JP3037589B2 - Molded article or sheet of ethylene copolymer - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an ethylene-based copolymer and a molded article thereof, and more particularly, to an ethylene-based copolymer which gives a molded article having excellent molding properties and high mechanical strength, and an ethylene-based copolymer. The present invention relates to a blow molded article or sheet having a high mechanical strength obtained by molding an article.

[0002]

2. Description of the Related Art Hitherto, ethylene copolymers such as ethylene-α-olefin copolymers have been widely used in many fields as general-purpose resins. This ethylene-based copolymer has conventionally been produced with a heterogeneous catalyst, but the ethylene-based copolymer obtained using this heterogeneous catalyst has a wide molecular weight distribution and a broad branching degree distribution. , High branching degree and low molecular weight components. As a result, it is known that a film obtained from this ethylene-based copolymer is inferior in heat sealability and environmental stress crack resistance (ESCR property). However, since the film has little anisotropy (unbalance in the vertical and horizontal strengths), the film has an advantage of being excellent in tear strength, which is an important physical property of the film. On the other hand, in recent years, homogeneous metallocene catalysts having high catalytic activity and excellent copolymerizability have been developed. Ethylene copolymer obtained using this metallocene catalyst,
Since the molecular weight distribution is narrow, the distribution of branching degree is narrow, and the number of low molecular weight compounds having highly branched components is small, the heat sealability, impact resistance, E
It is known that the SCR property and the like are improved.

[0003] In general, a measure of the molecular weight distribution (Polydispersity) derived from the rheological properties of a polymer.
It is known that the swell ratio used as one measure of the elasticity term is related to the primary structure (eg, molecular weight, molecular weight distribution). In recent years, ethylene-based copolymers obtained using commercially available single-site catalysts (metallocene catalysts) have a problem that rheological properties are reduced due to narrow molecular weight distribution, resulting in poor moldability. Further, the ethylene copolymer disclosed in US Pat. No. 5,272,236 has a small amount of long-chain branching despite its narrow molecular weight distribution, so that a slight improvement in rheological properties can be expected. However, this ethylene-based copolymer requires various types of molding in order to be used in a wide range of applications, but the rheological properties are still insufficient for such various types of molding.

[0004]

DISCLOSURE OF THE INVENTION The present invention provides an ethylene copolymer which provides a molded article having excellent molding properties and high mechanical strength under such circumstances, and this ethylene copolymer. It is an object of the present invention to provide a blow-molded article or sheet having high mechanical strength obtained by molding a sheet.

[0005]

Means for Solving the Problems The inventors of the present invention have conducted intensive studies to achieve the above object, and have found that (a) ethylene and (b) α-olefin and diene compounds having 3 to 20 carbon atoms. It has been found that the object can be achieved by an ethylene copolymer obtained by copolymerization with at least one selected from cyclic olefins and having specific properties. The present invention has been completed based on such findings. That is, the present invention relates to (a) ethylene,
(B) α-olefin having 3 to 20 carbon atoms and cyclic olefin
At least one selected from monoolefins
And the monoolefin content is 1
In the ethylene copolymer in the range of 20 mol%, (1) the resin density is in the range of 0.85~0.95g / cm ^3, the polyethylene measured by (2) Gel permeation chromatography Ratio Mw / M between converted weight average molecular weight (Mw) and number average molecular weight (Mn)
n is in the range of 1.5 to 4, and the weight average molecular weight (M
w) is in the range of 3000 to 1,000,000, and (3) the weight average molecular weight (M) measured by the light scattering method.
w ′) and the radius of inertia <Rg ² > ^1/2 (Å) satisfy the formula <Rg ² > ^1/2 ≧ 4.00 × (Mw ′) ^0.372. It provides a polymer.

Further, the present invention relates to (a) ethylene,
(B) α-olefin having 3 to 20 carbon atoms and cyclic olefin
At least one selected from monoolefins
And the monoolefin content is 1
In the ethylene-based copolymer in the range of ２０20 mol% , while satisfying the above conditions (1) to (3),
(4) In the storage elastic modulus (G ′) curve in the frequency dependence of dynamic viscoelasticity measured at a temperature of 190 ° C., the elastic modulus
^The frequency corresponding to ³ dyne / cm ² is ω ₁ and the elastic modulus is 10 ⁵ dyn
Assuming that the frequency corresponding to e / cm ² is ω ₂ , the formula ω ₂ / (ω ₁ × 10) ≧ −1.35 + 1.66 × (Mw / M
n) and 3 ≦ ω ₂ / (ω ₁ × 10) ≦ 100, and (5) steady-state compliance [Je ⁰ (cm ²⁾ determined from creep behavior measured by changing stress at a temperature of 190 ° C. / dyne)] satisfies the relationship of 1 × 10 ⁻⁶ <Je ⁰ <1 × 10 ⁻² , and (6) a creep behavior at a temperature of 190 ° C. applied a stress of 5 × 10 ⁴ dyne. In this case, the elastic recovery strain (γ _r ) after stopping the application is 5 to 1500%.
And a blow molded article or sheet obtained by molding the copolymer.

The ethylene copolymer of the present invention is a copolymer of (a) ethylene and (b) at least one selected from α-olefins, diene compounds and cyclic olefins having 3 to 20 carbon atoms. It is. In this copolymer,
(Ii) 3 to 2 carbon atoms used as a comonomer of the component
As the α-olefin of 0, for example, propylene, 1-
Butene, 1-pentene, 4-methyl-1-pentene, 1
-Hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-octadecene, 1-eicosene and the like. In addition, a conjugated diolefin or a non-conjugated diolefin can be used as the diene compound. Examples of the conjugated diolefin include 1,3-butadiene; isoprene; chloroprene; 1,3-cyclohexadiene; 1,3-cyclooctadiene, and the like. Further, examples of non-conjugated diolefins include 1,5
-Hexadiene; α, ω- such as 1,7-octadiene
Diene compounds and derivatives thereof, norbornadiene; dicyclopentadiene; 5-vinylnorbornene; and cyclic diolefins such as ethylidene norbornene and derivatives thereof.

On the other hand, examples of the cyclic olefin include norbornene; 5-methylnorbornene; 5-ethylnorbornene; 5-propylnorbornene; 5,6-dimethylnorbornene; 1-methylnorbornene; 7-methylnorbornene; -Trimethylnorbornene;
5-phenylnorbornene; 5-benzylnorbornene; 1,4,5,8-dimetano-1,2,3,4,4
a, 5,8,8a-octahydronaphthalene; 2-methyl-1,4,5,8-dimethano-1,2,3,4,4
a, 5,8,8a-octahydronaphthalene; 2-cyclohexyl-1,4,5,8-dimethano-1,2,3
4,4a, 5,8,8a-octahydronaphthalene;
2,3-dichloro-1,4,5,8-dimethano-1,
2,3,4,4a, 5,8,8a-octahydronaphthalene; 2-isobutyl-1,4,5,8-dimethano-
1,2,3,4,4a, 5,8,8a-octahydronaphthalene; 1,2-dihydrodicyclopentadiene; 5
5,5-dichloronorbornene; 5-fluoronorbornene; 5,5,6-trifluoro-6-trifluoromethylnorbornene; 5-chloromethylnorbornene; 5-methoxynorbornene;
5,6-dicarboxyl norbornene anhydrate;
5-dimethylaminonorbornene; 5-cyanonorbornene; 2-ethyl-1,4,5,8-dimetano-1,
2,3,4,4a, 5,8,8a-octahydronaphthalene; 2,3-dimethyl-1,4,5,8-dimethano-
1,2,3,4,4a, 5,8,8a-octahydronaphthalene; 2-hexyl-1,4,5,8-dimethano-
1,2,3,4,4a, 5,8,8a-octahydronaphthalene; 2-ethylidene-1,4,5,8-dimethano-1,2,3,4,4a, 5,8,8a- Octahydronaphthalene; 2-fluoro-1,4,5,8-dimetano-1,2,3,4,4a, 5,8,8a-octahydronaphthalene; 1,5-dimethyl-1,4,5 8-Dimethano-1,2,3,4,4a, 5,8,8a-octahydronaphthalene and the like can be mentioned. These comonomers of the component (b) may be used alone or in combination of two or more. Particularly, α-olefins having 3 to 20 carbon atoms are preferable.

When the ethylene copolymer of the present invention is a copolymer of ethylene and an α-olefin and / or a cyclic olefin, the content of all comonomer units is determined so that the copolymer has desired properties. For this purpose, a range of 1 to 20 mol% is necessary . When the ethylene copolymer uses at least a diene compound as a comonomer, the content of the diene compound unit in the ethylene copolymer is preferably 1 mol% or less. If the content of the diene compound unit exceeds 1 mol%, the copolymer may gel due to crosslinking. From the viewpoint of preventing gelation, the content of the diene compound unit is more preferably 0.8 mol% or less,
More preferably 0.6 mol% or less, particularly preferably 0.4 mol%.
Mol% or less. The total content of the other comonomer units is preferably in the range of 0.01 to 20 mol% in order for the copolymer to have desired properties.

The ethylene copolymer of the present invention has the following properties. First, (1) resin density is 0.
It needs to be in the range of 85 to 0.95 g / cm ³ . The resin density can be arbitrarily controlled within the above range by increasing or decreasing the content of the comonomer unit. A copolymer having a resin density in the range of 0.85 to 0.95 g / cm ³ can be used as a base material for a highly functional film having excellent strength. The density is a value obtained by preparing a press sheet at a temperature of 190 ° C. and rapidly cooling the press sheet by a density gradient tube method. Next, (2) a weight-average molecular weight (M) in terms of polyethylene measured by gel permeation chromatography (GPC method).
w) and the number average molecular weight (Mn) of Mw / Mn is 1.5 to
4 and Mw is 3000 to 1,000,000
Must be in the range of If the Mw / Mn ratio is less than 1.5, the moldability is poor, and if it exceeds 4.0, physical properties such as impact strength are reduced. From the viewpoint of the balance between molding processability and physical properties, preferred Mw / Mn is in the range of 1.8 to 3.8,
Particularly, the range of 2.0 to 3.5 is preferable. Also, if Mw is 30
If it is less than 00, sufficient mechanical properties cannot be obtained.
If it exceeds 00, the moldability deteriorates. From the viewpoint of balance between mechanical properties and moldability, preferable Mw is 100.
In the range of from 00 to 800,000, especially from 15,000 to 6
A range of 00000 is preferred. Note that Mw and M
n is a device: Waters ALC / GPC 150C,
Column: TSK HM + GMH 6 × 2, flow rate: 1.0 ml / min, solvent: 1,2,4-trichlorobenzene, measurement temperature: 135 ° C., which is a value in terms of polyethylene determined by the GPC method. The comonomer content was measured using ¹ JH-JSK-400 manufactured by JEOL Ltd. (JNM).
-NMR measurement (400 MHz, measurement temperature: 130 ° C,
Solvent: 1,2,4-trichlorobenzene / deuterated benzene)
And determined from the peak intensity ratio of methyl group and methylene group.

Further, (3) measured by a light scattering method.
Weight average molecular weight (Mw ') and radius of gyration <Rg^Two>
^1/2The relationship with (Å) is expressed by the formula <Rg^Two>^1/2≧ 4.00 × (Mw ′)^0.372 It is necessary to satisfy the relationship. <Rg^Two>^1/2of
The value is 4.00 x (Mw ')^{0. 372}If smaller than molecular weight
The fabric is narrow and has no higher molecular weight components. Mw 'is 1 ×
10^FourIn the above case, the relationship between Mw ′ and Rg is expressed by the formula <Rg^Two>^1/2≧ 3.28 × (Mw ′)^0.394 Is preferably satisfied. In addition, measurement by light scattering method
Was performed according to the method shown below. That is, Otsuka Electric
Using a dynamic light scattering photometer (DLS 7000) manufactured by Koshiro
He-Ne laser (wavelength 632.8 nm) as the light source
And the solvent α-chloronaphthalene at a measurement temperature of 135 ° C.
Total scattering intensity in the range of scattering angle 20 to 150 degrees under the conditions
Was measured. And the weight average molecular weight (Mw ') and inertia
Square radius <Rg ^Two>^1/2Was calculated from the Zimm Plot.

The ethylene copolymer of the present invention preferably satisfies all of the above conditions (1) to (3) and (4) determines the frequency dependence of dynamic viscoelasticity measured at a temperature of 190 ° C. In the storage modulus (G ′) curve,
Assuming that the frequency corresponding to the elastic modulus of 10 ³ dyne / cm ² is ω ₁ and the frequency corresponding to the elastic modulus of 10 ⁵ dyne / cm ² is ω ₂ , the formula ω ₂ / (ω ₁ × 10) ≧ −1.35 + 1 .66 × (Mw / M
n) and those satisfying the relationship of 3 ≦ ω ₂ / (ω ₁ × 10) ≦ 100. ω ₂ /
(Ω ₁ × 10) is [−1.35 + 1.66 × (Mw / M
n)], the workability is reduced due to the high content of low molecular weight components. If ω ₂ / (ω ₁ × 10) is less than 3, the moldability is poor, and if it exceeds 100, the non-Newtonian property increases, but the parison drop time during blow molding becomes longer, which causes inconvenience in moldability. . From the viewpoint of moldability and elasticity, preferably 4 ≦ ω ₂ / (ω ₁ × 10) ≦ 100, more preferably 6 ≦ ω ₂ / (ω ₁ × 10) ≦ 100, particularly preferably 10 ≦ ω ₂ / ( ω ₁ × 10) ≦ 100 Most preferably, 12 ≦ ω ₂ / (ω ₁ × 10) ≦ 100. The frequency dependence of the dynamic viscoelasticity was determined by inserting a sample between parallel plates or cone plates using RMS800 manufactured by Rheometrics, and measuring the temperature at 190 ° C.
° C, linear region with distortion of 10% or less, frequency 0.01-100
The measurement was performed under the conditions in the rad / sec range.

The ethylene copolymer of the present invention is more preferably one which satisfies all of the above conditions (1) to (4) and (5) has a creep behavior measured at 190 ° C. while changing the stress. The calculated steady-state compliance [Je ⁰ (cm ² / dyne)] may satisfy the relationship of 1 × 10 ⁻⁶ <Je ⁰ <1 × 10 ⁻² . This Je
^{When the value of 0} is 1 × 10 ⁻⁶ cm ² / dyne or less, the spinning property is excellent, but the processing characteristics required for drawdown and neck-in cannot be sufficiently satisfied. Further, those having a Je ⁰ of 1 × 10 ⁻² cm ² / dyne or more have a wide molecular weight distribution, a large amount of long-chain branches, excellent processing properties, are suitably used for blow molded articles and pipes, and However, it is usually less than 1 × 10 ^-2 cm ² / dyne. From the viewpoint of processing characteristics, it is preferably 1 × 10 ⁻⁵ ≦ Je ⁰ <1 × 10 ^−2, more preferably 3 × 10 ⁻⁵ ≦ Je ⁰ <1 × 10 ⁻² . The steady compliance Je ⁰ is a value obtained by the following method. That is, a dynamic stress rheometer manufactured by Rheometrics (DSR2
00) at an applied stress of 100 to 5 × 1 at 190 ° C.
0 ⁴ optionally varied in the range of dyne, measuring the creep behavior. The compliance [Je (cm ² / dyne)] is determined from each creep behavior, and a value (showing a constant value) independent of stress is calculated as a steady-state compliance [Je ⁰ (c
m ² / dyne)].

Particularly preferred examples of the ethylene copolymer of the present invention satisfy all of the above conditions (1) to (5) and (6) have a creep behavior at a temperature of 190 ° C. of 5 × 10 ⁴ dyne. When the stress is applied, the elastic recovery strain (γ _r ) after the application is stopped is in the range of 5 to 1500%. The gamma _r is less than 5% can not maintain the shape in a molten state, inferior in moldability, a longer molding cycle properties in the molten state than 1500% results in a disadvantage. In view of the balance of moldability and molding cycle performance, the preferred range of gamma _r is from 10 to 1400%, it is preferable particularly from 15 to 1300%. The elastic recovery strain (γ _r ) is a value obtained by the following method. That is, a dynamic stress rheometer manufactured by Rheometrics (DS)
R200) at a temperature of 190 ° C. and a stress of 5 × 10 ⁴
The dyne is applied (application time: 10 seconds), and the amount of strain at which the recovery after the application is stopped is balanced is referred to as elastic recovery strain (γ _r ). In addition,
This elastic recovery strain corresponds well with the die swell value used as a general elasticity term evaluation. Further, the ethylene copolymer of the present invention usually has the following characteristics. That is, generally, when the copolymerization of an α-olefin and ethylene proceeds, there are two insertion directions of the α-olefin component, but when a normal metallocene catalyst is used, it is known that the α-olefin component is inserted from only one direction. And no heterogeneous bonds such as inversion bonds are observed. On the contrary,
In the ethylene copolymer of the present invention, a heterogeneous bond such as an inversion bond is generally observed in a nuclear magnetic resonance spectrum ( ¹³ C-NMR) of isotope carbon.

The present invention also provides a blow molded article or sheet obtained by molding the ethylene copolymer of the present invention, which satisfies all of the above conditions (1) to (6). The blow-molded article of the present invention may contain, if desired, various additional components such as an antioxidant, an ultraviolet absorber, a light stabilizer, a heat stabilizer, a neutralizer, a lubricant, a flame retardant, and a coloring agent. It is obtained by blending an agent or the like and performing blow molding. The blow molding method is not particularly limited, and a method commonly used for blow molding of a conventional polyethylene resin can be used. On the other hand, the sheet of the present invention is prepared by blending the above-mentioned various components with the ethylene-based copolymer, if necessary, furthermore, an anti-blocking agent, an anti-fogging agent, etc., for example, by ordinary air-cooled inflation molding or air-cooled two-stage inflation molding. , Water-cooled inflation molding, T
It is obtained by molding by a melt extrusion processing method such as die casting. The sheet of the present invention may have either a single-layer structure or a multilayer structure, and its thickness is not particularly limited, but is usually in the range of 10 μm to 3 mm. Therefore, the sheet of the present invention also includes a so-called film. The sheet formed in this manner is subjected to, for example, a dry laminating method or an extruding laminating method (sandwich laminating method) to form a barrier material such as nylon, polyethylene terephthalate, ethylene-vinyl alcohol copolymer, or aluminum (evaporated film). Or a foil) and an adhesive or a polyolefin-based resin, and can be used as a composite sheet such as a laminated sheet or a laminated sheet. At this time, the sheet of the present invention is preferably used as a heat seal layer.

The method for producing the ethylene copolymer of the present invention is not particularly limited as long as it has the above-mentioned properties, and various methods can be used. A method of copolymerizing ethylene and a desired comonomer using a polymerization catalyst is advantageous. That is, in the production of the ethylene copolymer of the present invention, (A) a general formula (I) CpML ₃ ... (I) wherein M represents titanium, zirconium or hafnium; Cp is a cyclic compound group having 5 to 30 carbon atoms having a cyclopentadienyl or substituted cyclopentadienyl skeleton, L represents a σ ligand, and three Ls may be the same or different. A transition metal compound represented by the formula:
A polymerization catalyst containing (B) an aluminum oxy compound and (C) a phenolic compound and / or water is preferably used.

In the polymerization catalyst, the transition metal compound as the component (A) is represented by the above general formula (I). In the general formula (I), M represents titanium, zirconium or hafnium. Cp has 5 to 30 carbon atoms having a cyclopentadienyl or substituted cyclopentadienyl skeleton coordinated with M by a π bond in an η ⁵ -bonding mode.
And L is a σ ligand coordinated to the M by σ bond. As the σ ligand, for example,
R ′, OR ′, SR ′, SO ₃ R ′, NR′R ″, P
R'R ", NO _2, halogen atom, 1-pyrrolyl and 1
-Pyrrolidinyl can be mentioned preferably. Here, R ′ and R ″ are a hydrocarbon group having 1 to 20 carbon atoms or a silyl group containing a hydrocarbon group. At least one of the σ ligands is OR ′, NR′R ″ or PR′R And three L's may be the same or different.

The group consisting of a cyclic compound having 5 to 30 carbon atoms and having a cyclopentadienyl or substituted cyclopentadienyl skeleton which is coordinated with M by a π bond in an η ⁵ -bonding mode is one, Further, the substituents on the substituted cyclopentadienyl skeleton may be mutually bonded to form a new cyclic structure. That is, a group having an indenyl skeleton, a substituted indenyl skeleton, a fluorenyl skeleton, or a substituted fluorenyl skeleton is also included in the cyclic compound group. In the above R ′ and R ″, the carbon number is 1 to 2;
Examples of the 0 hydrocarbon group include an alkyl group, a cycloalkyl group, an aryl group, and an aralkyl group. Examples of the alkyl group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group,
Isobutyl group, sec-butyl group, t-butyl group, pentyl group, hexyl group, octyl group, decyl group, dodecyl group and the like; cycloalkyl group such as cyclopentyl group and cyclohexyl group; and aryl group as aryl group For example, a phenyl group or a tolyl group can be mentioned, and as an aralkyl group, for example, a benzyl group or a phenethyl group can be mentioned. Examples of the silyl group containing a hydrocarbon group include a trimethylsilyl group and a triphenylsilyl group. Specific examples of OR 'include a methoxy group, an ethoxy group, an n-propoxy group,
Isopropoxy group, n-butoxy group, isobutoxy group,
sec-butoxy group, t-butoxy group, pentoxy group,
Examples include an alkoxy group such as a hexoxy group, an octoxy group and a cyclohexoxy group, and an aryloxy group such as a phenoxy group. Further, specific examples of SR ′ include a methylthio group, an ethylthio group, a cyclohexylthio group, and a phenylthio group. Specific examples of SO ₃ R ′ include a methanesulfonyl group, an ethanesulfonyl group, an n-propanesulfonyl group,
Isopropanesulfonyl group, n-butanesulfonyl group,
Examples thereof include an alkylsulfonyl group such as a sec-butanesulfonyl group, a t-butanesulfonyl group, and an isobutanesulfonyl group, and an arylsulfonyl group such as a benzenesulfonyl group. Further, specific examples of NR'R "include a dimethylamino group, a diethylamino group, a di (n-propyl) amino group, a diisopropylamino group,
Di (n-butyl) amino group, diisobutylamino group, di (sec-butyl) amino group, di (t-butyl) amino group, dipentylamino group, dihexylamino group, dioctylamino group, diphenylamino group, dibenzylamino Group, methylethylamino group, (t-butyl) trimethylsilylamino group, methyltrimethylsilylamino group and the like. Specific examples of PR′R ″ include a dimethyl phosphide group, a diethyl phosphide group, a di (n-propyl) phosphide group, a diisopropyl phosphide group, a di (n-butyl) phosphide group,
Diisobutyl phosphide group, di (sec-butyl) phosphide group, di (t-butyl) phosphide group, dipentyl phosphide group, dihexyl phosphide group, dioctyl phosphide group, diphenyl phosphide group,
Dibenzyl phosphide group, methyl ethyl phosphide group, (t-butyl) trimethylsilyl phosphide group,
Methyltrimethylsilyl sulfide group and the like can be mentioned. Further, examples of the halogen atom include chlorine, bromine and iodine.

Examples of the transition metal compound represented by the general formula (I) include cyclopentadienyl titanium trimethyl; cyclopentadienyl titanium triethyl; cyclopentadienyl titanium tri (n-propyl); Enyl titanium triisopropyl; cyclopentadienyl titanium tri (n-butyl); cyclopentadienyl titanium triisobutyl; cyclopentadienyl titanium tri (sec-butyl); cyclopentadienyl titanium tri (t-butyl); methyl Cyclopentadienyl titanium trimethyl; 1,2-dimethylcyclopentadienyl titanium trimethyl; 1,2,4-trimethylcyclopentadienyl titanium trimethyl; 1,2,3,4-tetramethylcyclopentadienyl titanium trimethyl; Pentamethylcyclope Tadienyl titanium trimethyl; pentamethylcyclopentadienyl titanium triethyl; pentamethylcyclopentadienyl titanium tri (n-propyl); pentamethylcyclopentadienyl titanium triisopropyl; pentamethylcyclopentadienyl titanium tri (n-butyl) ); Pentamethylcyclopentadienyl titanium triisobutyl; pentamethylcyclopentadienyl titanium tri (sec-butyl); pentamethylcyclopentadienyl titanium tri (t-butyl); cyclopentadienyl titanium trimethoxide; cyclo Pentadienyl titanium triethoxide; cyclopentadienyl titanium tri (n-propoxide); cyclopentadienyl titanium triisopropoxide; cyclopentadienyl titanium triphenoxide; methylcycl Pentadienyl titanium trimethoxide; (n-butyl) cyclopentadienyl titanium trimethoxide; dimethylcyclopentadienyl titanium trimethoxide; dimethylcyclopentadienyl titanium triethoxide; dimethylcyclopentadienyl titanium trimethoxide n-propoxide); dimethylcyclopentadienyltitanium triisopropoxide; dimethylcyclopentadienyltitanium triphenoxide; di (t
-(Butyl) cyclopentadienyltitanium trimethoxide; di (t-butyl) cyclopentadienyltitanium triethoxide; di (t-butyl) cyclopentadienyltitanium tri (n-propoxide); di (t- Butyl) cyclopentadienyltitanium triisopropoxide; di (t
-Butyl) cyclopentadienyltitanium triphenoxide; bis (trimethylsilyl) cyclopentadienyltitanium trimethoxide; bis (trimethylsilyl) cyclopentadienyltitanium triethoxide; bis (trimethylsilyl) cyclopentadienyltitanium tri (n- Propoxide); bis (trimethylsilyl) cyclopentadienyltitanium triisopropoxide; bis (trimethylsilyl) cyclopentadienyltitanium triphenoxide; trimethylcyclopentadienyltitanium trimethoxide; trimethylcyclopentadienyltitanium triethoxide; Trimethylcyclopentadienyl titanium tri (n-propoxide); trimethylcyclopentadienyl titanium triisopropoxide; trimethylcyclopentadienyl titanium tri Phenoxide; triethylcyclopentadienyltitanium trimethoxide; [bis (dimethylsilyl), methyl] cyclopentadienyltitanium trimethoxide; [di (t-butyl, methyl)] cyclopentadienyltitanium triethoxide; tetra Methylcyclopentadienyl titanium trimethoxide; tetramethylcyclopentadienyl titanium triethoxide; tetramethylcyclopentadienyl titanium tri (n-propoxide); tetramethylcyclopentadienyl titanium triisopropoxide; tetramethyl Cyclopentadienyl titanium tri (n-butoxide); tetramethylcyclopentadienyl titanium triisobutoxide; tetramethylcyclopentadienyl titanium tri (sec-butoxide); tetramethylcyclopentadienyl tita Tri (t-butoxide); tetramethylcyclopentadienyltitanium triphenoxide; [tetramethyl, 4-methoxyphenyl] cyclopentadienyltitanium trimethoxide; [tetramethyl, 4-methoxyphenyl] cyclopentadienyltitanium trimethoxide Ethoxide; [tetramethyl, 4-methoxyphenyl] cyclopentadienyltitanium tri (n-propoxide); [tetramethyl, 4-methoxyphenyl] cyclopentadienyltitanium triisopropoxide; [Methoxyphenyl] cyclopentadienyltitanium triphenoxide;
[Tetramethyl, 4-methylphenyl] cyclopentadienyltitanium trimethoxide; [tetramethyl, 4-methylphenyl] cyclopentadienyltitanium triethoxide; [tetramethyl, 4-methylphenyl] cyclopentadienyltitanium Tri (n-propoxide); [tetramethyl, 4-methylphenyl] cyclopentadienyl titanium triisopropoxide; [tetramethyl, 4-methylphenyl] cyclopentadienyl titanium triphenoxide; [tetramethyl, benzyl] Cyclopentadienyl titanium trimethoxide; [tetramethyl, benzyl] cyclopentadienyl titanium triethoxide; [tetramethyl, benzyl] cyclopentadienyl titanium tri (n-propoxide); [tetramethyl, benzyl]
Cyclopentadienyl titanium triisopropoxide;
[Tetramethyl, benzyl] cyclopentadienyl titanium triphenoxide; [tetramethyl, 2-methoxyphenyl] cyclopentadienyl titanium trimethoxide;
[Tetramethyl, 2-methoxyphenyl] cyclopentadienyltitanium triethoxide; [tetramethyl, 2-methoxyphenyl]
[Methoxyphenyl] cyclopentadienyl titanium triphenoxide; [tetramethyl, ethyl] cyclopentadienyl titanium trimethoxide; [tetramethyl, ethyl] cyclopentadienyl titanium triethoxide; [tetramethyl, ethyl] cyclopentadiene [Tetramethyl, ethyl] cyclopentadienyl titanium triisopropoxide; [tetramethyl, ethyl] cyclopentadienyl titanium triphenoxide; [tetramethyl, n-butyl] cyclopenta Dienyl titanium trimethoxide; [tetramethyl, n
[Butyl] cyclopentadienyltitanium triethoxide; [tetramethyl, n-butyl] cyclopentadienyltitanium tri (n-propoxide);
[n-butyl] cyclopentadienyltitanium triisopropoxide; [tetramethyl, n-butyl] cyclopentadienyltitanium triphenoxide; [tetramethyl, phenyl] cyclopentadienyltitanium trimethoxide;
[Tetramethyl, phenyl] cyclopentadienyltitanium triethoxide; [tetramethyl, phenyl] cyclopentadienyltitanium triphenoxide; [tetramethyl, trimethylsilyl] cyclopentadienyltitanium trimethoxide; [tetramethyl, trimethylsilyl] Cyclopentadienyl titanium triphenoxide; pentamethylcyclopentadienyl titanium trimethoxide; pentamethylcyclopentadienyl titanium triethoxide;
Pentamethylcyclopentadienyl titanium tri (n-propoxide); pentamethylcyclopentadienyl titanium triisopropoxide; pentamethylcyclopentadienyl titanium tri (n-butoxide); pentamethylcyclopentadienyl titanium triiso Butoxide; pentamethylcyclopentadienyl titanium tri (sec-butoxide); pentamethylcyclopentadienyl titanium tri (t-butoxide); pentamethylcyclopentadienyl titanium tri (cyclohexoxide); pentamethylcyclopentadienyl Titanium triphenoxide; cyclopentadienyl titanium tribenzyl; indenyl titanium trimethoxide; indenyl titanium triethoxide; indenyl titanium trimethyl; indenyl titanium tribenzyl; cyclopen Dienyl titanium tri (methanesulfonyl); trimethyl cyclopentadienyl titanium (tri benzenesulfonyl); tetramethylcyclopentadienyl titanium tri (ethanesulfonyl); pentamethylcyclopentadienyltitanium tri (methanesulfonyl);
Cyclopentadienyl titanium tris (dimethylamide); trimethylcyclopentadienyl titanium tris (dimethylamide); pentamethylcyclopentadienyl titanium tris (dibenzylamide); pentamethylcyclopentadienyl titanium tris (dimethylamide);
Pentamethylcyclopentadienyltitanium tris (diethylamide); cyclopentadienyltitanium tri (nitro); pentamethylcyclopentadienyltitanium tri (nitro), etc., and compounds obtained by substituting titanium in these compounds with zirconium or hafnium. No.

Further, cyclopentadienyl titanium dimethyl monochloride; cyclopentadienyl titanium monoethyl dichloride; cyclopentadienyl titanium di (n
-Propyl) monochloride; cyclopentadienyl titanium diisopropyl monochloride; cyclopentadienyl titanium di (n-butyl) monochloride; cyclopentadienyl titanium diisobutyl monochloride; cyclopentadienyl titanium di (sec-butyl) mono Chloride; cyclopentadienyl titanium di (t-butyl) monochloride; 1,2-dimethylcyclopentadienyl titanium dimethyl monochloride; 1,2,4-trimethylcyclopentadienyl titanium dimethyl monochloride; 3,
4-tetramethylcyclopentadienyltitanium dimethylmonochloride; pentamethylcyclopentadienyltitanium dimethylmonochloride; cyclopentadienyltitanium monochlorodimethoxide; cyclopentadienyltitaniumdichloromonomethoxide; cyclopentadienyltitaniumdichloromono Ethoxide; cyclopentadienyltitanium monochlorodioxide (n-propoxide); cyclopentadienyltitanium monochlorodithiopropoxide; cyclopentadienyltitanium monochlorodiphenoxide; dimethylcyclopentadienyltitanium monochlorodimethoxide;
Dimethylcyclopentadienyl titanium monochlorodioxide; dimethylcyclopentadienyl titanium monochlorodioxide (n-propoxide); dimethylcyclopentadienyl titanium monochlorodiisopropoxide; dimethylcyclopentadienyl titanium monochlorodiphenoxide;
Di (t-butyl) cyclopentadienyltitanium monochlorodimethoxide; bis (trimethylsilyl) cyclopentadienyltitanium monochlorodimethoxide; trimethylcyclopentadienyltitanium monochlorodimethoxide;
Trimethylcyclopentadienyltitanium monochlorodimethoxide; triethylcyclopentadienyltitanium monochlorodimethoxide; [bis (dimethylsilyl), methyl] cyclopentadienyltitanium monochlorodimethoxide; tetramethylcyclopentadienyltitanium monochlorodimethoxide; tetra Methylcyclopentadienyltitanium dichloromonomethoxide; tetramethylcyclopentadienyltitanium monochloride (n-butoxide);
Tetramethylcyclopentadienyl titanium monochlorodiisobutoxide; tetramethylcyclopentadienyl titanium monochlorodioxide (sec-butoxide); tetramethylcyclopentadienyl titanium monochlorodioxy (t-butoxide); [tetramethyl, 4-methoxyphenyl ] Cyclopentadienyl titanium monochloromethoxide;
[Tetramethyl, 4-methylphenyl] cyclopentadienyl titanium monochlorodimethoxide; [tetramethyl, benzyl] cyclopentadienyl titanium monochlorodimethoxide; [tetramethyl, benzyl] cyclopentadienyl titanium monochlorodimethoxide; [Methyl, 2-methoxyphenyl] cyclopentadienyltitanium monochlorodimethoxide; [tetramethyl, ethyl] cyclopentadienyltitanium monochlorodimethoxide; [tetramethyl, ethyl] cyclopentadienyltitanium monochlorodimethoxide; [N-butyl] cyclopentadienyltitanium monochlorodioxide; [tetramethyl, n-butyl] cyclopentadienyltitanium monochlorodioxide (n-propoxide); [tetramethyl, n-butyl] Cyclopentadienyl titanium monochlorodimethoxypropoxide; [tetramethyl, phenyl] cyclopentadienyl titanium monochlorodimethoxide; [tetramethyl, trimethylsilyl] cyclopentadienyl titanium monochlorodimethoxymethoxide; pentamethylcyclopentadienyl titanium monochlorodioxide Dimethoxide;
Pentamethylcyclopentadienyl titanium monochlorodimethoxide; pentamethylcyclopentadienyl titanium monochlorodioxide; pentamethylcyclopentadienyl titanium monochlorodioxide (cyclohexoxide); pentamethylcyclopentadienyl titanium monochlorodiphenoxide; Indenyl titanium monochlorodimethoxide; cyclopentadienyl titanium monochlorodioxide (methanesulfonyl); pentamethylcyclopentadienyl titanium monochlorobis (diethylamide); pentamethylcyclopentadienyl titanium monochlorobis [di (n-butyl) amide] Pentamethylcyclopentadienyltitanium dichloro (dimethylamide); pentamethylcyclopentadienyltitanium dichloro (diphenylamide);
Pentamethylcyclopentadienyl titanium dichloro (methylethylamide); pentamethylcyclopentadienyl titanium dichloro (t-butyltrimethylsilylamide); pentamethylcyclopentadienyl titanium dimethoxy (diphenylamide); pentamethylcyclopentadienyl titanium Monochlorobis (diethyl phosphide); pentamethylcyclopentadienyl titanium monochlorobis [di (n-butyl) phosphide]; pentamethylcyclopentadienyl titanium dichloro (dimethyl phosphide); pentamethylcyclopentadienyl titanium dimethoxy ( Dimethylphosphido); pentamethylcyclopentadienyltitaniumdichloro (diphenylphosphide); pentamethylcyclopentadienyltitaniumdichloro (methylethyl) Sulfide); pentamethylcyclopentadienyltitanium dichloro (t-butyltrimethylsilyl phosphide); pentamethylcyclopentadienyl titanium trichloride; pentamethylcyclopentadienyltitanium dimethoxy (diphenyl phosphide); In addition, there may be mentioned corresponding compounds containing zirconium and hafnium instead of titanium in the compounds. In the polymerization catalyst, the transition metal compound of the component (A) may be used alone or in combination of two or more.

In this polymerization catalyst, the aluminum oxy compound used as the component (B) is represented by the general formula (II):

[0022]

Embedded image

[Wherein, R ¹ represents an alkyl group, alkenyl group, aryl group having 1 to 20, preferably 1 to 12 carbon atoms,
Represents a hydrocarbon group such as an arylalkyl group, which may be the same or different (for example, a hydrolyzate of a plurality of alkylaluminums). s indicates the degree of polymerization and is usually an integer of 2 to 50, preferably 3 to 40. Aluminoxane represented by the general formula (II
I)

[0024]

Embedded image

[In the formula, R ¹ is the same as described above, and p indicates the degree of polymerization, and is usually an integer of 3 to 50, preferably 7 to 40. And the cyclic aluminoxane represented by the formula: Examples of the method for producing the aluminoxane include a method in which an alkylaluminum is brought into contact with a condensing agent such as water. The method is not particularly limited, and the reaction may be performed according to a known method. For example, a method in which an organoaluminum compound is dissolved in an organic solvent and then brought into contact with water, a method in which an organoaluminum compound is initially added during polymerization and then water is added, and a crystal water contained in a metal salt or the like is used. A method of reacting water adsorbed by an inorganic or organic substance with an organoaluminum compound, a method of reacting a trialkylaluminum with a tetraalkyldialuminoxane, and further reacting water. The aluminoxane may be toluene-insoluble.

These aluminoxanes can be classified as shown below. (A) an alkylaluminoxane produced using a single alkylaluminum (organoaluminum) compound,
For example, methylaluminoxane, ethylaluminoxane, n-propylaluminoxane, isopropylaluminoxane, n-butylaluminoxane, isobutylaluminoxane, sec-butylaluminoxane, t-butylaluminoxane and the like. (B) A mixed alkylaluminoxane in which two or more kinds are selected from the alkylaluminoxanes produced in the above (a), and these are mixed at a predetermined ratio. (C) A copolymerization type alkylaluminoxane obtained by mixing two or more kinds of alkylaluminum (organoaluminum) compounds at a predetermined ratio during the production in the above-mentioned methods, for example, methyl-ethylaluminoxane, methyl-n-propyl Aluminoxane, methyl-isopropylaluminoxane, methyl-n-butylaluminoxane,
Methyl-isobutylaluminoxane, ethyl-n-propylaluminoxane, ethyl-isopropylaluminoxane, ethyl-n-butylaluminoxane, ethyl-isobutylaluminoxane and the like. These aluminoxanes may be used alone or in a combination of two or more. Further, among aluminoxanes, alkylaluminoxanes are particularly preferred. In addition, in the aluminoxane thus obtained, the alkylaluminum as a synthesis raw material remains and may be contained as an impurity, but in the present invention,
You can use it as it is.

The activity of the polymerization catalyst is further increased.
Phenolic compound as component (C) for the purpose of improving
And / or water, but especially phenol
Sex compounds are preferred. As this phenolic compound
Is an aromatic compound such as a benzene ring or naphthalene ring.
A hydrogen atom bonded to the ring has at least one hydroxyl group or
At least one hydroxyl group and other than at least one hydroxyl group
Compounds substituted with the above substituents can be mentioned. This
Here, as the substituent other than the hydroxyl group, for example, R^Two, OR
^Two, SR^Two, NR^TwoR^Three, Halogen atom, nitro group, etc.
Is mentioned. R^Two, R^ThreeIs a hydrocarbon having 1 to 20 carbon atoms
Groups such as alkyl, cycloalkyl, aryl,
And aralkyl groups. As the alkyl group, for example,
Methyl group, ethyl group, n-propyl group, isopropyl
Group, n-butyl group, isobutyl group, sec-butyl group,
t-butyl group, pentyl group, hexyl group, octyl group,
Decyl, dodecyl, etc. as cycloalkyl
Is, for example, a cyclopentyl group or a cyclohexyl group
As the aryl group, for example, a phenyl group or tolyl
Aralkyl group, for example, benzyl group
And a phenethyl group. OR^TwoUtensils
Examples include methoxy, ethoxy and n-propoxy.
Group, isopropoxy group, n-butoxy group, isobutoxy
Si group, sec-butoxy group, t-butoxy group, pentoxy
Si group, hexoxy group, octoxy group, cyclohexoxy
Groups such as alkoxy groups and phenoxy groups
And the like. NR ^TwoR^ThreeExamples of
Dimethylamino group, diethylamino group, di (n
-Propyl) amino group, diisopropylamino group, di
(N-butyl) amino group, diisobutylamino group, di
(Sec-butyl) amino group, di (t-butyl) amino
Group, dipentylamino group, dihexylamino group, dioctyl
Tylamino group, diphenylamino group, dibenzylamino
And the like. Also, as a halogen atom
Can include chlorine, bromine, iodine and fluorine
You.

As the component (C), a phenolic compound and / or water is used. Here, as the phenolic compound, a phenolic compound substituted with a hydrocarbon group having 1 to 20 carbon atoms is preferable. In particular, the α, α′-position of the hydroxyl group is substituted with a hydrocarbon group having 1 to 20 carbon atoms. Phenolic compounds are preferred. Specific examples of the phenolic compound include phenol; 2-methylphenol; 2-ethylphenol; 2-n-propylphenol; 2-isopropylphenol; 2-n-butylphenol;
-Sec-butylphenol; 2-tert-butylphenol; 3-tert-butylphenol; 4-te
tert-butylphenol; 4-tert-octylphenol; 2-n-dodecylphenol; 2-phenylphenol; 4-phenylphenol; 2,6-dimethylphenol; 2,6-diethylphenol; 2,6-di-tert-butylphenol 2,4-di-tert;
-Tert-butyl-4-methylphenol; 2-tert-butyl-5-methylphenol; 2-tert-butyl-6-methylphenol; 2-n-dodecyl-4-methylphenol; 4-n
-Dodecyl-2-methylphenol; 2,6-diphenylphenol; 2,6-di-tert-butyl-4-methylphenol; 2,6-di-tert-butyl-4-
Ethylphenol; 2,4,6-tri-tert-butylphenol; 2,2′-methylenebis (4-methyl-
2,2'-methylenebis (4-ethyl-6-tert-butylphenol); 4,4'-methylenebis (2,6-di-tert)
-Butylphenol); 4,4'-butylidenebis (6
-Tert-butyl-m-cresol); 4,4′-thiobis (6-tert-butyl-m-cresol); α
-Naphthol; β-naphthol; 2-fluorophenol; 3-fluorophenol; 4-fluorophenol; 2,4-difluorophenol; 2,5-difluorophenol; 2,6-difluorophenol; 2-methoxyphenol; Methoxyphenol; 4-methoxyphenol; 2,6-di-tert-butyl-4-
Methoxyphenol; N, N-dimethyl-3-aminophenol; N, N-diethyl-3-aminophenol;
N, N-di-n-butyl-3-aminophenol; 2,
6-di-tert-butyl-4-dimethylaminophenol; 2-nitrophenol; 3-nitrophenol;
4-nitrophenol; 2-nitro-4-methylphenol; 3-nitro-4-methylphenol; 4-nitro-3-methylphenol; 5-nitro-2-methylphenol; catechol; resorcinol;
3-methylcatechol; 4-methylcatechol; 4-t
ert-butylcatechol; 2-methylresorcinol; 5-methylresorcinol; methylhydroquinone;
tert-butylhydroquinone; 2,5-di-tert
-Butylhydroquinone; 1,2-dihydroxynaphthalene; 1,4-dihydroxynaphthalene; 1,5-dihydroxynaphthalene; 1,6-dihydroxynaphthalene;
1,7-dihydroxynaphthalene; 2,3-dihydroxynaphthalene; 2,7-dihydroxynaphthalene; pyrogallol; phloroglucinol; 1,2,4-trihydroxybenzene; hexahydroxybenzene. These phenolic compounds may be used alone or in combination of two or more.

The ratio of the component (A) to the component (B) in the polymerization catalyst is such that the molar ratio of the aluminum oxy compound (in terms of aluminum) of the component (B) / the transition metal compound of the component (A) is usually 1%. It is selected to be in the range of 10,000 to 10,000. If the molar ratio is less than 1, the activity is not sufficiently exhibited, and if it exceeds 10,000, the aluminum oxy compound is wasted and causes a large amount to remain in the obtained polymer. The preferred molar ratio is from 10 to 50 from the viewpoints of activity, economy, and quality of the obtained polymer.
00, and particularly preferably in the range of 20 to 2,000.

The phenolic compound of component (C) and / or water has a molar ratio of hydroxyl group in component (C) / aluminum oxy compound (in terms of aluminum) of component (B).
It is preferable to use it in the range of 0.001 to 0.8. When the molar ratio is less than 0.001, the effect of improving the activity is insufficient, and when it exceeds 0.8, the activity tends to decrease. From the viewpoint of activity improvement, a more preferable molar ratio is in the range of 0.01 to 0.6, and particularly preferably in the range of 0.05 to 0.5. The calculation was made on the assumption that one mole of water had 2 moles of hydroxyl groups. The order of contact of the catalyst components is not particularly limited. However, after the components (B) and (C) are brought into contact, the components (A) are brought into contact, or the components (B) and (A) are brought into contact with each other. It is preferable to bring the component (C) into contact after contacting with (C) from the viewpoint of catalytic activity.

The polymerization catalyst may contain, if desired, other catalyst components in addition to the components (A), (B) and (C) as long as the object of the present invention is not impaired. May be. Further, if desired, each catalyst component may be brought into contact with an appropriate carrier to be carried on the carrier. Examples of the carrier include inorganic oxides such as silica and alumina, inorganic halides such as magnesium chloride, inorganic alkoxides such as diethoxymagnesium, and polymers such as polystyrene.

The polymerization method in the present invention is not particularly limited, and any polymerization method such as a slurry polymerization method, a high temperature solution polymerization method, a gas phase polymerization method and a bulk polymerization method can be employed. When a polymerization solvent is used, the solvent is, for example, an inert solvent such as an aliphatic hydrocarbon having 5 to 18 carbon atoms, an alicyclic hydrocarbon, or an aromatic hydrocarbon having 6 to 20 carbon atoms, specifically, n -Pentane, isopentane, hexane, heptane, octane, nonane, decane, tetradecane, cyclohexane, benzene, toluene, xylene,
Ethylbenzene and the like can be mentioned. These may be used alone or in combination of two or more. Further, the polymerization temperature is not particularly limited, but is usually from 0 to 3
The temperature is selected in the range of 50 ° C, preferably 20 to 250 ° C.
On the other hand, the polymerization pressure is not particularly limited, but is usually 0 to 10.
150kg / cm ² G, preferably selected in the range of 0~100kg / cm ² G.

The use ratio of the catalyst to the raw material monomer is as follows:
Raw material monomer / component (A) (molar ratio) is preferably 1 to 10 ^8, it is preferable that the particular 100 to 10 ⁵ range. The polymerization time is usually about 5 minutes to 10 hours. Methods for adjusting the molecular weight of the polymer include selection of the type and amount of each catalyst component used, the polymerization temperature, and polymerization in the presence of hydrogen. The molecular weight of the polymer thus obtained is not particularly limited, but the intrinsic viscosity [η]
(Measured in 135 ° C decalin) is 0.1 deciliter /
g or more, particularly preferably 0.2 deciliter / g or more.

In the present invention, preliminary polymerization can be performed using the polymerization catalyst. The prepolymerization can be carried out by bringing a small amount of olefin into contact with the solid catalyst component, but the method is not particularly limited,
A known method can be used. The olefin used for the prepolymerization is not particularly limited, and may be ethylene or the same as those exemplified above, for example, α having 3 to 20 carbon atoms.
Olefins, or mixtures thereof, and the like, but it is advantageous to use the same olefins as those used in the polymerization. The prepolymerization temperature is usually -20 to 200C, preferably -10 to 1C.
The temperature is 30 ° C, more preferably 0 to 80 ° C. In the prepolymerization, an inert hydrocarbon, an aliphatic hydrocarbon, an aromatic hydrocarbon, a monomer, or the like can be used as a solvent. Particularly preferred among these are aliphatic hydrocarbons. Further, the prepolymerization may be performed without a solvent. In the prepolymerization, the intrinsic viscosity of the prepolymerized product [η] (135
C. (measured in decalin) at 0.2 deciliters / g or more, especially 0.5 deciliters / g or more.
The amount of the prepolymerized product per 1 mmol is 1 to 10
It is desirable to adjust the conditions so as to be 000 g, especially 10 to 1000 g. Thus, the ethylene copolymer of the present invention can be obtained efficiently.

[0035]

Next, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples.

Example 1 (1) Preparation of aluminum catalyst component A solution of methylaluminoxane toluene (manufactured by Albemarle) having a concentration of 1.4 mol / liter (as Al atom) was prepared using A
0.2 mol was used as 1 atom, and at room temperature, nitrogen containing water was introduced with stirring. The introduction was carried out gradually over 16 hours, and water was introduced in an amount of 0.16 times the mole of Al atoms. Thereafter, the reaction was performed for 5 hours to obtain an aluminum catalyst component. (2) Production of ethylene / octene-1 copolymer In a pressure-resistant autoclave with a stirrer of 4 liters in internal volume,
Under a nitrogen atmosphere, 1560 ml of toluene, 40 ml of octene-1 and 4 mmol (as an Al atom) of the methyl aluminoxane prepared in the above (1) were added, and the temperature was raised to 60 ° C. with stirring. After maintaining this state for 5 minutes, a catalyst solution of pentamethylcyclopentadienyltitanium trimethoxide was added in an amount of 40 μmol in terms of Ti atoms, and the temperature was raised to 65 ° C. Hydrogen
1.0 kg / cm ² G charged, and 4 kg / cm ² G ethylene
While maintaining the pressure at a constant pressure, the mixture was continuously introduced, and a copolymerization reaction was carried out at 65 ° C. for 30 minutes. After the reaction, after depressurizing,
After deactivation with alcohol, the copolymer was recovered and dried, yielding 76 g of ethylene / octene-1 copolymer. (3) Evaluation of copolymer The copolymer obtained in the above (2) was evaluated. Table 1 shows the results.

Example 2 (1) Production of ethylene / octene-1 copolymer In Example 1- (2), the charge pressure of hydrogen was 0.2 kg.
/ cm ² G and the polymerization temperature was changed to 90 ° C.
It carried out similarly to (2) and obtained 104 g of copolymers. (2) Evaluation of copolymer The copolymer obtained in the above (1) was evaluated. The result is
It is shown in the table.

Example 3 (1) Production of Ethylene / Octene-1 Copolymer In Example 1- (2), the charging pressure of hydrogen was 0.5 kg / c.
Example 1 except that m ² G and the polymerization temperature were 90 ° C.
It carried out similarly to (2) and obtained 114 g of copolymers. (2) Evaluation of copolymer The copolymer obtained in the above (1) was evaluated. The result is
It is shown in the table.

Comparative Examples Sample A (hexene-1 unit content 1.8 mol%), which is an ethylene / hexene-1 copolymer, and Sample B (octene-1 unit content, which is an ethylene / octene-1 copolymer) 4.1 mol%) and Sample C (octene-1 unit content 4.4 mol%), which is an ethylene / octene-1 copolymer. Table 1 shows the results.

[0040]

[Table 1]

[0041]

[Table 2]

[0042]

As described above, the ethylene copolymer of the present invention can provide a molded article having excellent molding properties and high mechanical strength, such as a blow molded article or a sheet.
Since the ethylene-based copolymer can particularly reduce the processing load energy, it can be expected to expand the application field.

Continuation of front page (72) Inventor Mitsuru Kanzawa 1280 Kamiizumi, Sodegaura-shi, Chiba Idemitsu Kosan Co., Ltd. (56) References JP-A-8-319313 (JP, A) (58) Fields investigated (Int. . ^7, DB name) C08F 210/02 B29C 49/00 C08J 5/18

Claims (4)

(57) [Claims] (1) ethylene and (b) a carbon number of 3 to 2.
Α-olefin and cyclic olefin monoole
From at least one of the fins,
And the content of the monoolefin is in the range of 1 to 20 mol%.
In the ethylene copolymer in, is (1) Resin Density
In the range of 0.85~0.95g / cm ^3, (2) the ratio Mw / Mn of the weight average molecular weight in terms of polyethylene were measured by gel permeation chromatography (Mw) to number average molecular weight (Mn) Is in the range of 1.5 to 4 and the weight average molecular weight (Mw) is 3000 to 100
000, and (3) the weight average molecular weight (Mw ') measured by the light scattering method and the radius of gyration <Rg ²
> ^1/2 (Å), a blow molding obtained by molding an ethylene copolymer satisfying the formula <Rg ² > ^1/2 ≧ 4.00 × (Mw ′) ^0.372
Form or sheet . (4) In the storage elastic modulus (G ′) curve in the frequency dependence of dynamic viscoelasticity measured at a temperature of 190 ° C., the frequency corresponding to the elastic modulus of 10 ³ dyne / cm ² is represented by ω ₁ ,
Assuming that the frequency corresponding to the elastic modulus of 10 ⁵ dyne / cm ² is ω ₂ , the equation ω ₂ / (ω ₁ × 10) ≧ −1.35 + 1.66 × (Mw / M
_2. The ethylene copolymer according to claim 1, which satisfies the following relationship: n) and 3 ≦ ω ₂ / (ω ₁ × 10) ≦ 100.
A blow molded article or sheet formed by molding . (4) In the storage elastic modulus (G ′) curve in the frequency dependence of dynamic viscoelasticity measured at a temperature of 190 ° C., the frequency corresponding to the elastic modulus of 10 ³ dyne / cm ² is represented by ω ₁ ,
Assuming that the frequency corresponding to the elastic modulus of 10 ⁵ dyne / cm ² is ω ₂ , the equation ω ₂ / (ω ₁ × 10) ≧ −1.35 + 1.66 × (Mw / M
n) and 3 ≦ ω ₂ / (ω ₁ × 10) ≦ 100, and (5) steady-state compliance [Je ⁰ (cm ²⁾ determined from creep behavior measured by changing stress at a temperature of 190 ° C. / dyne)] is an ethylene copolymer according to claim 1, wherein satisfying the relationship of expression ^{1 × 10 -6 <Je 0 <} 1 × 10 -2 to
A blow molded article or sheet formed by molding . (4) In a storage elastic modulus (G ′) curve in a frequency dependence of dynamic viscoelasticity measured at a temperature of 190 ° C., a frequency corresponding to an elastic modulus of 10 ³ dyne / cm ² is represented by ω ₁ ,
Assuming that the frequency corresponding to the elastic modulus of 10 ⁵ dyne / cm ² is ω ₂ , the equation ω ₂ / (ω ₁ × 10) ≧ −1.35 + 1.66 × (Mw / M
n) and 3 ≦ ω ₂ / (ω ₁ × 10) ≦ 100, and (5) steady-state compliance [Je ⁰ (cm ²⁾ determined from creep behavior measured by changing stress at a temperature of 190 ° C. / dyne)] satisfies the relationship of 1 × 10 ⁻⁶ <Je ⁰ <1 × 10 ⁻² , and (6) applied a stress of 5 × 10 ⁴ dyne in creep behavior at a temperature of 190 ° C. In this case, the elastic recovery strain (γ _r ) after stopping the application is 5 to 1500.
% By molding the ethylene-based copolymer according to claim 1.
Blow molded article or sheet .