JPH0912634A - Ethylene copolymer and its molded product - Google Patents

Abstract

PURPOSE: To obtain an ethylene copolymer having excellent moldability and giving a molded product having high mechanical strengths by copolymerizing ethylene with a specified copolymer component so as to form a copolymer having specified properties. CONSTITUTION: This ethylene copolymer is obtained from ethylene and at least one member selected from among 3-20C α-olefins, diene compounds and cycloolefins and has the following properties: (1) the resin density is 0.85-0.95g/cm<3> ; (2) the Mw/Mn ratio is in the range of 1.5-4 (wherein Mw is the weight-average molecular weight (in terms of the polyethylene) as measured by gel permeation chromatography, and Mn is the number - average molecular weight in terms of the polyetHylene) as measured by the same method) and the Mw is in the range of 3,000-1,000-000; and (3) the formula: <Rg<2> ><1/2> >=4.00(Mw')<0.372> (wherein Mw' us the weight - average molecular weight as measured by the light scattering method, and <WRg<2> ><1/2> (Å) is the inertia radius) is satisfied.

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 product thereof, and more specifically, an ethylene-based copolymer which is excellent in molding processing characteristics and has a high mechanical strength, and The present invention relates to a blow-molded body or sheet having a high mechanical strength obtained by molding a product.

[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 been conventionally produced by a heterogeneous catalyst. The ethylene-based copolymer obtained by using this heterogeneous catalyst has a wide molecular weight distribution and a wide branching degree distribution. , High branching degree A large amount of low molecular weight components are contained. As a result, it is known that the film obtained from this ethylene copolymer is inferior in heat sealability and environmental stress crack resistance (ESCR property). However, since the film has little anisotropy (the longitudinal and lateral strengths are unbalanced), it has an advantage of excellent tear strength, which is important as a 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. The ethylene-based copolymer obtained by using this metallocene catalyst is
The molecular weight distribution is narrow, and the branching degree distribution is narrow accordingly, and there are few low molecular weight substances having highly branched components. Therefore, the resulting film has heat sealability, impact resistance, and E
It is known that the SCR property is improved.

By the way, in general, a measure of the molecular weight distribution derived from the rheological properties of a polymer (Polydispersity)
It is known that the swell ratio, which is used as one measure of the index (PI) or the elastic term, correlates with the primary structure (for example, molecular weight, molecular weight distribution). In recent years, an ethylene-based copolymer obtained by using a single-site catalyst (metallocene catalyst) that has been put on the market has a problem that its rheological property is deteriorated due to its narrow molecular weight distribution, resulting in poor moldability. Further, the ethylene-based copolymer disclosed in US Pat. No. 5,272,236 has a small amount of long chain branching despite its narrow molecular weight distribution, and therefore, some improvement in rheological properties can be expected. However, this ethylene-based copolymer requires various moldings in order to be used for a wide range of applications, but its rheological properties are still insufficient to support such various moldings.

[0004]

SUMMARY OF THE INVENTION Under the circumstances, the present invention provides an ethylene-based copolymer which gives a molded product having excellent molding processing characteristics and high mechanical strength, and this ethylene-based copolymer. It is an object of the present invention to provide a blow-molded body or sheet having high mechanical strength obtained by molding.

[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 is (a) ethylene,
(B) In an ethylene copolymer obtained from an α-olefin having 3 to 20 carbon atoms, at least one selected from a diene compound and a cyclic olefin, (1) the resin density is 0.85 to 0. Within the range of 95 g / cm ³ ,
(2) Weight average molecular weight (M equivalent to polyethylene measured by gel permeation chromatography)
The ratio Mw / Mn of w) to the number average molecular weight (Mn) is 1.5 to
4 and a weight average molecular weight (Mw) of 300
And the relationship between the weight average molecular weight (Mw ′) measured by the light scattering method and the radius of gyration <Rg ² > ^1/2 (Å) is expressed by the formula <Rg ² > ¹ There is provided an ethylene-based copolymer characterized by satisfying ^{/ 2} ≧ 4.00 × (Mw ′) ^0.372 .

The present invention also provides (a) ethylene,
(B) An ethylene-based copolymer obtained from at least one selected from an α-olefin having 3 to 20 carbon atoms, a diene compound and a cyclic olefin, wherein the above (1)
~ (3) satisfy the condition, (4) temperature 190 ℃
In the storage elastic modulus (G ') curve in the frequency dependence of the dynamic viscoelasticity measured in step ₁ , the frequency corresponding to the elastic modulus 10 ³ dyne / cm ² is ω ₁ , and the frequency corresponding to the elastic modulus 10 ⁵ dyne / cm ² is when was the omega _2, wherein _{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 / dyne)] satisfies the formula 1 × 10 ⁻⁶ <Je ⁰ <1 × 10 ⁻² , and (6) a stress of 5 × 10 ⁴ dyne was applied in the creep behavior at a temperature of 190 ° C. , The elastic recovery strain (γ _r ) after the application is stopped is 5 to 1500%
The present invention provides a blow-molded product or sheet obtained by molding the above-mentioned copolymer.

The ethylene-based copolymer of the present invention is a copolymer of (a) ethylene and (b) at least one selected from α-olefins having 3 to 20 carbon atoms, diene compounds and cyclic olefins. Is. In this copolymer,
(B) 3 to 2 carbon atoms used as a comonomer of the component
Examples of the α-olefin of 0 include 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. Further, a conjugated diolefin or a non-conjugated diolefin can be used as the diene compound. Examples of conjugated diolefins include 1,3-butadiene; isoprene; chloroprene; 1,3-cyclohexadiene; 1,3-cyclooctadiene. Furthermore, examples of non-conjugated diolefins include 1,5
-Hexadiene; α, ω- such as 1,7-octadiene
Examples thereof include diene compounds and derivatives thereof, norbornadiene; dicyclopentadiene; 5-vinylnorbornene; 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, and α-olefin having 3 to 20 carbon atoms is particularly preferable.

When the ethylene copolymer of the present invention is a copolymer of ethylene and α-olefin and / or cyclic olefin, the content of all comonomer units is such that the copolymer has desired properties. Therefore, the range of 1 to 20 mol% is preferable. When the ethylene-based copolymer uses at least a diene compound as a comonomer, the content of the diene compound unit in the ethylene-based 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% or less. Further, 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 should 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. The 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 forming a press sheet at a temperature of 190 ° C., quenching it, and measuring it by a density gradient tube method. Next, (2) the weight average molecular weight (M) in terms of polyethylene measured by gel permeation chromatography method (GPC method)
The ratio Mw / Mn of w) to the number average molecular weight (Mn) is 1.5 to
4 and Mw of 3000 to 1000000
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 of molding processability and physical properties, the preferable Mw / Mn is in the range of 1.8 to 3.8,
The range of 2.0 to 3.5 is particularly preferable. Also, Mw is 30
If it is less than 00, sufficient mechanical properties cannot be obtained, and 10,000
If it exceeds 00, the moldability is deteriorated. From the viewpoint of the balance of mechanical properties and molding processability, the preferable Mw is 100.
The range is from 00 to 800,000, especially from 15000 to 6
A range of 00000 is preferred. The above Mw and M
n is a device: Waters ALC / GPC 150C,
Column: TSK HM + GMH6 × 2, flow rate: 1.0 ml / min, solvent: 1,2,4-trichlorobenzene, measurement temperature: polyethylene conversion value determined by GPC method under the conditions of 135 ° C. The comonomer content is ¹ H using JSK-400 manufactured by JEOL Ltd.
-NMR measurement (400 MHz, measurement temperature: 130 ° C,
Solvent: 1,2,4-trichlorobenzene / heavy benzene)
Then, the peak intensity ratio of the methyl group and the methylene group was determined.

Further, (3) measurement by a light scattering method
Weight average molecular weight (Mw ') and radius of gyration <Rg^Two>
^1/2The relationship with (Å) is the formula <Rg^Two>^1/2≧ 4.00 × (Mw ')^0.372 It is necessary to satisfy the relationship. <Rg^Two>^1/2of
Value is 4.00 x (Mw ')^{0. 372}Molecular weight if smaller
The cloth is narrow and has no higher molecular weight components. Mw 'is 1x
10^FourIn the above case, the relation between Mw ′ and Rg is expressed by the formula <Rg^Two>^1/2≧ 3.28 × (Mw ')^0.394 It is preferable to satisfy Measurement by light scattering method
Was performed according to the method described below. That is, Otsukaden
Uses a dynamic light scattering photometer (DLS 7000) made by a child company.
A He-Ne laser (wavelength 632.8 nm) as a light source
Then, the solvent α-chloronaphthalene, the measurement temperature of 135 ℃
Total scattering intensity in the scattering angle range of 20 to 150 degrees under the conditions
Was measured. And weight average molecular weight (Mw ') and inertia
Square radius <Rg ^Two>^1/2Was calculated from Zimm Plot.

The preferred ethylene-based copolymer of the present invention satisfies all the above conditions (1) to (3) and (4) in the frequency dependence of the dynamic viscoelasticity measured at a temperature of 190 ° C. In the storage modulus (G ') curve,
When 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 x (Mw / M
n) and 3 ≦ ω ₂ / (ω ₁ × 10) ≦ 100 can be mentioned. ω ₂ /
(Ω ₁ × 10) is [−1.35 + 1.66 × (Mw / M
n)], the amount of the low molecular weight component is large and the processability is deteriorated. When ω ₂ / (ω ₁ × 10) is less than 3, the moldability is poor, and when it exceeds 100, the non-Newtonian property is increased, but the parison drop time during blow molding becomes long and the moldability becomes inconvenient. . From the viewpoint of molding processability and elastic term, it is 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 this dynamic viscoelasticity was measured by using RMS800 manufactured by Rheometrics and inserting a sample between parallel plates or cone plates to obtain a temperature of 190.
℃, linear range below 10% strain, frequency 0.01-100
It was measured under the condition of rad / sec range.

The more preferable ethylene-based copolymer of the present invention is that, while satisfying all the above conditions (1) to (4), (5) the creep behavior measured by changing the stress at a temperature of 190 ° C. An example is one in which the obtained steady-state compliance [Je ⁰ (cm ² / dyne)] satisfies the formula 1 × 10 ⁻⁶ <Je ⁰ <1 × 10 ⁻² . This Je
^{When 0} is 1 × 10 ⁻⁶ cm ² / dyne or less, spinnability is excellent, but drawdown and neck-in cannot sufficiently satisfy the required processing characteristics. 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, are excellent in processing characteristics, and are suitable for use in blow-molded products, pipes, etc. 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, and} more preferably 3 × 10 ⁻⁵ ≦ Je ⁰ <1 × 10 ⁻² . The steady compliance Je ⁰ is a value obtained by the method described below. That is, Rheometrics dynamic stress rheometer (DSR2
00), and the applied stress at 190 ° C. is 100 to 5 × 1.
The creep behavior is measured by arbitrarily changing it within the range of 0 ⁴ dyne. The compliance [Je (cm ² / dyne)] was calculated from each creep behavior, and the value independent of stress (showing a constant value) was calculated as the steady-state compliance [Je ⁰ (c
m ² / dyne)].

Particularly preferred ethylene-based copolymers of the present invention satisfy all of the above conditions (1) to (5) and (6) 5 × 10 ⁴ dyne in creep behavior at a temperature of 190 ° C. When the above stress is applied, the elastic recovery strain (γ _r ) after the application is stopped is in the range of 5 to 1500%. If this γ _r is less than 5%, the shape cannot be maintained in the molten state, and the moldability is poor. If it exceeds 1500%, the molding cycle property in the molten state becomes long, which causes problems. From the viewpoint of the balance between molding processability and molding cycle property, the preferable range of γ _r is 10 to 1400%, and the range of 15 to 1300% is particularly preferable. The elastic recovery strain (γ _r ) is a value obtained by the method described below. That is, Rheometrics dynamic stress rheometer (DS
R200) at a temperature of 190 ° C. and a stress of 5 × 10 ⁴
Dyne is applied (application time: 10 seconds), and the amount of strain at which the recovery is in equilibrium after the application is stopped is the elastic recovery strain (γ _r ). In addition,
This elastic recovery strain corresponds well with the die swell value used as a general elastic term evaluation. Further, the ethylene-based copolymer of the present invention usually has the following characteristics. That is, in general, when the copolymerization of α-olefin and ethylene proceeds, there are two insertion directions of the α-olefin component, but it is known that when an ordinary metallocene catalyst is used, the α-olefin component is inserted from only one direction. Therefore, heterogeneous bonds such as inversion bonds are not observed. On the contrary,
In the ethylene-based copolymer of the present invention, a heterogeneous bond such as an inversion bond is usually observed in the nuclear magnetic resonance spectrum ( ¹³ C-NMR) of isotope carbon.

The present invention also provides a blow-molded product or sheet obtained by molding the ethylene-based copolymer of the present invention satisfying all the above conditions (1) to (6). The blow-molded product of the present invention is obtained by adding various additives to the ethylene-based copolymer, if desired, 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 can be obtained by blending agents and the like and performing blow molding. The blow molding method is not particularly limited, and a method conventionally used for blow molding of conventional polyethylene resins can be used. On the other hand, in the sheet of the present invention, the above ethylene-based copolymer is optionally blended with the above-mentioned various additive components, further, an anti-blocking agent, an anti-fog agent, etc. , 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 multi-layer structure, and the thickness thereof is not particularly limited, but is usually in the range of 10 μm to 3 mm. Therefore, the sheet of the present invention includes a so-called film. The sheet formed in this manner is subjected to, for example, a dry laminating method or an extrusion laminating method (sandwich laminating method), nylon, polyethylene terephthalate, ethylene-vinyl alcohol copolymer, or the like, or a barrier material metal such as aluminum (a vapor deposition film). Alternatively, it can be used as a composite sheet such as a laminated sheet or a laminated sheet by laminating it with a foil) via an adhesive or a polyolefin resin. At this time, the sheet of the present invention is preferably used as a heat seal layer.

The method for producing the ethylene-based 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-based copolymer of the present invention, as a polymerization catalyst, (A) general formula (I) CpML ₃ ... (I) [In the formula, M represents titanium, zirconium or hafnium, Cp is a cyclopentadienyl or cyclic compound group having a substituted cyclopentadienyl skeleton and having 5 to 30 carbon atoms, L represents a σ ligand, and three Ls may be the same or different from each other. ] A transition metal compound represented by
A polymerization catalyst containing (B) an aluminum oxy compound and (C) a phenolic compound and / or water is preferably used.

In this polymerization catalyst, the transition metal compound as the component (A) is represented by the above general formula (I). In this 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 through a π bond in a η ⁵ -bonding manner.
Is a cyclic compound group, and L is a σ ligand coordinated to M by a bond. As this σ ligand, for example,
R ', OR', SR ', SO ₃ R', NR'R ", P
R'R ", NO ₂ , halogen atom, 1-pyrrolyl and 1
Preference is given to pyrrolidinyl. Here, R ′ and R ″ are a hydrocarbon group having 1 to 20 carbon atoms or a silyl group containing a hydrocarbon group, and at least one of the σ ligands is OR ′, NR′R ″ or PR′R. It is preferable that each of the three L's is the same or different.

There is one group consisting of a cyclic compound having 5 to 30 carbon atoms and having a cyclopentadienyl or substituted cyclopentadienyl skeleton which is coordinated by a π bond in the above M and η ⁵ -bonding mode, Further, the substituents on the substituted cyclopentadienyl skeleton may bond with each other 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. Further, in the above R ′ and R ″, the number of carbon atoms is 1-2.
Examples of the hydrocarbon group of 0 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 methoxy group, ethoxy group, n-propoxy group,
Isopropoxy group, n-butoxy group, isobutoxy group,
sec-butoxy group, t-butoxy group, pentoxy group,
Examples thereof include alkoxy groups such as hexoxy group, octoxy group and cyclohexoxy group, aryloxy groups such as phenoxy group and the like. Specific examples of SR 'include a methylthio group, an ethylthio group, a cyclohexylthio group and a phenylthio group. Then, 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 sec-butanesulfonyl group, t-butanesulfonyl group, isobutanesulfonyl group and other alkylsulfonyl groups, and benzenesulfonyl group and other arylsulfonyl groups. Further, specific examples of NR'R "include 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, dioctylamino group, diphenylamino group, dibenzylamino Group, methylethylamino group, (t-butyl) trimethylsilylamino group, methyltrimethylsilylamino group and the like. In addition, specific examples of PR′R ″ include a dimethylphosphido group, a diethylphosphido group, a di (n-propyl) phosphido group, a diisopropylphosphido group, a di (n-butyl) phosphido group,
Diisobutylphosphido group, di (sec-butyl) phosphido group, di (t-butyl) phosphido group, dipentylphosphido group, dihexylphosphido group, dioctylphosphido group, diphenylphosphido group,
Dibenzylphosphido group, methylethylphosphido group, (t-butyl) trimethylsilylphosphido 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); cyclopentadiene. Cyclopentadienyl titanium tri (n-butyl); cyclopentadienyl titanium triisobutyl; cyclopentadienyl titanium tri (sec-butyl); cyclopentadienyl titanium tri (t-butyl); methyl 1,2-dimethylcyclopentadienyl titanium trimethyl; 1,2,4-trimethylcyclopentadienyl titanium trimethyl; 1,2,3,4-tetramethylcyclopentadienyl titanium trimethyl; Pentamethylcyclope 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; Pentadienyl titanium trimethoxide; (n-butyl) cyclopentadienyl titanium trimethoxide; dimethylcyclopentadienyl titanium trimethoxide; dimethylcyclopentadienyl titanium triethoxide; dimethylcyclopentadienyl titanium tri ( n-propoxide); dimethylcyclopentadienyl titanium triisopropoxide; dimethyl cyclopentadienyl titanium triphenoxide; di (t
-Butyl) cyclopentadienyl titanium trimethoxide; di (t-butyl) cyclopentadienyl titanium triethoxide; di (t-butyl) cyclopentadienyl titanium tri (n-propoxide); di (t- Butyl) cyclopentadienyl titanium triisopropoxide; di (t
-Butyl) cyclopentadienyl titanium triphenoxide; bis (trimethylsilyl) cyclopentadienyl titanium trimethoxide; bis (trimethylsilyl) cyclopentadienyl titanium triethoxide; bis (trimethylsilyl) cyclopentadienyl titanium tri (n- Propoxide); bis (trimethylsilyl) cyclopentadienyl titanium triisopropoxide; bis (trimethylsilyl) cyclopentadienyl titanium triphenoxide; trimethylcyclopentadienyl titanium trimethoxide; trimethylcyclopentadienyl titanium triethoxide; Trimethylcyclopentadienyl titanium tri (n-propoxide); Trimethylcyclopentadienyl titanium triisopropoxide; Trimethylcyclopentadienyl titanium tri Enoxide; triethylcyclopentadienyl titanium trimethoxide; [bis (dimethylsilyl), methyl] cyclopentadienyl titanium trimethoxide; [di (t-butyl, methyl)] cyclopentadienyl titanium 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; Tetramethyl cyclopentadienyl titanium tri (sec-butoxide); Tetramethyl cyclopentadienyl tita Tri (t-butoxide); tetramethylcyclopentadienyl titanium triphenoxide; [tetramethyl, 4-methoxyphenyl] cyclopentadienyl titanium trimethoxide; [tetramethyl, 4-methoxyphenyl] cyclopentadienyl titanium tri Ethoxide; [Tetramethyl, 4-methoxyphenyl] cyclopentadienyl titanium tri (n-propoxide); [Tetramethyl, 4-methoxyphenyl] cyclopentadienyl titanium triisopropoxide; [Tetramethyl, 4- Methoxyphenyl] cyclopentadienyl titanium triphenoxide;
[Tetramethyl, 4-methylphenyl] cyclopentadienyl titanium trimethoxide; [Tetramethyl, 4-methylphenyl] cyclopentadienyl titanium triethoxide; [Tetramethyl, 4-methylphenyl] cyclopentadienyl titanium 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] cyclopentadienyl titanium triethoxide; [Tetramethyl, 2-
Methoxyphenyl] cyclopentadienyl titanium triphenoxide; [Tetramethyl, ethyl] cyclopentadienyl titanium trimethoxide; [Tetramethyl, ethyl] cyclopentadienyl titanium triethoxide; [Tetramethyl, ethyl] cyclopentadioxide Phenyl titanium tri (n-propoxide); [tetramethyl, ethyl] cyclopentadienyl titanium triisopropoxide; [tetramethyl, ethyl] cyclopentadienyl titanium triphenoxide; [tetramethyl, n-butyl] cyclopenta Dienyl titanium trimethoxide; [tetramethyl, n
-Butyl] cyclopentadienyl titanium triethoxide; [tetramethyl, n-butyl] cyclopentadienyl titanium tri (n-propoxide); [tetramethyl,
[n-butyl] cyclopentadienyl titanium triisopropoxide; [tetramethyl, n-butyl] cyclopentadienyl titanium triphenoxide; [tetramethyl, phenyl] cyclopentadienyl titanium trimethoxide;
[Tetramethyl, phenyl] cyclopentadienyl titanium triethoxide; [Tetramethyl, phenyl] cyclopentadienyl titanium triphenoxide; [Tetramethyl, trimethylsilyl] cyclopentadienyl titanium 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);
Pentamethylcyclopentadienyl titanium tris (diethylamide); cyclopentadienyl titanium tri (nitro); pentamethylcyclopentadienyl titanium tri (nitro), etc., and compounds in which titanium in these compounds is replaced with zirconium or hafnium Can be mentioned.

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) cyclopentadienyl titanium monochlorodimethoxide; Bis (trimethylsilyl) cyclopentadienyl titanium monochlorodimethoxide; Trimethylcyclopentadienyl titanium monochlorodimethoxide;
Trimethylcyclopentadienyl titanium monochlorodiphenoxide; triethylcyclopentadienyl titanium monochlorodimethoxide; [bis (dimethylsilyl), methyl] cyclopentadienyl titanium monochlorodimethoxide; tetramethylcyclopentadienyl titanium monochlorodimethoxide; tetra Methylcyclopentadienyl titanium dichloromonomethoxide; Tetramethylcyclopentadienyl titanium monochlorodi (n-butoxide);
Tetramethylcyclopentadienyl titanium monochloroisobutoxide; Tetramethylcyclopentadienyl titanium monochlorolog (sec-butoxide); Tetramethylcyclopentadienyl titanium monochlorolog (t-butoxide); [Tetramethyl, 4-methoxyphenyl ] Cyclopentadienyl titanium monochlorodimethoxide;
[Tetramethyl, 4-methylphenyl] cyclopentadienyl titanium monochlorodimethoxide; [Tetramethyl, benzyl] cyclopentadienyl titanium monochlorodimethoxide; [Tetramethyl, benzyl] cyclopentadienyl titanium monochlorodiphenoxide; [Tetra Methyl, 2-methoxyphenyl] cyclopentadienyl titanium monochlorodimethoxide; [Tetramethyl, ethyl] cyclopentadienyl titanium monochlorodimethoxide; [Tetramethyl, ethyl] cyclopentadienyl titanium monochlorodiethoxide; [Tetramethyl , N-Butyl] cyclopentadienyl titanium monochlorodiethoxide; [Tetramethyl, n-butyl] cyclopentadienyl titanium monochlorodiethyl (n-propoxide); [Tetramethyl, n-butyl ] Cyclopentadienyl titanium monochlorodiisopropoxide; [Tetramethyl, phenyl] cyclopentadienyl titanium monochlorodimethoxide; [Tetramethyl, trimethylsilyl] cyclopentadienyl titanium monochlorodimethoxide; pentamethylcyclopentadienyl titanium monochloro Dimethoxide;
Pentamethylcyclopentadienyl titanium dichloromonomethoxide; pentamethylcyclopentadienyl titanium monochlorodiethoxide; pentamethylcyclopentadienyl titanium monochlorodioxide (cyclohexoxide); pentamethylcyclopentadienyl titanium monochlorodiphenoxide; Indenyl titanium monochlorodimethoxide; cyclopentadienyl titanium monochlorodimethane (methanesulfonyl); pentamethylcyclopentadienyl titanium monochlorobis (diethylamide); pentamethylcyclopentadienyl titanium monochlorobis [di (n-butyl) amide] Pentamethylcyclopentadienyl titanium dichloro (dimethylamide); pentamethylcyclopentadienyl titanium dichloro (diphenylamide);
Pentamethylcyclopentadienyl titanium dichloro (methylethylamide); Pentamethylcyclopentadienyl titanium dichloro (t-butyltrimethylsilylamide); Pentamethylcyclopentadienyl titanium dimethoxy (diphenylamide); Pentamethylcyclopentadienyl titanium Monochlorobis (diethylphosphide); pentamethylcyclopentadienyl titanium monochlorobis [di (n-butyl) phosphide]; pentamethylcyclopentadienyl titanium dichloro (dimethylphosphide); pentamethylcyclopentadienyl titanium dimethoxy ( Dimethyl phosphide); pentamethylcyclopentadienyl titanium dichloro (diphenyl phosphide); pentamethyl cyclopentadienyl titanium dichloro (methyl ethyl) ); Pentamethylcyclopentadienyl titanium dichloro (t-butyltrimethylsilyl phosphide); pentamethyl cyclopentadienyl titanium trichloride; pentamethyl cyclopentadienyl titanium dimethoxy (diphenyl phosphide), etc. In addition, instead of titanium in the compound, the corresponding compounds containing zirconium and hafnium can be mentioned. 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) has the general formula (II)

[0022]

Embedded image

[Wherein R ¹ is an alkyl group, an alkenyl group, an aryl group having 1 to 20 carbon atoms, 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. ] A chain aluminoxane represented by the general formula (II
I)

[0024]

Embedded image

[In the formula, R ¹ is the same as above, p is the degree of polymerization, and is an integer of usually 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 and a condensing agent such as water are brought into contact with each other, but the means therefor 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, water of crystallization contained in a metal salt, etc. There are a method of reacting adsorbed water of an inorganic substance and an organic substance with an organoaluminum compound, a method of reacting a tetraalkyldialuminoxane with a trialkylaluminum, and further reacting with 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) Copolymerized alkylaluminoxane obtained by mixing two or more kinds of alkylaluminum (organoaluminum) compounds in a predetermined ratio during the production by the above-mentioned methods (1), 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 combination of two or more. Further, among aluminoxanes, alkylaluminoxanes are particularly preferred. In the aluminoxane thus obtained, the alkylaluminum that is the starting material for its synthesis may remain and may be contained as an impurity.
It can be used as is.

In this polymerization catalyst, the activity is further improved.
Phenolic compound as component (C) for the purpose of improving
And / or water can be used, especially phenol
Suitable compounds are preferred. As this phenolic compound
Is an aromatic group such as a benzene ring or naphthalene ring.
A hydrogen atom bonded to the ring has at least one hydroxyl group or
Other than at least one hydroxyl group and at least one hydroxyl group
The compound substituted by the substituent of can be mentioned. This
Here, examples of the substituent other than the hydroxyl group include 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
Group, alkyl group, cycloalkyl group, aryl group,
For example, Ralkyl group. 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 and dodecyl groups as cycloalkyl groups
Is, for example, a cyclopentyl group or a cyclohexyl group.
Examples of the aryl group include phenyl group and tolyl group.
Examples of the aralkyl group include a benzyl group.
And a phenethyl group. OR^TwoUtensils
Examples of the body include methoxy group, ethoxy group, and n-propoxy group.
Si group, isopropoxy group, n-butoxy group, isobutoxy group
Si group, sec-butoxy group, t-butoxy group, pentoxy group
Si group, hexoxy group, octoxy group, cyclohexoxy
Alkoxy groups such as groups, aryloxy groups such as phenoxy groups
Si group and the like can be mentioned. NR ^TwoR^ThreeWith a concrete example of
Then, 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
Cylamino group, diphenylamino group, dibenzylamino
A group etc. can be mentioned. Also, as a halogen atom
Examples include chlorine, bromine, iodine, and fluorine.
You.

As the component (C), a phenolic compound and / or water is used. Here, the phenolic compound is preferably a phenolic compound substituted with a hydrocarbon group having 1 to 20 carbon atoms, and particularly 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; 2
-Sec-butylphenol; 2-tert-butylphenol; 3-tert-butylphenol; 4-te
rt-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
-Butylphenol; 2-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-)
6-tert-butylphenol); 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; 3- 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; hydroquinone;
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 and the like. These phenolic compounds may be used alone or in combination of two or more.

The ratio of the component (A) and the component (B) used in this polymerization catalyst is usually such that the molar ratio of the aluminum oxy compound of the component (B) (in terms of aluminum) / the transition metal compound of the component (A) is 1. It is selected to be in the range of 10,000. If this 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 a large amount remains in the obtained polymer. From the viewpoint of activity, economy, quality of the obtained polymer, etc., the preferable molar ratio is 10 to 50.
The range is 00, and the range from 20 to 2000 is particularly preferable.

Further, the phenolic compound and / or water as the component (C) have a molar ratio of the hydroxyl group in the component (C) / the aluminum oxy compound of the component (B) (in terms of aluminum).
It is preferable to use it in the range of 0.001 to 0.8. If this molar ratio is less than 0.001, the activity improving effect is insufficient, and if it exceeds 0.8, the activity tends to decrease. From the viewpoint of improving the activity, a more preferable molar ratio is in the range of 0.01 to 0.6, 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. Further, the order of contacting each catalyst component is not particularly limited, but after the component (B) and the component (C) are contacted, the component (A) is contacted, or the component (B) and the component (A) are contacted. From the viewpoint of catalytic activity, it is preferable to bring the component (C) into contact with the above.

The polymerization catalyst may contain other catalyst components, if desired, in addition to the components (A), (B) and (C) as long as the object of the present invention is not impaired. You may let me. 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 slurry polymerization method, high temperature solution polymerization method, gas phase polymerization method, bulk polymerization method and the like can be adopted. 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 usually 0 to 3
It 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 usually 0 to
150kg / cm ² G, preferably selected in the range of 0~100kg / cm ² G.

The ratio of the catalyst used to the raw material monomer is
The raw material monomer / component (A) (molar ratio) is preferably in the range of 1 to 10 ⁸ , particularly 100 to 10 ⁵ . The polymerization time is usually about 5 minutes to 10 hours. The method for controlling the molecular weight of the polymer includes the selection of the type and amount of each catalyst component, the polymerization temperature, and further the 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 decalin at 135 ° C) is 0.1 deciliter /
It is preferably at least g, particularly preferably at least 0.2 deciliter / g.

In the present invention, prepolymerization can be carried out using the above-mentioned 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 ethylene and the same ones as those exemplified above, for example, α having 3 to 20 carbon atoms can be used.
-Olefin, or a mixture thereof can be mentioned, but it is advantageous to use the same olefin as that used in the polymerization. The prepolymerization temperature is usually -20 to 200 ° C, preferably -10 to 1
It 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 [η] (135) of the prepolymerized product is
C. decalin) of 0.2 deciliter / g or more, especially 0.5 deciliter / g or more, transition metal component 1 in the catalyst 1
The amount of prepolymerized product per millimole is 1 to 10
It is desirable to adjust the conditions so that the amount is 000 g, particularly 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 methylaluminoxane toluene solution (manufactured by Albemarle) having a concentration of 1.4 mol / liter (as Al atom) was added to A
0.2 mol was used as 1 atom, and nitrogen containing water was introduced into this at room temperature with stirring. The introduction was gradually performed over 16 hours, and 0.16 times mol of water was introduced with respect to Al atoms. Then, the reaction was carried out for 5 hours to obtain an aluminum catalyst component. (2) Production of ethylene / octene-1 copolymer In a pressure-resistant autoclave with an agitator having an internal capacity of 4 liters,
Under a nitrogen atmosphere, 1560 ml of toluene, 40 ml of octene-1 and 4 mmol (as Al atom) of methylalnoxane 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 atom, and the temperature was raised to 65 ° C. Hydrogen
Charge 1.0 kg / cm ² G and ethylene 4 kg / cm ² G
Was continuously introduced while maintaining a constant pressure at, and a copolymerization reaction was carried out at 65 ° C. for 30 minutes. After finishing the reaction, depressurizing,
After deactivating with alcohol, the copolymer was recovered and dried to obtain 76 g of an ethylene / octene-1 copolymer. (3) Evaluation of Copolymer The copolymer obtained in (2) above was evaluated. Table 1 shows the results.

Example 2 (1) Production of ethylene / octene-1 copolymer In Example 1- (2), the hydrogen charging pressure was 0.2 kg.
/ cm ² G, Example 1-except that the polymerization temperature was changed to 90 ℃
The same procedure as in (2) was carried out to obtain 104 g of a copolymer. (2) Evaluation of Copolymer The copolymer obtained in (1) above 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 hydrogen charging pressure was 0.5 kg / c.
Example 1-except that m ² G and the polymerization temperature were 90 ° C.
The same procedure as in (2) was carried out to obtain 114 g of a copolymer. (2) Evaluation of Copolymer The copolymer obtained in (1) above was evaluated. The result is
It is shown in the table.

Comparative Example Sample A (hexene-1 unit content 1.8 mol%) which is an ethylene / hexene-1 copolymer, 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 were evaluated. Table 1 shows the results.

[0040]

[Table 1]

[0041]

[Table 2]

[0042]

Industrial Applicability The ethylene-based copolymer of the present invention can provide a molded product having excellent molding processing characteristics and high mechanical strength, such as a blow molded product or a sheet.
Since this ethylene-based copolymer can particularly reduce the processing load energy, it can be expected to expand the fields of application.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Mitsuru Kanzawa 1280, Kamizumi, Sodegaura-shi, Chiba Idemitsu Kosan Co., Ltd.

Claims (5)

[Claims] (1) ethylene and (b) a carbon number of 3 to 2.
An ethylene-based copolymer obtained from at least one selected from an α-olefin, a diene compound and a cyclic olefin of 0, (1) a resin density of 0.85 to 0.9
It is in the range of 5 g / cm ³ , and (2) the weight average molecular weight (Mw) and the number average molecular weight (M) in terms of polyethylene measured by gel permeation chromatography method.
n), the ratio Mw / Mn is in the range of 1.5 to 4, and the weight average molecular weight (Mw) is in the range of 3,000 to 1,000,000, and (3) the weight average molecular weight measured by the light scattering method ( Mw ') and radius of inertia <Rg ² > ^1/2 (Å)
The ethylene-based copolymer is characterized by satisfying a relation of <Rg ² > ^1/2 ≧ 4.00 × (Mw ′) ^0.372 . (4) In a storage elastic modulus (G ') curve in the 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 ω ₁ ,
When 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 3 ≦ ω ₂ / (ω ₁ × 10) ≦ 100, the ethylene copolymer according to claim 1. (4) In a storage elastic modulus (G ') curve in the 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 ω ₁ ,
When 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 3 ≦ ω ₂ / (ω ₁ × 10) ≦ 100, and (5) steady-state compliance [Je ⁰ (cm ² / dyne)] satisfies the formula 1 × 10 ⁻⁶ <Je ⁰ <1 × 10 ⁻² . 2. The ethylene-based copolymer according to claim 1, wherein 4. A storage elastic modulus (G ′) curve in the frequency dependence of dynamic viscoelasticity measured at a temperature of 190 ° C., wherein a frequency corresponding to an elastic modulus of 10 ³ dyne / cm ² is ω ₁ ,
When 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 3 ≦ ω ₂ / (ω ₁ × 10) ≦ 100, and (5) steady-state compliance [Je ⁰ (cm ² / dyne)] satisfies the formula 1 × 10 ⁻⁶ <Je ⁰ <1 × 10 ⁻² , and (6) a stress of 5 × 10 ⁴ dyne was applied in the creep behavior at a temperature of 190 ° C. In this case, the elastic recovery strain (γ _r ) after the application is stopped is 5 to 1500
%, The ethylene-based copolymer according to claim 1. 5. A blow-molded body or sheet formed by molding the ethylene-based copolymer according to claim 4.