular weight distribution (Mw / Mn), it is preferable to increase the hydrogen concentration, and from the viewpoint of narrowing the molecular weight distribution (Mw / Mn), it is preferable to decrease the hydrogen concentration.

  You may make the ethylene-alpha-olefin copolymer of this invention contain an additive as needed. Examples of the additive include antioxidants, weathering agents, lubricants, antiblocking agents, antistatic agents, antifogging agents, dripping agents, pigments, fillers, and the like.

  The ethylene-α-olefin copolymer of the present invention is a known molding method, for example, an extrusion molding method such as an inflation film molding method or a T-die film molding method, a hollow molding method, an injection molding method, or a compression molding method. These are molded into various molded bodies (films, sheets, bottles, trays, etc.) by a cross-linked foam molding method, etc., and as the molding processing method, a cross-linked foam molding method, an extrusion molding method and a hollow molding method are preferably used.

  The ethylene-α-olefin copolymer of the present invention is excellent in the balance between mechanical strength and processability, and can also be excellent in rigidity. Therefore, it is suitably used for extrusion molded products, particularly food packaging films, food packaging containers, surface protective films, hollow molded products, particularly crosslinked foamed molded product blow bottles and squeeze bottles.

  Hereinafter, the present invention will be described by examples and comparative examples.

  The measured value of each item in the examples and comparative examples was measured according to the following method.

(1) Melt flow rate (MFR, unit: g / 10 minutes)
According to the method defined in JIS K7210-1995, the measurement was performed by the A method under the conditions of a load of 21.18 N and a temperature of 190 ° C.

(2) Density (Unit: Kg / m ³ )
It measured according to the method prescribed | regulated to A method among JISK7112-1980. The sample was annealed according to JIS K6760-1995.

(3) Molecular weight distribution (Mw / Mn)
The polystyrene-reduced weight average molecular weight (Mw) and number average molecular weight (Mn) obtained by gel permeation chromatography (GPC) measurement are calculated, and the value obtained by dividing Mw by Mn is the molecular weight distribution (Mw / Mn). did.
Apparatus: Waters 150C manufactured by Waters
Separation column: TOSOH TSKgelGMH-HT
Measurement temperature: 145 ° C
Carrier: Orthodichlorobenzene Flow rate: 1.0 mL / min Injection volume: 500 μL

(4) η ^* _0.1 / η ^* ₁₀₀
After measuring the dynamic complex viscosity at an angular frequency of 0.1 rad / sec to 100 rad / sec using a viscoelasticity measuring device under the following conditions, the dynamic complex viscosity (η ^* _{0.1 at} an angular frequency of 0.1 rad / sec) is measured. ) Divided by the dynamic complex viscosity (η ^* ₁₀₀ ) at an angular frequency of 100 rad / sec (η ^* _0.1 / η ^* ₁₀₀ ).
Apparatus: Rheometrics manufactured by Rheometrics
Mechanical Spectrometer RMS-800
Temperature: 190 ° C
Geometry: Parallel plate Plate diameter: 25mm
Plate spacing: 1.5-2mm
Strain: 5%
Angular frequency: 0.1 to 100 rad / sec Measurement atmosphere: Nitrogen

(5) Tensile impact strength (unit: kJ / m ² )
The tensile impact strength of a sheet having a thickness of 2 mm that was compression-molded under conditions of a molding temperature of 190 ° C., a preheating time of 10 minutes, a compression time of 5 minutes, and a compression pressure of 5 MPa was measured according to ASTM D1822-68. The larger this value, the better the mechanical strength.

(6) Melt tension (MT, unit: cN)
Using a melt tension tester manufactured by Toyo Seiki Seisakusho, a molten resin filled in a 9.5 mmφ barrel at a temperature of 190 ° C. was used at a piston lowering speed of 5.5 mm / min (shear speed of 7.4 sec ⁻¹ ). Immediately before the molten resin breaks, the extruded molten resin is extruded through an orifice having a diameter of 2.09 mmφ and a length of 8 mm, and the extruded molten resin is wound at a winding speed of 40 rpm / min using a winding roll having a diameter of 50 mmφ. The tension value at was measured. The larger this value is, the higher the melt tension is, indicating that the processability is excellent.

(7) Melt flow rate ratio (MFRR)
According to the method defined in JIS K7210-1995, the melt flow rate value measured by the A method under the conditions of a load of 211.8 N and a temperature of 190 ° C. is a value measured by the A method under the conditions of a load of 21.18 N and a temperature of 190 ° C. The value divided by was designated as MFRR. The larger this value is, the lower the extrusion torque at the time of molding processing is, indicating that the processability is excellent.

Example 1
(1) Treatment of silica In a reactor equipped with a nitrogen-replaced stirrer, 500 ml of toluene as a solvent and silica heat-treated at 300 ° C. under a nitrogen stream (Sypolol 948 manufactured by Devison; average particle size = 55 μm; pore volume) = 1.67 ml / g; specific surface area = 325 m ² / g) was added and stirred. Then, after cooling to 5 ° C., a mixed solution of 28.5 ml of 1,1,1,3,3,3-hexamethyldisilazane and 38.3 ml of toluene was maintained while keeping the temperature in the reactor at 5 ° C. It was dripped in 30 minutes. After completion of the dropping, the mixture was stirred at 5 ° C. for 1 hour and then at 95 ° C. for 3 hours and filtered. The obtained solid component was washed 6 times with 500 ml of toluene and twice with 500 ml of hexane. Thereafter, the solid component was dried at 23 ° C. under reduced pressure for 1 hour to obtain 52.2 g of surface-treated silica gel.

(2) Preparation of cocatalyst carrier After drying under reduced pressure, in a 100 ml four-necked flask purged with nitrogen, 5.38 g of the surface-treated silica gel obtained in Example 1 (1) above, 37.5 ml of toluene, Was introduced. Next, 13.5 ml of a diethylzinc hexane solution having a diethylzinc concentration of 2 mmol / ml was added and stirred. After cooling to 5 ° C., 5.56 ml of a 3,4,5-trifluorophenol toluene solution having a 3,4,5-trifluorophenol concentration of 2.42 mmol / ml was added to the reactor. While maintaining the temperature at 5 ° C., the solution was added dropwise over 60 minutes. After completion of dropping, the mixture was stirred at 5 ° C. for 1 hour and at 40 ° C. for 1 hour. Thereafter, 0.36 ml of water was added dropwise over 1.5 hours while maintaining the temperature in the reactor at 5 ° C. After completion of dropping, the mixture was stirred at 5 ° C for 1.5 hours, at 40 ° C for 2 hours, and further at 80 ° C for 2 hours. After the stirring was stopped, the mixture was allowed to stand, 30 ml of the supernatant was extracted, 30 ml of toluene was added, the temperature was raised to 95 ° C., the mixture was stirred for 4 hours, and after stirring, the supernatant was extracted to obtain a solid component. The obtained solid component was washed 4 times with 30 ml of toluene and 3 times with 30 ml of hexane. Then, the solid component (henceforth a promoter support (A)) was obtained by drying.

(3) Polymerization After drying under reduced pressure, the inside of a 5 liter autoclave with a stirrer substituted with argon was evacuated, hydrogen was added so that the partial pressure was 0.003 MPa, 10 mL of 1-hexene and 1195 g of butane were charged, After raising the temperature to 70 ° C., ethylene was introduced so that the partial pressure was 1.6 MPa to stabilize the system. As a result of gas chromatography, the gas composition in the system was hydrogen = 0.09 mol%. To this, 1.5 mL of a heptane solution of triisobutylaluminum having a triisobutylaluminum concentration of 1 mmol / mL was added. Next, 2.3 mL of a toluene solution of racemic-ethylenebis (1-indenyl) zirconium diphenoxide having a racemic-ethylenebis (1-indenyl) zirconium diphenoxide concentration of 2 μmol / mL was added, and then Example 1 ( 36.5 mg of the promoter support (A) obtained in 2) was added. The polymerization was carried out at 70 ° C. for 60 minutes while continuously supplying an ethylene / hydrogen mixed gas (hydrogen = 0.09 mol%) so that the total pressure and the hydrogen concentration in the gas were kept constant during the polymerization. Thereafter, butane, ethylene and hydrogen were purged to obtain 128 g of an ethylene-1-hexene copolymer. The physical properties of the obtained ethylene-1-hexene copolymer are shown in Table 1.

Example 2
After drying under reduced pressure, the inside of a 5 liter autoclave equipped with a stirrer substituted with argon is evacuated, hydrogen is added so that the partial pressure is 0.0007 MPa, 20 mL of 1-hexene and 1189 g of butane are charged, and the temperature in the system is adjusted. After heating up to 70 degreeC, ethylene was introduce | transduced so that the partial pressure might be set to 1.6 Mpa, and the system inside was stabilized. As a result of gas chromatography, the gas composition in the system was hydrogen = 0.04 mol%. To this, 4.5 mL of a heptane solution of triisobutylaluminum having a triisobutylaluminum concentration of 1 mmol / mL was added. Next, 2.3 mL of a toluene solution of racemic-ethylenebis (1-indenyl) zirconium diphenoxide having a racemic-ethylenebis (1-indenyl) zirconium diphenoxide concentration of 2 μmol / mL was added, and then Example 1 ( 25.4 mg of the promoter support (A) obtained in 2) was added. The polymerization was carried out at 70 ° C. for 60 minutes while continuously supplying an ethylene / hydrogen mixed gas (hydrogen = 0.08 mol%) so that the total pressure and the hydrogen concentration in the gas were kept constant during the polymerization. Thereafter, butane, ethylene, and hydrogen were purged to obtain 152 g of an ethylene-1-hexene copolymer. The physical properties of the obtained ethylene-1-hexene copolymer are shown in Table 1.

Example 3
After drying under reduced pressure, the autoclave with a 5 liter stirrer substituted with argon is evacuated, hydrogen is added so that its partial pressure is 0.0001 MPa, 20 mL of 1-hexene and 1186 g of butane are charged, and the temperature in the system is adjusted. After heating up to 70 degreeC, ethylene was introduce | transduced so that the partial pressure might be set to 1.6 Mpa, and the system inside was stabilized. As a result of gas chromatography, the gas composition in the system was hydrogen = 0.03 mol%. To this, 4.5 mL of a heptane solution of triisobutylaluminum having a triisobutylaluminum concentration of 1 mmol / mL was added. Next, 2.3 mL of a toluene solution of racemic-ethylenebis (1-indenyl) zirconium diphenoxide having a racemic-ethylenebis (1-indenyl) zirconium diphenoxide concentration of 2 μmol / mL was added, and then Example 1 ( 25.8 mg of the promoter support (A) obtained in 2) was added. During the polymerization, the polymerization was carried out at 70 ° C. for 70 minutes while continuously supplying an ethylene / hydrogen mixed gas (hydrogen = 0.05 mol%) so as to keep the total pressure and the hydrogen concentration in the gas constant. Thereafter, butane, ethylene, and hydrogen were purged to obtain 160 g of an ethylene-1-hexene copolymer. The physical properties of the obtained ethylene-1-hexene copolymer are shown in Table 1.

Example 4
After drying under reduced pressure, the inside of an autoclave with a 5 liter stirrer substituted with argon is evacuated, hydrogen is added so that the partial pressure is 0.004 MPa, 10 mL of 1-hexene and 1194 g of butane are charged, and the temperature in the system is adjusted. After heating up to 70 degreeC, ethylene was introduce | transduced so that the partial pressure might be set to 1.6 Mpa, and the system inside was stabilized. As a result of gas chromatography, the gas composition in the system was hydrogen = 0.18 mol%. To this, 1.5 mL of a heptane solution of triisobutylaluminum having a triisobutylaluminum concentration of 1 mmol / mL was added. Next, 2.3 mL of a toluene solution of racemic-ethylenebis (1-indenyl) zirconium diphenoxide having a racemic-ethylenebis (1-indenyl) zirconium diphenoxide concentration of 2 μmol / mL was added, and then Example 1 ( 28.6 mg of the promoter support (A) obtained in 2) was added. The polymerization was carried out at 70 ° C. for 60 minutes while continuously supplying an ethylene / hydrogen mixed gas (hydrogen = 0.09 mol%) so that the total pressure and the hydrogen concentration in the gas were kept constant during the polymerization. Thereafter, butane, ethylene and hydrogen were purged to obtain 106 g of an ethylene-1-hexene copolymer. The physical properties of the obtained ethylene-1-hexene copolymer are shown in Table 1.

Comparative Example 1
(1) Preparation of co-catalyst support Example 53 (Patent WO 02/051878) except that silica previously contacted with 1,1,1,3,3,3-hexamethyldisilazane was used as silica. A solid component (hereinafter referred to as a promoter support (C)) was obtained in the same manner as in component (A) of 1).

(2) Polymerization After drying under reduced pressure, the inside of a 5 liter autoclave with a stirrer substituted with argon was evacuated, hydrogen was added so that the partial pressure was 0.003 MPa, and 1-hexene 50 mL and butane 1166 g were charged. After raising the temperature to 70 ° C., ethylene was introduced so that the partial pressure was 1.6 MPa to stabilize the system. As a result of gas chromatography, the gas composition in the system was hydrogen = 0.88 mol%. 6.0 mL of a heptane solution of triisobutylaluminum having a triisobutylaluminum concentration of 1 mmol / mL was added thereto. Next, 3 mL of a toluene solution of racemic-ethylenebis (1-indenyl) zirconium diphenoxide having a racemic-ethylenebis (1-indenyl) zirconium diphenoxide concentration of 2 μmol / mL was added, and then, Comparative Example 2 (1 ) 36.5 mg of the co-catalyst support (C) prepared in step 1 The polymerization was carried out at 70 ° C. for 100 minutes while continuously supplying an ethylene / hydrogen mixed gas (hydrogen = 0.96 mol%) so that the total pressure and the hydrogen concentration in the gas were kept constant during the polymerization. Thereafter, butane, ethylene and hydrogen were purged to obtain 77 g of an ethylene-1-hexene copolymer. The physical properties of the obtained ethylene-1-hexene copolymer are shown in Table 1.

Comparative Example 2
Table 1 shows the physical properties of a commercially available ethylene copolymer (Affinity HF1030 manufactured by Dow Chemical Company).

Claims (1)

It has a monomer unit based on ethylene and a monomer unit based on an α-olefin having 3 to 20 carbon atoms, has a melt flow rate (MFR) of 0.01 to 100 g / 10 min, and a density of 860 to 600 970 kg / m ³ , molecular weight distribution (Mw / Mn) of 2 to 8, dynamic complex viscosity (η ^* _0.1 ) at a temperature of 190 ° C. and an angular frequency of _0.1 rad / sec, a temperature of 190 ° C. and an angular frequency of 100 rad Ethylene / α-olefin copolymer having a ratio (η ^* _0.1 / η ^* ₁₀₀ ) to dynamic complex viscosity (η ^* ₁₀₀ ) at 15 / sec of 15 to ₁₀₀ .