JPH0859723A - Ethylenic polymer and its production - Google Patents

Abstract

PURPOSE: To obtain the subject polymer, having a sufficiently high melt tension and elongational viscosity in strain curing and excellent in uniform wall thickness and shape stability of a molded resin. CONSTITUTION: This polymer contains Zr, Al or B, has >=2.0 to <6.0 value of λ indicating the magnitude of the nonlinearity of the elongational viscosity [λ1 /λ0 ) (λ0 is the elongational viscosity at the displacement point; λ1 is the elongational viscosity when the strain is twice based on that at the displacement point)] and preferably plural nonconjugated vinyl type double bonds and comprises 0.05-2wt.% 5-80C polyvalent salt. The polymer is obtained by carrying out the polymerization using a catalyst system comprising at least one metallocene compound of formula I to III [R<1> to R<10> are each H, a 1-20C alkyl, etc.; R<11> is a 1-10C alkylene, etc.; Q<1> and Q<10> are each H, a 1-20C aryl, etc.; Y is O, S, etc. ; Me is a group III to VI transition metal of the periodic table; (p) is 0 or 1] and an aluminoxane compound or a noncoordinating ionic compound.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an ethylene polymer having a large non-linearity in melt tension and extensional viscosity and a method for producing the same. More specifically, the present invention relates to an ethylene polymer in which the melting characteristics of conventional polyethylene are improved, and the molding resin has excellent levelness and shape stability, and a method for producing the same.

[0002]

2. Description of the Related Art Ethylene polymers have been provided for various uses, and the required properties differ depending on the molding method and uses. For example, in high-speed molding of an inflation film, a sufficiently large melt tension and elongational viscosity at the time of strain hardening are required to perform stable molding in which bubble fluctuation and breakage are prevented and uniform thickness is maintained. Further, these melting characteristics are required to prevent neck-in and drawdown at the time of T-die molding, and to minimize tearing and drawdown at the time of hollow molding and to maintain uniform thickness and shape stability.

The low density polyethylene produced by the high pressure method has a large melt tension and is excellent in film, lamination and blow moldability, but is inferior in mechanical properties and heat resistance. The linear ethylene polymer obtained by the medium / low pressure method using a Ziegler catalyst is excellent in mechanical properties and heat resistance, but is inferior in various moldability because of insufficient melt tension. A method for improving melting characteristics is disclosed in JP-A-56-908.
10 or JP-A-60-106806. However, since the ethylene-based polymer generally obtained using a Ziegler-based catalyst has a wide composition distribution, the low-molecular weight component causes problems such as smoke generation and stickiness during film formation.

On the other hand, it is general that an ethylene polymer having a narrow molecular weight distribution and a narrow composition distribution can be obtained by using a metallocene catalyst. A method has been proposed in which a metallocene catalyst is used and the composition distribution is narrow and the melt tension is improved. For example, Japanese Patent Application Laid-Open No. 4-213306 discloses a method of copolymerizing ethylene with an α-olefin such as 1-butene, and Japanese Patent Laid-Open No. 1-50163 discloses a method of copolymerizing ethylene with 1,3-butadiene. Flat 4-506372
Has proposed a method of copolymerizing ethylene and 1,4-hexadiene. However, these methods do not sufficiently improve the melting characteristics when a small amount of comonomer branch or crosslinked structure is introduced. If introduced in a large amount, the mechanical properties inherent to the polymer will be deteriorated, and gelation will be a problem. In addition, since a sufficient elongational viscosity is not developed during strain hardening during molding, the uniformity and shape stability of the molding resin are poor.

Further, there has been proposed a method of introducing a crosslinked structure by post-treating a polymer to improve melting characteristics. A method of introducing a crosslinked structure by mixing an organic peroxide and performing heat treatment is generally performed. As a method of mixing the organic peroxide, a method of dissolving the polymer in an organic solvent in which the polymer is soluble, mixing the organic peroxide therein, and then removing the solvent, or dissolving the organic peroxide in the organic solvent A method of immersing the polymer therein and then removing the organic solvent is used. However, these methods are not economical because a large amount of organic peroxide is required to introduce an effective crosslinked structure and a step of removing the solvent is required.

On the other hand, a method of irradiating an electron beam to introduce a crosslinked structure is also common. However, while cross-linking is promoted by electron beam irradiation, deterioration of the polymer also occurs in parallel and the original characteristics of the polymer are likely to be impaired. Further, a complicated process for electron beam irradiation is required, which is not economical.

[0007]

SUMMARY OF THE INVENTION The object of the present invention is to solve the above problems in the prior art and to provide an ethylene polymer having a sufficiently large melt tension and elongation viscosity upon strain hardening, and an economical method for producing the same. To do.

[0008]

Means for Solving the Problems As a result of intensive studies to solve the above problems, the present inventors have found that ethylene and a small amount of polyvalent ene are copolymerized by using a specific metallocene catalyst. The present invention has been accomplished by finding that an ethylene-based polymer having a sufficiently high melt tension and elongational viscosity upon strain hardening can be obtained, and an effective production method thereof.

That is, the gist of the present invention is that it contains zirconium and aluminum or boron, and that the λ value (λ ₁ / λ ₀ ) showing the magnitude of the nonlinearity of extensional viscosity is 2.0 or more and less than 6.0. Characteristic ethylene polymer. Where [λ ₀
Is the extensional viscosity at the displacement point, and λ ₁ is the extensional viscosity when the strain is twice the strain at the displacement point. Displacement points are linear regions of elongational viscosity (small deformation region) and nonlinear regions (large deformation region).
Is the point of displacement. ] And at least non-conjugated vinyl-type double using a catalyst system comprising at least one metallocene compound represented by the general formula (1), (2) or (3) and an aluminoxane compound or a non-coordinating ionic compound. The method for producing an ethylene polymer as described above, which comprises polymerizing so as to contain 0.05 to 2% by weight of a polyvalent ene having two or more bonds and having 5 to 80 carbon atoms.

[Chemical 4]

[Chemical 5]

[Chemical 6] [Wherein R ^{1 to} R ¹⁰ are hydrogen or a hydrocarbon group (having 1 carbon atom).
To alkyl, alkenyl, aryl, alkylaryl, arylalkyl, etc.), an alkylsilylene group, an alkylgermanium group, or a 4- to 6-membered ring having a carbon-carbon bond, which may be the same or different. , R ¹¹ is an alkylene group having 1 to 20 carbon atoms, an alkylidene group, an alkylgermane group or an alkylsilylene group, and Q ¹ and Q ² are aryl, alkyl, alkenyl, alkylaryl, arylalkyl having 1 to 20 carbon atoms, etc. Hydrocarbon groups, alkoxy, allyloxy,
Siloxy, hydrogen or halogen, which may be the same or different, and Y is -O-, -S-, -NR.
¹² -, - PR ¹² - a whether, also -OR ^12, -SR ^12,
-NR ¹² R ¹³ , -PR ¹² R ¹³ (R ¹² and R ¹³ are hydrogen or a hydrocarbon group having 1 to 20 carbon atoms such as alkyl, alkenyl, aryl, alkylaryl, arylalkyl, or a halogenated alkyl or halogenated group. Is an aryl) and is a neutral electron-donating ligand, Me is a transition metal of Groups 3, 4, 5 and 6 of the Periodic Table, and p is 0 or 1. ] It is in.

The metallocene compound used in the present invention is
It is represented by the general formula (1), (2) or (3).

[Chemical 7]

Embedded image

[Chemical 9] [Wherein R ^{1 to} R ¹⁰ are hydrogen or a hydrocarbon group (having 1 carbon atom).
To alkyl, alkenyl, aryl, alkylaryl, arylalkyl, etc.), an alkylsilylene group, an alkylgermanium group, or a 4- to 6-membered ring having a carbon-carbon bond, which may be the same or different. , R11 is an alkylene group having 1 to 20 carbon atoms, an alkylidene group, an alkylgermane group or an alkylsilylene group, and Q ¹ and Q ² are aryl, alkyl, alkenyl, alkylaryl, arylalkyl having 1 to 20 carbon atoms. Hydrocarbon group, alkoxy, allyloxy,
Siloxy, hydrogen or halogen, which may be the same or different, and Y is -O-, -S-, -NR.
¹² -, - PR ¹² -, a is one, also -OR ^12, -S
^{R 12, -NR 12 R 13,} -PR 12 R 13 (R 12 and R ¹³ is an alkyl having 1 to 20 carbon hydrogen or carbon, alkenyl, aryl, alkylaryl hydrocarbon group or a halogenated alkyl such as arylalkyl Or an aryl halide) and Me is a transition metal of Groups 3, 4, 5 and 6 (according to the 1990 rules of inorganic chemistry nomenclature) of the Periodic Table. ,
p is 0 or 1. ]

In the above formula, R ^{1 to} R ¹⁰ are hydrogen or a hydrocarbon group (such as an alkyl, alkenyl, aryl, alkylaryl or arylalkyl having 1 to 20 carbon atoms) or 4 to 6 having a carbon-carbon bond. It is a member ring and may be the same or different. Examples of the hydrocarbon group as described above include a methyl group, an ethyl group, a propyl group, a butyl group, an isobutyl group, a tertiary butyl group, an amyl group, an isoamyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, and a decyl group. Group, cetyl group, phenyl group and the like, alkylsilyl group and trimethylsilyl group, and alkylgermyl group and the like. Examples of the above-mentioned cyclopentadienyl ligand include cyclopentadienyl group, methylcyclopentadienyl group, ethylcyclopentadienyl group, n-butylcyclopentadienyl group, t-butylcyclopentadienyl group. Alkyl-substituted cyclopentadienyl groups such as enyl group, trimethylsilylcyclopentadienyl group, dimethylcyclopentadienyl group, pentamethylcyclopentadienyl group, and indenyl group with or without similar substituents, fluorenyl group Etc. can be illustrated.

In the above formula, R ¹¹ is an alkylene group having 1 to 20 carbon atoms, alkylgermylene or alkylsilylene. Examples of the alkylene group include a methylene group, an ethylene group, a propylene group, an isopropylidene group, a cyclopentylidene group, a cyclohexylidene group, a tetrahydropyran-4-ylidene group, a diphenylmethylene group, and the like. , A dimethylsilylene group, a diphenylsilylene group, and the like, and an alkylgermylene group includes a dimethylgermylene group, a diphenylgermylene group, and the like. In the above formula, Q is aryl having 1 to 20 carbons, alkyl,
It is a hydrocarbon group such as alkenyl, alkylaryl, arylalkyl or halogen, which may be the same or different.

In the above formula, Y is --O--, --S--,-.
NR ¹² -, - PR ¹² - a either, also -OR ^12, -SR
It is an electron donor ligand consisting of ¹² , -NR ¹² R ¹³ , and -PR ¹² R ¹³ . Here, R ¹² and R ¹³ are hydrogen or a hydrocarbon group having 1 to 20 carbon atoms such as alkyl, alkenyl, aryl, alkylaryl, arylalkyl, or a halogenated alkyl or a halogenated aryl. Specifically, a methyl group, an ethyl group, a propyl group,
Examples thereof include a butyl group, an isobutyl group, a tertiary butyl group, an amyl group, an isoamyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, a cetyl group, a phenyl group and a benzyl group. In this, -NR ¹² -, -
PR ¹² - type ligand is preferred.

Specific examples of the transition metal compound represented by the general formula (1), (2) or (3) in the case where Me is zirconium will be illustrated below. As the transition metal compound represented by the general formula (1), biscyclopentadienyl zirconium dichloride, bis (methylcyclopentadienyl) zirconium dichloride, bis (n-butylcyclopentadienyl) zirconium dichloride, bis (n- Butylcyclopentadienyl) zirconium dimethyl, bis (1,3-dimethylcyclopentadienyl) zirconium dichloride, bis (pentamethylcyclopentadienyl) zirconium dichloride,
(Cyclopentadienyl) (methylcyclopentadienyl) zirconium dichloride, (cyclopentadienyl) (n-butylcyclopentadienyl) zirconium dichloride, (cyclopentadienyl) (indenyl)
Zirconium dichloride, (cyclopentadienyl)
Examples thereof include (fluorenyl) zirconium dichloride, cyclopentadienylzirconium trichloride, cyclopentadienylzirconium trimethyl, pentamethylcyclopentadienylzirconium trichloride, pentamethylcyclopentadienylzirconium trimethyl and the like.

As the transition metal compound represented by the general formula (2), dimethylsilylenebis (methylcyclopentadienyl) zirconium dichloride, isopropylidenebis (methylcyclopentadienyl) zirconium dichloride, ethylenebis (indenyl) ) Zirconium dichloride, ethylenebis (4,5,6,7, -tetrahydro-1-indenyl) zirconium dichloride, isopropylidene (cyclopentadienyl) (fluorenyl) zirconium dichloride, isopropylidene (cyclopentadienyl) (indenyl) Zirconium dichloride, isopropylidene (t-butylcyclopentadienyl) (t-butylindenyl) Zirconium dichloride, isopropylidene (t-butylcyclopentadienyl) (t-butyl Ndeniru) zirconium dimethyl and the like.

As the transition metal compound represented by the general formula (3), ethylene (t-butylamide) (tetramethylcyclopentadienyl) zirconium dichloride, ethylene (methylamido) (tetramethylcyclopentadienyl) zirconium Dichloride, dimethylsilylene (t-butylamide) (tetramethylcyclopentadienyl) zirconium dichloride, dimethylsilylene (t-butylamide) (tetramethylcyclopentadienyl) zirconium dibenzyl, dimethylsilylene (benzylamide) (tetramethylcyclopenta) (Dienyl)
Examples thereof include zirconium dibenzyl, dimethylsilylene (phenylamide) (tetramethylcyclopentadienyl) zirconium dichloride and the like. In the zirconium compound as described above, a transition metal compound in which zirconium is changed to hafnium or titanium can be used.

The aluminoxane compound and the non-coordinating ionic compound used for the polymerization will be described below.
The aluminoxane compound used in the present invention is an organoaluminum compound represented by the general formula (4) or the general formula (5).

General formula (4)

[Chemical 10] General formula (5)

[Chemical 11] R ¹⁴ is a methyl group, an ethyl group, a propyl group, a butyl group,
It is a hydrocarbon group such as an isobutyl group, preferably a methyl group. m is an integer of 4 to 100, preferably 6 or more and particularly 10 or more.

A method for producing a compound of this kind is known, for example, a salt having water of crystallization is obtained by adding trialkylaluminum to a hydrocarbon solvent suspension of (copper sulfate hydrate, aluminum sulfate hydrate). A method can be illustrated. The aluminoxane compound can be used by supporting it on a carrier such as silica, alumina or magnesium chloride. It is also possible to modify it so as to be suitable for each process. For example, when used in a non-liquid phase polymerization method, it can be modified with water or an electron donating compound.

The non-coordinating ionic compound is represented by the following formula. ^{(MX 1 X 2 X 3 X} 4) (nm) - · C (nm) + ( wherein, M is a metal selected from 5 to Group 15 in the periodic ^{table, X 1, X 2, X} 3, X ⁴ is a hydrogen atom, a dialkylamino group, an alkoxy group, an aryloxy group,
It represents an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an alkylaryl group, an arylalkyl group, a substituted alkyl group, a halogen-substituted aryl group, an organic metalloid group or a halogen atom. C is carbonium,
Indicates a counter cation such as ammonium. m is M
Is an integer of 1 to 7, and n is an integer of 2 to 8. )

Specific examples of these compounds include triethylammonium tetraphenylboron, tripropylammonium tetraphenylboron, tri (n-butylammonium tetraphenylboron, trimethylammonium tetra (p-tolyl) boron, tributylammonium tetrakis ( Pentafluorophenyl) borate, dimethylanilinium tetrakis (pentafluorophenyl) borate, triphenylcarbonium tetrakis (pentafluorophenyl) borate, tripropylammonium tetrakis (3,5trifluoromethylphenyl) borate, etc. can be exemplified. Preferably, triphenylcarbonium tetrakis (pentafluorophenyl) borate or dimethylanilinium tetrakis. Pentafluorophenyl) borate.

In the ethylene polymerization method of the present invention,
It is desirable to copolymerize a small amount of polyvalent ene. The polyvalent ene used for the polymerization has a plurality of non-conjugated vinyl groups and has at least two vinyl type double bonds and has 5 to 8 carbon atoms.
A polyvalent ene having a molecular weight of 0 and a molecular weight of 1100 or less is effective. A particularly effective polyvalent ene has 8 to 20 carbon atoms. When the number of vinyl type double bonds is one, it is impossible to effectively increase the melt tension and the extensional viscosity at the time of strain hardening. As a specific example,
1,4-pentadiene, 1,5-hexadiene, 1,6
-Heptadiene, 1,7-octadiene, 1,8-nonadiene, 1,9-decadiene, 1,13-tetradecadiene, 3-methyl-1,4-pentadiene, 4-methyl-1,5-hexadiene, 3 -Methyl-1,5-hexadiene, 1,5,9-decatriene and the like can be mentioned. In the present invention, the content of polyvalent ene introduced into the obtained polyolefin is 0.05 to 2% by weight. 0.0
If it is less than 5% by weight, the effect of improving the melting property is not remarkable, and if it is 2% by weight or more, the generation of gel or the like is seen, which is a practical problem. It is preferably 0.05 to 1% by weight, and 0.05 to 1% by weight in the field of films and the like where appearance is important.
0.2 wt% is desirable. The λ value in the present invention is an index of the degree of non-linearity of elongational viscosity, and represents the magnitude of strain hardening in various moldings by the elongational viscosity ratio before and after that. Here, λ = λ ₁ / λ ₀ [λ ₀ is the extensional viscosity at the displacement point, and λ ₁ is the extensional viscosity when the strain is twice the strain at the displacement point. The displacement point is a point at which the linear region (extreme deformation region) and the non-linear region (large deformation region) of extensional viscosity are displaced. The range of the λ value is preferably 2.0 or more and less than 6.0, and particularly preferably 3.0 or more and less than 5.0 when importance is attached to thickness uniformity. When the λ value is less than 2.0, sufficient strain hardening does not occur, so that the uniformity and shape stability of the molding resin are poor, and when it is 6.0 or more, the melt fluidity of the polymer decreases and the actual Molding becomes difficult. in addition,
The generation of gel becomes noticeable.

The polymerization method used in the present invention can be any of liquid phase polymerization, slurry polymerization and gas phase polymerization. Further, multistage polymerization in which a plurality of the same or different processes are continuously performed is also possible. When an aluminoxane compound is used in the polymerization, a mixture of both components of the metallocene compound and the aluminoxane compound may be supplied in advance to the reaction system, or both components may be supplied to the reaction system. In either case, the concentration molar ratio of both components in the polymerization system is not particularly limited, but is preferably 10 ⁻³ to 10 ⁻¹⁰ mol / l in complex concentration,
The molar ratio of Al / complex is preferably 10 or more, and particularly preferably 100 or more.

When a non-coordinating ionic compound is used in the polymerization, a mixture of the metallocene compound, the trialkylaluminum and the non-coordinating ionic compound may be fed to the reaction system. Each component may be supplied individually. In any case, the molar concentration of each component in the polymerization system is not particularly limited, but preferably, the complex concentration is 10 ⁻³ to 10 ⁻¹⁰ m 2.
The molar ratio of trialkylaluminum / complex is preferably in the range of 50 to 1000, and the molar ratio of non-coordinating ionic compound / complex is in the range of 0.5 to 10, particularly preferably in the range of 1 to 5. To be The olefin pressure of the reaction system is not particularly limited, but is preferably in the range of normal pressure to 50 kg / cm ² G. The amount of polyvalent ene supplied is 0.01 to 10% by weight, preferably 0.1 to 5% by weight, based on the olefin in the reaction system. The polymerization temperature is not limited, but preferably −
It is in the range of 30 ° C to 200 ° C, particularly preferably 0
It is in the range of 80 ° C to 80 ° C. The molecular weight at the time of polymerization can be controlled by a known means such as selection of temperature or introduction of hydrogen. The production method of the present invention can also be used in combination with other olefins. For example, olefins such as propylene, butene, hexene, octene, 4-methyl-1-pentene can be combined.

The ethylene polymer obtained in the present invention can be applied to the fields which can be conventionally used. Examples include fields such as injection molded products, films, sheets, blows, laminae, and fibers. Further, it can be molded by a usual molding method. As the additives such as the stabilizer, those used in the relevant industry can be applied. Furthermore, it can be used by mixing with other commonly known resins, for example, rubbers such as polypropylene, EPR, EBR and EPDM. In addition, nucleating agents, inorganic fillers,
It can also be used in combination with fibers and the like. Further, it is also possible to carry out modification such as grafting reaction, maleic anhydride, etc., crosslinking, bisbreak, etc., as in conventional polyolefins.

[0026]

EXAMPLES Next, the present invention will be specifically described by way of examples. The analytical instruments used for measuring the physical properties are shown below. ¹³
The content of polyvalent ene by C-NMR is EX- manufactured by JEOL.
It was determined by measurement using 400. MFR is JIS K
It is a value measured according to 6760 under the conditions of a temperature of 190 ° C. and a load of 2.16 kg. The melt tension (MT) value was measured using a melt tension tester type II manufactured by Toyo Seiki Co., Ltd., orifice diameter 2.095 ± 0.005 mm, orifice length 8.000 ± 0.025 mm, resin temperature 190.
℃, take-off speed 6.5m / min, extrusion speed 15m /
It is a value measured in minutes. The elongational viscosity was measured using a capillary rheometer manufactured by Toyo Seiki Co., Ltd., using a uniform strand with a diameter of 3 mm obtained at a molding temperature of 150 ° C. as a sample, and using an elongational viscosity measurement device manufactured by Toyo Seiki Co., a measurement temperature of 150 ° C., strain rate. It was measured at 0.1 s ^-1 . Further, the presence or absence of gel component was confirmed by a film having a thickness of about 20 μm formed by a biaxial stretching device manufactured by Toyo Seiki Co., Ltd.

(Example 1) [Preparation of triethyl phosphate modified methylaluminoxane]
Tosoh Akzo methylaluminoxane (aluminum equivalent 1.3 mol
/ L toluene solution) and 50 ml of toluene
And then triethyl phosphate 1.16 g was added, 8
The mixture was heated and stirred at 0 ° C. for 4 hours. Washing with toluene gave a solid modified methylaluminoxane. [Polymerization] 2.5 ml of a hexane solution of triisobutylaluminum (0.5 mol / l) was added to an autoclave made of SUS having an internal volume of 1.2 l sufficiently replaced with nitrogen, and 50 ml of the above-prepared triethyl phosphate modified methylaluminoxane was prepared.
mg, and 0.6 mg of bis (n-butylcyclopentadienyl) zirconium dichloride were introduced. After that, 1.0 mmol of hydrogen and 600 ml of isobutane were added,
The temperature was raised to ° C. Then, polymerization was started by introducing 3 g of 1,4-pentadiene together with ethylene. Polymerization was carried out at an ethylene pressure of 10 kg / cm ^{2 for} 20 minutes, and 72
g of polymer was obtained. 36,000 activity per complex
It was g polymer / g complex · hr · atm. The results are shown in Table 1.

(Example 2) Polymerization was carried out according to Example 1 except that 1,7-octadiene was used in place of 1,4-pentadiene to obtain 69 g of a polymer. The results are shown in Table 1.
Shown in

(Example 3) Polymerization was carried out according to Example 1 except that 1,9-decadiene was used instead of 1,4-pentadiene to obtain 92 g of a polymer. The results are shown in Table 1.

Example 4 Polymerization was carried out according to Example 3 except that the amount of 1,9-decadiene used was 1.5 g.
98 g of polymer were obtained. The results are shown in Table 1.

(Example 5) Polymerization was carried out according to Example 1 except that 1,13-tetradecadiene was used instead of 1,4-pentadiene to obtain 71 g of a polymer. The results are shown in Table 1.

Example 6 According to Example 3, except that 1.5 ml of Tosoh Akzo's methylaluminoxane (a toluene solution of 1.3 mol / l in terms of aluminum) was used in place of the triethyl phosphate modified methylaluminoxane. Polymerization was performed to obtain 105 g of polymer. The results are shown in Table 1.

(Example 7) 1.3 m of ethylenebis (indenyl) zirconium dichloride instead of bis (n-butylcyclopentadienyl) zirconium dichloride
Polymerization was performed according to Example 3 except that 43 g was used.
A polymer of The results are shown in Table 1.

(Example 8) 1.3 m of ethylenebis (indenyl) zirconium dichloride instead of bis (n-butylcyclopentadienyl) zirconium dichloride
Polymerization was carried out according to Example 6, except that 48 g was used.
A polymer of The results are shown in Table 1.

(Example 9) 2.5 ml of a hexane solution of triisobutylaluminum (0.5 mol / l) and (t-butylamide) were placed in an autoclave made of SUS and having an internal volume of 1.2 l which had been sufficiently replaced with nitrogen. ) (Tetramethylcyclopentadienyl) zirconium dichloride 2 μmo
1.5 ml of a 1 / ml toluene solution and 2.3 ml of a 2 μmol / ml toluene solution of triphenylcarbonium tetrakis (pentafluorophenyl) borate were introduced. Then 1.0 mmol hydrogen and 600 isobutane
ml was added and the temperature was raised to 70 ° C. Then, the polymerization was initiated by introducing 3 g of 1,9-decadiene together with ethylene. Polymerization was carried out at an ethylene pressure of 10 kg / cm ^{2 for} 20 minutes to obtain 46 g of a polymer. The results are shown in Table 1.

(Example 10) Polymerization was carried out according to Example 9 except that the amount of 1,9-decadiene used was 1.5 g, to obtain 52 g of a polymer. The results are shown in Table 1.

(Example 11) Polymerization was carried out according to Example 9 except that dimethylanilinium tetrakis (pentafluorophenyl) borate was used in place of triphenylcarbonium tetrakis (pentafluorophenyl) borate to obtain 44 g of a polymer. It was The results are shown in Table 1.

(Example 12) 2.5 ml of a hexane solution of triisobutylaluminum (0.5 mol / l) was added to an SUS autoclave having an internal volume of 1.2 l which had been sufficiently replaced with nitrogen, and the triethyl phosphate modified as described above was modified. 50 mg of methylaluminoxane and 0.6 mg of bis (n-butylcyclopentadienyl) zirconium dichloride were introduced. After that, 1.0 mmol hydrogen and 6 isobutane
00 ml was added and the temperature was raised to 70 ° C. Then, 15 g of 1-hexene and 3 g of 1,9-decadiene were introduced together with ethylene to initiate polymerization. Ethylene pressure 10k
Polymerization was carried out at g / cm ^{2 for} 20 minutes to obtain 79 g of a polymer. The density was 0.921. The results are shown in Table 1.

(Comparative Example 1) Polymerization was carried out according to Example 1 except that 1,4-pentadiene was not used to obtain 80 g of a polymer. The melt tension is as small as 3.2 g, and the nonlinearity of extensional viscosity is also small.

(Comparative Example 2) Polymerization was carried out according to Example 3 except that the amount of 1,9-decadiene used was 0.02 g, to obtain 75 g of a polymer. The melt tension is as small as 4.8 g, and the nonlinearity of extensional viscosity is also small.

(Comparative Example 3) Polymerization was carried out according to Example 3 except that the amount of 1,9-decadiene used was 43 g.
4 g of polymer was obtained. Gel was observed in the biaxially stretched film.

(Comparative Example 4) Polymerization was carried out according to Example 1 except that 1,3-butadiene was used in place of 1,4-pentadiene to obtain 68 g of a polymer. The melt tension is as small as 7.0 g, and the nonlinearity of extensional viscosity is also small.

(Comparative Example 5) Polymerization was carried out according to Example 12 except that 1,9-decadiene was not used, and 73 g of a polymer was obtained. The density was 0.920. The melt tension is as small as 5.1 g, and the nonlinearity of extensional viscosity is also small.

(Comparative Example 6) Polymerization was carried out according to Example 7 except that the amount of 1,9-decadiene used was 43 g.
9 g of polymer was obtained. Gel was observed in the biaxially stretched film.

(Comparative Example 7) Polymerization was carried out according to Example 9 except that 1,9-decadiene was not used, to obtain 46 g of a polymer. The melt tension is as small as 4.5 g, and the nonlinearity of extensional viscosity is also small. The results of the comparative examples are also summarized in Table 1.
Shown in

[0046]

[Table 1]

[0047]

EFFECTS OF THE INVENTION According to the present invention, it is possible to provide an ethylene polymer in which the non-linearity of melt tension and extensional viscosity is sufficiently large, and the molding resin is excellent in thickness uniformity and shape stability.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Shintaro Inazawa, Oita City, Oita Prefecture, No. 2 Nakasu, Showa Denko K.K.

Claims (3)

[Claims] 1. A λ value (λ, which contains zirconium and aluminum or boron, and which indicates the magnitude of nonlinearity of extensional viscosity.
Ethylene polymer characterized in that ₁ / λ ₀ ) is 2.0 or more and less than 6.0. Here, [λ ₀ is the extensional viscosity at the displacement point, and λ ₁ is the extensional viscosity when the strain is twice the strain at the displacement point. The displacement point is a point at which the linear region (extreme deformation region) and the non-linear region (large deformation region) of extensional viscosity are displaced. ] 2. The ethylene according to claim 1, which contains at least two non-conjugated vinyl type double bonds and contains from 0.05 to 2% by weight of a polyvalent ene having 5 to 80 carbon atoms. Polymer. 3. Polymerization using a catalyst system comprising at least one metallocene compound represented by the general formula (1), (2) or (3) and an aluminoxane compound or a non-coordinating ionic compound. The method for producing an ethylene-based polymer according to claim 1 or 2. Embedded image Embedded image [Chemical 3] [Wherein R ^{1 to} R ¹⁰ are hydrogen or a hydrocarbon group (having 1 carbon atom).
To alkyl, alkenyl, aryl, alkylaryl, arylalkyl, etc.), an alkylsilylene group, an alkylgermanium group, or a 4- to 6-membered ring having a carbon-carbon bond, which may be the same or different. , R ¹¹ is an alkylene group having 1 to 20 carbon atoms, an alkylidene group, an alkylgermane group or an alkylsilylene group, and Q ¹ and Q ² are aryl, alkyl, alkenyl, alkylaryl, arylalkyl having 1 to 20 carbon atoms, etc. Hydrocarbon groups, alkoxy, allyloxy,
Siloxy, hydrogen or halogen, which may be the same or different, and Y is -O-, -S-, -NR.
¹² -, - PR ¹² - a whether, also -OR ^12, -SR ^12,
-NR ¹² R ¹³ , -PR ¹² R ¹³ (R ¹² and R ¹³ are hydrogen or a hydrocarbon group having 1 to 20 carbon atoms such as alkyl, alkenyl, aryl, alkylaryl, arylalkyl, or a halogenated alkyl or halogenated group. Is an aryl) and is a neutral electron-donating ligand, Me is a transition metal of Groups 3, 4, 5 and 6 of the Periodic Table, and p is 0 or 1. ]