JP3375168B2 - Polyethylene composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [0001] BACKGROUND OF THE INVENTION 1. Field of the Invention
, Swell ratio, etc.), flow characteristics (processing characteristics)
Excellent mechanical properties (impact resistance, tensile strength, etc.)
Ethylene / α-olefin copolymer with extremely wide molecular weight distribution
Combined compositions, especially high-speed moldability and low-temperature machines
Excellent mechanical properties, high melt tension and high die swell ratio
From a critical point, large hollow molding such as gasoline tank
Suitable for extruded products, such as large-diameter pipes and large-diameter pipes
-It relates to an α-olefin copolymer composition. [0002] 2. Description of the Related Art Conventionally, in order to improve flow characteristics, an ethyl resin is used.
To broaden the molecular weight distribution of the α-olefin copolymer
The method has been reported (for example, Japanese Patent Application Laid-Open No. 57-21409).
Gazette, Japanese Patent Publication No. 63-47741)
Just by broadening the molecular weight distribution as shown
Are the melt elasticity and mechanical properties, especially at low temperatures.
It does not improve, but rather drops significantly. Also mechanical properties
For the improvement of flow characteristics,
Ethylene / α-olefin copolymer comprising molecular weight component
The degree of short chain branching of the high molecular weight component of
Introduce a lot of short-chain branching into the mechanical properties and fluidity only
To improve environmental stress cracking resistance (ESCR)
(Japanese Patent Application Laid-Open No. 54-100444,
Japanese Patent Publication No. 64-7096). However, these improvements
Mechanical properties, especially at low temperatures,
Sex is not satisfactory. Further, JP-A-2-305
No. 811 discloses impact resistance, ESCR, pinch
In order to improve off-fusibility, a catalyst and a polymerization strip of two-stage polymerization are used.
There has been a proposed way to identify the
Although some improvements are seen in ESCR and melt elasticity,
Inadequate for improving mechanical properties, especially at low temperatures
Minutes. In addition, polyethylene compositions for hollow molding
Draw-down resistance, die swell and ESCR
Improved ones (JP-A-59-89341, JP-A-60-89341)
No. -20946) and the two-stage polymerization method.
A three-stage polymerization method has been proposed as a method for improving the disadvantages.
(JP-B-59-10724, JP-A-62-25105)
No. 62-25106, No. 62-25107, No.
Nos. 62-25108 and 62-25109).
In these proposals as well, improvements in the melt elasticity and flow characteristics were made.
Good is still inadequate, and mechanical properties, especially at low temperatures, have changed.
There is no good. [0003] SUMMARY OF THE INVENTION The present invention has been made in view of the above points.
Melt elasticity (melt tension, die swell ratio
), Dynamic characteristics (processing characteristics, etc.), mechanical characteristics (impact resistance,
Excellent balance of various physical properties such as tensile strength, etc., and molecular weight distribution
Wide range of ethylene / α-olefin copolymer composition
Products, especially high-speed moldability and mechanical properties at low temperatures
Excellent in melt tension and die swell ratio
Large hollow molded products such as gasoline tanks, large diameter pie
To provide compositions suitable for extruded articles such as
It is the purpose. [0004] SUMMARY OF THE INVENTION The present inventors have achieved the above object.
As a result of intensive studies along with the
Tylene / α-olefin copolymer and short chain between molecules
Specific ethylene / α-olefin with extremely wide branch distribution
Ethylene copolymer without ethylene copolymer or short-chain branching
Combining a total of 4 kinds of 2 kinds of ingredients consisting of union
More physical properties such as melt elasticity, flow properties, mechanical properties, etc.
Excellent balance, especially high-speed moldability and mechanical properties at low temperatures
Ethylene / α-olefin copolymer composition with excellent properties
Was obtained, and reached the present invention. Ie
The present invention provides (I) a super-ultrameter which satisfies the following conditions (a) and (b):
High molecular weight ethylene homopolymer or ethylene α-O
1 to 50% by weight of a refin copolymer, (a) Intrinsic viscosity (η ₁ ) 9-45dl / g, (b) Density (d ₁ 0.890-0.935 g / cm ³ , (II) Highly active Ziegler supported on a solid support
That satisfy the following conditions (c) to (f)
Tylene homopolymer or ethylene / α-olefin copolymer
5 to 89% by weight, (c) Intrinsic viscosity (η ₂ ) 0.3-3.0dl / g, (d) Density (d ₂ 0.890-0.980g / cm ³ , (e) In the elution temperature-elution amount curve by the continuous heating elution fractionation method
To the area Ia under the elution temperature of 90 ° C. or higher.
Of the area Ib under the elution temperature 25-90 ° C.
b / Ia) is calculated from the following equation: ₁ Less than, S ₁ = 20η ₂ ^-1 exp [−50 (d ₂ −0.900)] (f) Orthodichlorobenzene soluble matter at 25 ° C
W calculated from the formula ₁ Less than,           W ₁ = 100η ₂ ^-0.5 exp [−50η ₂ ^0.5 (d ₂ −0.900)], (III) ethylene satisfying the following conditions (g) and (h):
Copolymer with α-olefin having 3 to 18 carbon atoms 5-89
weight%, (g) Intrinsic viscosity (η ₃ ) 1.2 dl / g or more, less than 9.0 dl / g, (h) Density (d ₃ 0.890-0.960 g / cm ³ , [However, (k) Elution temperature by continuous heating elution fractionation method-Elution
In the quantity curve, the area under the elution temperature of 90 ° C or higher
Ratio S of the area Ib at an elution temperature of 25 to 90 ° C. to Ia
(Ib / Ia) is calculated from the following equation._TwoHereinafter, S_Two= 2
0η_Three ^-1exp [−50 (d_Three−0.900)], and (l) 25 ° C.
Orthodichlorobenzene soluble matter W weight% is calculated from the following formula.
W to be calculated_TwoW_Two= 20exp (-η_Three)
And (IV) Ethylene alone which satisfies the following conditions (i) and (j)
Polymer or ethylene and α-olefin having 3 to 18 carbon atoms
5-89% by weight of a copolymer with (i) Intrinsic viscosity (η ₄ ) 0.2-1.6 dl / g, (j) Density (d ₄ ) 0.940-0.980 g / cm ³ And components (I), (II), (III) and (I
V) is 100% by weight and η ₁ , Η ₂ , Η ₃ You
And η ₄ Are different from each other, η ₃ Is η ₄ Greater than
A mixture having a limiting viscosity of 1.0 to 6.0.
0dl / g, Density 0.890-0.970g / cm ³ And the following equation
Echile whose N-value calculated from Equation 2 is 1.7 to 3.5
And α-olefin copolymer compositions.
You. [0005] (Equation 2) Hereinafter, the contents of the present invention will be described in detail. Of the present invention
The ultrahigh molecular weight component (I) is an ethylene homopolymer or
An ethylene / α-olefin copolymer,
Α-olefins having 3 to 18 carbon atoms
, Especially those with 4 to 10 carbon atoms in terms of mechanical properties
Are preferred. Specifically, 1-butene, 1-pentene,
1-hexene, 4-methyl-1-pentene, 1-octe
, 1-nonene, 1-decene and the like. Note that α-
Two or more olefins may be used in combination. [0007] Ethylene as the ultrahigh molecular weight component (I)
Homopolymer or ethylene / α-olefin copolymer
Is the (a) intrinsic viscosity (η₁) Is 9 to 45 dl / g, preferably 1
0-40 dl / g, more preferably in the range of 12-40 dl / g
Things are used. η₁Is less than 9 dl / g, the resulting set
Poor melt elasticity and mechanical properties of the product, and 45dl / g
If it exceeds, surface roughness and fish eye of the molded product will occur
And the moldability decreases. The component (I) (b)
Density (d₁) Is 0.890-0.935 g / cm^ThreeRange, good
0.890-0.930 g / cm^ThreeOf the range
Can be. d₁Is 0.890 g / cm^ThreeLess than
Difficult and causes the resulting composition to become sticky
Therefore, it is not preferable. While d₁Is 0.935 g / cm^ThreeExceeds
Sometimes the mechanical properties of the composition, especially at low temperatures
Is undesirably reduced. The component (II) of the present invention comprisesSupported on solid carrier
Polymerized with a highly active Ziegler-type catalystEtch
Rene homopolymer or ethylene / α-olefin copolymer
Body. Α-O of ethylene / α-olefin copolymer
As the fin, as in the case of the component (I), the number of carbon atoms is 3 to
18 are used, preferably having 4 to 10 carbon atoms.
1-butene, 1-pentene, 1-hexene
Sen, 4-methyl-1-pentene, 1-octene, 1-
Nonene, 1-decene, etc. are preferred in terms of mechanical properties, etc.
No. Α-olefins may be used in combination of two or more.
Absent. The component (II) (c) intrinsic viscosity (η_Two) Is
It is in the range of 0.3 to 3.0 dl / g, preferably 0.6 to 3.0 dl / g.
It is in the range of 0 dl / g. η_TwoIs less than 0.3 dl / g,
Mechanical properties of the composition, especially at low temperatures
On the other hand, if it exceeds 3.0 dl / g, its flow characteristics deteriorate.
Therefore, neither is preferable. The component (II) (d)
Degree (d_Two) Is 0.890-0.980 g / cm^ThreeRange, preferred
Or 0.900-0.975 g / cm^ThreeUsed in the range
Can be d_Two0.890 g / cm^ThreeLess than is difficult to manufacture
In addition to causing stickiness of the resulting composition.
Is not preferred. 0.980g / cm^ThreeWhen exceeds
Not only is it difficult to manufacture, but also the mechanical properties of the resulting composition
Similarly, the characteristics are unfavorably reduced. The above-mentioned component (II) used in the present invention
The condition (e) is that a component having a high degree of branching containing many short-chain branches is contained in a solvent.
Dissolves at low temperatures, but has a low degree of branching with few short-chain branches
Branching utilizing the property that it does not dissolve in solvents unless it is high temperature
The distribution is defined quantitatively. That is, to the solvent
Measuring branch distribution from melting temperature
Temperature elution fractionation (Temperature Rising Elution Fractiona
tion (TREF); Journal of Polymer Science: Polymer
Elution by Physics Edition, Vol.20, 441-455 (1982))
In the temperature-elution amount curve, the elution temperature is 90 ° C or higher.
Area Ia below and area I under the curve at an elution temperature of 25-90 ° C.
It is necessary that a specific relationship be established with b.
In the present invention, the area ratio S = Ib shown in the schematic diagram of FIG.
/ Ia is calculated by the following equation.₁If not
No. S₁= 20η_Two ^-1exp [−50 (d_Two−0.900)] The value of S is S₁Above, the distribution of branches approaches almost uniform
As a result, the mechanical properties, especially
The effective high branching component is relatively reduced.
Is not preferred. (F) 25 ° C. of the component (II) used in the present invention
Elution temperature of orthodichlorobenzene solubles is too low
To the extent that it cannot be quantified by the above-mentioned continuous heating elution fractionation method,
It indicates the amount of a component having a very large number of branches, and
Must have specific values corresponding to limiting viscosity and density
It is. However, this is also a low molecular weight
This low-molecular-weight component also indicates the presence of a component.
It is necessary to eliminate as much as possible. To do this,
Soluble content W weight% is obtained from the following equation.₁Must be
Must. Preferably W_ThreeIt is as follows. W₁= 100η_Two ^-0.5exp [−50η_Two ^0.5(d_Two−0.900)] W_Three= 90η_Two ^-0.5exp [−50η_Two ^0.5(d_Two−0.900)] W value is W₁In the above, components with a very large number of branches
Shows that there are low molecular weight components that are not useful outside
Mechanical properties, especially at low temperatures.
And The ethylene / α-O component (III) of the present invention
The refin copolymer is the same as the components (I) and (II)
Similarly, ethylene and an α-olefin having 3 to 18 carbon atoms
, Preferably having 4 to 10 carbon atoms
Is preferred in terms of mechanical properties and the like. Specifically, 1-bute
1-pentene, 1-hexene, 4-methyl-1-pe
1-octene, 1-nonene, 1-decene, etc.
I can do it. Note that even if two or more α-olefins are used in combination,
I do not support it. The component (III) (g) intrinsic viscosity (η_Three) Is
1.2 dl / g or more and less than 9.0 dl / g, preferably
Is from 1.4 to 8.5 dl / g, more preferably from 1.6 to 8.0 dl / g
Range. η_ThreeIs less than 1.2 dl / g, the composition obtained
Has poor melt elasticity and mechanical properties, while 9.0 dl / g
If it exceeds, surface roughness and fish eye of the molded product will occur
And the moldability decreases. The component (III) has an (h) density (d3) of 0.3.
It is in the range of 890 to 0.960 g / cm3, preferably 0.9.
The range is from 900 to 0.950 g / cm3. d3 is 0.89
Those with less than 0 g / cm3 are difficult to produce and are obtained
It is not preferable because it causes stickiness of the composition. The other
If it exceeds 0.960 g / cm3, the mechanical properties will deteriorate.
You.Component (III) is determined by (k) continuous heating elution fractionation
In the elution temperature-elution amount curve, the elution temperature is 90 ° C or higher.
At an elution temperature of 25 to 90 ° C. with respect to the area Ia under the curve of
The ratio S (Ib / Ia) of the area Ib is calculated by the following equation.
_Two Hereinafter, S _Two = 20η _Three ^-1 exp [−50 (d _Three −0.900)]
And (l) 25 ° C orthodichlorobenzene soluble matter W weight
W where% is calculated from the following formula _Two W _Two = 20exp (-η _Three )
Excluding those that satisfy the conditions of Component (IV) of the present invention, which is a low molecular weight component
Is ethylene homopolymer or ethylene α-olefin
Ethylene-α-olefin copolymer
When using α-olefin, component (I)
Use the one having 3 to 18 carbon atoms as in (III)
And preferably have 4 to 10 carbon atoms, particularly as described above.
1-butene, 1-pentene, 1-hexene, 4-methyl
-1-pentene, 1-octene, 1-nonene, 1-decene
Are preferable in terms of mechanical characteristics and the like. Α-Oleph
Two or more kinds can be used in combination. The component (IV) (i) intrinsic viscosity (η_Four) Is
It is in the range of 0.2 to 1.6 dl / g, preferably 0.3 to 1.0 dl / g.
5 dl / g, more preferably in the range of 0.4 to 1.4 dl / g
You. η_FourIs less than 0.2 dl / g, the mechanical
Poor properties, especially low temperature mechanical properties, while 1.6 dl / g
Above this point, the flow characteristics deteriorate, so both are preferred.
Not good. Further, the density (d) (d) of the component (IV)_Four) Is 0.9
40 ~ 0.980g / cm^ThreeAnd preferably 0.9.
40 ~ 0.970g / cm^ThreeRange. d_Four0.940g /
cm^ThreeIf less, it is difficult to produce a high-density composition.
It is not preferable because it becomes difficult. 0.980g / cm^ThreeBeyond
Is not only difficult to manufacture, but also the resulting composition
Similarly, the mechanical properties of the product are undesirably reduced. In the present invention, the components (I), (II) and (II)
The mixing ratio of I) and (IV) is 1 to 50% by weight of component (I).
%, Component (II) 5 to 89% by weight, component (III) 5 to 89
% By weight and 5-89% by weight of component (IV),
The total amount of components (I), (II), (III) and (IV) is 1
00% by weight, depending on the performance required for the composition.
These proportions are selected. Of the above components,
Minutes (I) and (II) also play important roles in the present invention.
Considering the properties of components (I) and (II)
It is preferable to select the compounding ratio of the composition. component
If the amount of (I) is less than 1% by weight, melt elasticity and mechanical
Properties, especially mechanical properties at low temperature, are not sufficient
If the content is more than 10% by weight, the flow characteristics will decrease.
Also cannot be used. When the amount of the component (II) is less than 5% by weight,
Has inferior mechanical properties at low temperature, and when it exceeds 89% by weight,
The flow characteristics decrease. However, components (I) to (IV)
It is important that the intrinsic viscosities are different from each other.
If this is not satisfied, it is one of the objects of the present invention.
The flow characteristics cannot be improved. The ethylene / α-olefin copolymer of the present invention
The body composition comprises components (I), (II), (III) and
And (IV) can be obtained by blending
The properties of the composition must be in a certain range. Sand
That is, the ultimate viscosity of the ethylene / α-olefin copolymer composition
The degree is 1.0 to 6.0 dl / g, preferably 2.0 to 5.0 dl / g.
dl / g. If the intrinsic viscosity is less than 1.0 dl / g, the melt viscosity
And mechanical properties, especially at low temperatures
On the other hand, if it exceeds 6.0 dl / g, the flow characteristics will be low.
Therefore, neither is preferable. Also ethylene / α-olef
The density of the vinyl copolymer composition is 0.890 to 0.970 g / cm.
^Three, Preferably 0.900 to 0.965 g / cm^ThreeIn
You. 0.890g / cm density^ThreeLess than is difficult to manufacture
In addition, it causes the composition to become sticky, and
970g / cm^ThreeIf it exceeds, the mechanical properties will be low. Change
The N-value of the ethylene / α-olefin copolymer composition
Must be 1.7 to 3.5, and preferably
1.7 to 3.0. High-speed molding when N-value is less than 1.7
Low and 3.5 or more may cause melt fracture
I'm sorry. The ethylene / α-olefin copolymer of the present invention
Method for producing body compositionIs each component of the composition
Satisfies certain conditionsThere is no particular limitation.
For example, components (I), (II), (III) and (IV)
After each of them is produced independently by one-stage polymerization,
May be mixed, or two-stage polymerization or more
Produced by a known polymerization method by multi-stage polymerization of
You may. When manufacturing by mixing the former, uniaxial
Or mix with a twin screw extruder or Banbury mixer
Use a known method such as a kneading method or a solution mixing method
can do.Two-stage polymerization or more multistage weight
Each component is polymerized individually with the composition manufactured by the combined method
After blending, the resulting compositions are all equivalent.
Has properties. The latter method using multi-stage polymerization includes a plurality of methods.
Performing two or more stages of polymerization using a reactor
In the case of the four-stage polymerization of the present invention, the first stage and the
And the second stage reactor, for example, component (I) and
The polymerization conditions for producing (III) are maintained, and the third and
The four-stage reactor was maintained under the polymerization conditions of components (II) and (IV).
Holding the polymer of the first stage continuously through the second stage to the third stage
And flow to the 4th stage, ethylene / α-olefin copolymer
A coalescing composition can be produced. In this case
Any of the components (I), (II), (III) and (IV)
May be manufactured in the reactor of
The number is not particularly limited. One or more stages above
There is no particular limitation on the polymerization method of
Using various polymerization methods such as phase method, solution method, high pressure ion method
Can be In these methods, too,
All the products have the same properties.Naoko
Well-known operating conditions such as reaction temperature and pressure in these methods
The subject is, for example, Chemical Engineering, 47, [5] (1983) Fuji
Field, Ushida, p329 and Convertec (1990.
1) Doi, p77. In addition, the actual
Component (II) B1-used in Examples and Comparative Examples
As can be seen from the production example of B4, the supply amount of comonomer
When the polymerization is reduced, the high branching degree component decreases, and the W value increases.
And the polymerization temperature and pressure are increased.
Then, the branching degree distribution becomes narrow, so the S value is large and the W value is
Tends to be smaller. PolymerizationThe catalyst is, For example, titanium and / or
Or Ziegler mainly composed of transition metals such as vanadium
TypeCatalystCan be used.Especially manufacture component (II)
The catalystHighly active cheeg supported on solid support
With a catalystNeed to beYes, the details below
State. The highly active Ziegler-type catalyst is supported on an inorganic solid.
Body, for example metallic magnesium, magnesium hydroxide, charcoal
Magnesium oxide, magnesium oxide, various aluminas,
Rica, silica alumina, magnesium chloride, etc.
Gnesium and silicon, aluminum and calcium
Double salts, double oxides, hydrated carbonates,
Oxygen-containing silicates and other inorganic solid carriers
Compounds, sulfur-containing compounds, hydrocarbons, and halogen-containing substances
Transfer to inorganic solid carriers such as those treated or reacted
Transfer metal compounds such as titanium, vanadium, zirconium
Halides, alkoxy halides
Carrying oxides, oxides, halogenated oxides, etc.
Is used as a solid component,
Compounds, preferably organometallic zinc or aluminum
Compounds or combinations of compounds
Pretreated by contact with olefins, etc.
Normal catalyst activity is 50g-polymer / g-catalyst ・ hr ・ kg / cm^Two-me
Above fin pressure, preferably 100g-polymer / g-catalyst.h
rkg / cm^Two-More than olefin pressure. Above
Highly active Ziegler containing magnesium halide
Type catalysts are particularly preferred. The ethylene / α-olefin copolymer of the present invention
In the body composition, it does not deviate from the gist of the present invention.
Other olefin polymers, rubber, etc., or antioxidants,
UV absorbers, light stabilizers, lubricants, antistatic agents, antifoggants,
Anti-blocking agent, processing aid, coloring pigment, cross-linking agent,
Known additives such as foaming agents, inorganic and organic fillers, and flame retardants
It can be used in combination. [0025] Now, the present invention will be described in detail with reference to Examples.
However, the present invention is not limited to them. First,
1 shows a test method used in the present invention. (1) Intrinsic viscosity [η] Measure in 135 ° C decalin solution. (2) Density Density gradient tube method according to JIS K6760 (23 ° C)
Measure with (3) Continuous heating elution fractionation method (TREF) As described above, the method of L. Wild et al. Was followed. Details of the measurement method
Is as follows. 8. Capacity filled with Celite 545
Concentrate the sample in a 5 liter stainless steel column
Heated and melted at 135 ° C to adjust to 0.05% by weight.
After injecting 5 ml of the prepared orthodichlorobenzene solution,
Cool the sample to 25 ° C at a cooling rate of 4 ° C / min.
Deposit on the surface. Next, the orthodichloro
50 ° C / hr while flowing benzene at a constant rate of 1 ml / min
And elute the sample sequentially. At this time,
The asymmetric stretching vibration of methylene
Wave number of motion 2925cm^-1Absorption detected by infrared detector
And record the relationship between elution temperature and elution volume.
Find the composition distribution. (4) Area ratio by continuous warming elution fractionation method (S) As described above and in FIG. (5) Soluble content of orthodichlorobenzene at 25 ° C (W) 0.5 g of the sample was placed in 20 ml of orthodichlorobenzene (ODC).
In B), heat at 135 ° C. for 2 hours to completely
And cooled to 25 ° C. in 2 hours. This solution
After standing at 25 ° C overnight, filter with a Teflon filter.
The filtrate was collected by filtration and the unpaired methylene was detected with an infrared spectrophotometer.
Wave number of nominal stretching vibration 2950cm^-1Measure the absorption for
From the results, the filtrate in the filtrate was
Quantify sample concentration. (6) N-value Use a high temperature flow tester (manufactured by Shimadzu Corporation) to measure the resin temperature.
Extruded from a 2mmφ × 40mm die at a temperature of 210 ° C.
Test pressure 20kg / cm^TwoAnd higher test pressure 150kg / cm^TwoAt
The apparent shear rate is determined and calculated by the following equation (3). (Equation 3) (7) Melt flow rate (MFR) It is measured according to JIS K6760. (Measurement temperature
190 ° C, load 2.16kg) (8) High load melt flow rate (HLMFR) Measured according to JIS K6760. (Measurement temperature 190
° C, load 21.6kg) (9) Flow parameter (FP) FP is represented by a calculated value obtained from the following equation. FP = log (HLMFR / MFR) (10) Tensile yield strength (YTS) According to JIS K6760. (Pulling speed 50mm / mi
n, specimen thickness 2mm) (11) Tensile impact value (TIS) Measured according to ASTM D1822. (Specimen thickness 1.
5mm) (12) Izod impact value (IIS) According to JIS K7110, at 23 ° C and -40 ° C
It is measured by the following method. By pressing from the sample, 2
When measuring at 3 ° C, the thickness should be 3mm, when measuring at -40 ° C.
In the case, a sheet with a thickness of 4 mm was prepared and the shape of the test piece was No. 2 A
And Sample preparation for 88 hours at 23 ° C and 50% humidity
At 23 ° C and -40 ° C. Where -40
For samples measured at ° C, adjust under the above conditions.
After that, in a low-temperature room where the temperature was further adjusted to -40 ° C in advance.
For about 3 hours and measure in a cold room. The test piece is
Five of each were made, and the average of the five measurements was taken as the measured value.
Used. (13) Bending stiffness It is measured according to JIS K7106. (Toyo Seiki
(Uses a bending stiffness tester manufactured by Co., Ltd.) (14) Melt tension (MT) Measured by a melt tension tester manufactured by Toyo Seiki Co., Ltd.
Fixed. (Measurement temperature 190 ° C) (15) Die swell ratio (DSR) Press the sample at a temperature of 210 ° C using a Koka flow tester.
The ratio between the diameter of the strand and the inner diameter of the die is determined. Shear
Cutting speed is 100sec^-1It is measured at an extrusion speed corresponding to (16) Critical shear rate (γc) With a capillary rheometer manufactured by INTESCO
Measurement. (Measurement temperature 190 ° C) (17) Melting point (Tm) The maximum value measured using a differential scanning calorimeter manufactured by Rigaku Denki Co., Ltd.
Use the temperature of the large peak. (Press Sea 0.2mm thick
Test pieces are prepared from (18) Environmental stress crack resistance (ESCR) F of constant strain ESCR according to JIS K6760₅₀The value of the
Ask for. <Example of production by two-stage polymerization>
Use a torr or 30 liter stirred reactor and dry
Titanium tetrachloride on a solid support containing magnesium chloride as a component
Solid catalyst with triethylaluminum (TE
Using the cocatalyst of A) under nitrogen atmosphere, the first catalyst shown in Table 1
Polymerization was carried out continuously under one-stage polymerization conditions. these
Polymer was continuously introduced into the unreacted gas separation tank,
The reaction gas was separated. Subsequently, the inner volume is 30 liters or
Using a 70-liter stirred reactor, the second reactor shown in Table 1 was used.
According to the polymerization conditions of the stage, polymerization was continuously performed, and
To D3 were obtained. From the first and second stage reactors
Table 2 shows the results of measuring the properties of the recovered polymerization products.
It was shown to. The physical properties of the polymer produced in the second reactor are
It was determined by calculation. [0027] [Table 1][0028] [Table 2]In the multi-stage polymerization process shown in FIG.
Stirring type reaction with inner volume of 30 liters as first stage reactor 1
Solids containing anhydrous magnesium chloride as a component
A solid catalyst with titanium tetrachloride supported on a carrier from line 2
And TEA as co-catalyst from line 3
And ethylene and comonomers continuously under the polymerization conditions shown in Table 3.
Was polymerized. The inside of the reactor 1 was kept full of liquid. Figure
Among them, reference numeral 4 is an ethylene supply line, and reference numeral 5 is a comonomer.
Supply line, 6 is hydrogen supply line, and 7 is solvent
Shows the supply line. Partly collect the polymerization product of the first stage reactor.
The polymer was collected, and the physical properties were measured. Then the first
The slurry polymerization product from the staged reactor is passed through line 8
Pressure to the second-stage stirred reactor 9 with an internal volume of 70 liters
And ethylene, comonomer and hydrogen in Table 1.
Add as shown, keep the liquid volume at 50 liters,
Continued. The polymerization product discharged from the second stage reactor 9 is
Introduced into the flushing tank 10 via the line 11 and continuously
And the two-stage polymerization product is withdrawn from the line 12;
The physical properties were evaluated. Types of α-olefins and polymerization conditions
Was changed to produce a polymer of E1 to E3 by two-stage polymerization.
Table 3 shows the polymerization conditions, and Table 4 shows the physical property evaluation results. Next, ethylene and 1 in the above two-stage polymerization
-Specific examples of the production of polymerization product E3 with butene
explain. The polymerization conditions for the first-stage reactor 1 are as follows:
° C, total pressure 12.1kg / cm^TwoG. Calculated from heat balance
Polymer production amount E₁Was 1.80 kg / hr. The second stage
The polymerization conditions of the reactor 9 were as follows: a polymerization temperature of 80 ° C. and a total pressure of 11.8 k.
g / cm^TwoG, the amount of polymer produced E calculated from the balance_TwoIs 2.
It was 03 kg / hr. The amount of polymer product finally recovered E
Is 3.83 kg / hr and E₁+ E_TwoWas calculated.
The average polymerization of the first-stage reactor 1 and the second-stage reactor 9
The times were 25 minutes and 40 minutes, respectively. [0031] [Table 3] [0032] [Table 4]<Example of production by one-stage polymerization> First, a 50-liter internal stirring reactor was used.
Titanium tetrachloride on a solid carrier containing magnesium chloride in water
Using a solid catalyst carrying tan and a co-catalyst of TEA,
One-stage polymerization is carried out under a nitrogen atmosphere, and polymer A1, A2 and
B1 to B4 were produced.B1, B2 and B4 are highly active tigs
Polymerized with a color catalyst, and the others were polymerized using a conventional catalyst.
did.The polymerization conditions and the physical properties of the resulting polymer
It is shown in Table 5. [0034] [Table 5]In the one-stage polymerization process shown in FIG.
Use a 70-liter stirred reactor as described above.
1 stage weight continuously under the polymerization conditions shown in Table 6 using the catalyst system of
The polymerization was performed to produce a polymer C1. At this time, the weight of the reactor
Combined pressure is 9.8kg / cm^TwoG, keep the liquid volume at 50 liters
Polymerized. The results of evaluating the physical properties of these polymers are shown in the table.
6 is shown. [0036] [Table 6]<Examples 1 to 6> The weight obtained by the above method was
Using the mixture, mixing was performed at the mixing ratios shown in Tables 7 and 8.
This was performed to obtain a polyethylene composition. Evaluate their physical properties
The results are shown in Tables 7 and 8. [0038] [Table 7][0039] [Table 8]<Comparative Examples 1 to 6>
Mixing using the compound at the mixing ratio shown in Table 9 and Table 10
Was performed to obtain a composition. Together with the results of evaluating their physical properties
The results are shown in Tables 9 and 10. [0041] [Table 9][0042] [Table 10]Next, the elution temperature by TREF shown in FIG.
In addition to the molecular weight as a parameter,
FIG. 4 is a schematic diagram showing the elution amount by contour lines.
In the figure, for example, the molecular weight range is 10,000 or more.
When the examples and comparative examples are compared, the composition of the examples
Is a component having a lower elution temperature than the composition of the comparative example.
That is, a component having many short-chain branches (orthodichlorobenzene at 25 ° C.)
Content in the higher molecular weight region.
It turns out that it has. This component of the composition of the present invention
Improves mechanical properties and ESCR at low temperatures
It is estimated that this is the main factor. [0044] The polyethylene composition of the present invention has an ultrahigh
Molecular weight component, specific ethylene / α-olefin copolymerization
Body and specific distribution of extremely wide short-chain branching between molecules
Presence of ethylene / α-olefin copolymer or short-chain branch
Of two types of non-existent ethylene homopolymer
Melt elasticity and flow characteristics are obtained by combining a total of 4 types.
Of molecular weight distribution with excellent balance of performance and mechanical properties
It has a wide composition, and specifically has the following characteristics. (1) Excellent in flow characteristics such as critical shear rate. (2) Mechanical characteristics at low temperature such as low temperature Izod impact value
Excellent cold resistance. (3) Melt elasticity such as melt tension and die swell ratio
Is excellent. (4) For this reason, the moldability such as high-speed moldability is good.
You. As a result of the above advantages, various films, sheets, pies
Used for containers, hollow containers, various coating materials, foam materials, etc.
However, especially high-speed moldability and melt elasticity are remarkably excellent.
Therefore, it is useful as a composition for extruded products such as large-diameter pipes.
It is for.

BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a schematic diagram of an area ratio S in an elution temperature-elution amount curve by a continuous heating elution fractionation method (TREF). FIG. 2 is a schematic flow chart of a multi-stage polymerization process used in Examples of the present invention. FIG. 3 is a schematic flow chart of a one-stage polymerization process used in Examples of the present invention. FIG. 4 is a contour diagram of elution temperature-molecular weight-elution amount of a composition. (A) Example 1, (b) Comparative Example 1 [Description of symbols] 1 First stage reactor 2 Catalyst supply line 3 Organometallic compound supply line 4 Ethylene supply line 5 Comonomer supply line 6 Hydrogen supply line 7 Polymerization solvent supply Line 8 First-stage polymerization product transfer line 9 Second-stage reactor 10 Flushing tank 11 Second-stage polymerization product transfer line 12 Polymer recovery line

──────────────────────────────────────────────────続 き Continued on the front page (58) Field surveyed (Int. Cl. ⁷ , DB name) C08L 23/00-23/36 C08F 4/64-4/69

Claims (1)

(57) [Claims] (1) Satisfies the following conditions (a) and (b)
Ultra-high molecular weight ethylene homopolymer or ethylene α
-1 to 50% by weight of an olefin copolymer, (a) Intrinsic viscosity (η ₁ ) 9-45dl / g, (b) Density (d ₁ 0.890-0.935 g / cm ³ , (II) Highly active Ziegler supported on a solid support
That satisfy the following conditions (c) to (f)
Tylene homopolymer or ethylene / α-olefin copolymer
5 to 89% by weight, (c) Intrinsic viscosity (η ₂ ) 0.3-3.0dl / g, (d) Density (d ₂ 0.890-0.980g / cm ³ , (e) In the elution temperature-elution amount curve by the continuous heating elution fractionation method
To the area Ia under the elution temperature of 90 ° C. or higher.
Of the area Ib under the elution temperature 25-90 ° C.
b / Ia) is calculated from the following equation: ₁ Less than, S ₁ = 20η ₂ ^-1 exp [−50 (d ₂ −0.900)] (f) Orthodichlorobenzene soluble matter at 25 ° C
W calculated from the formula ₁ Less than,           W ₁ = 100η ₂ ^-0.5 exp [−50η ₂ ^0.5 (d ₂ −0.900)], (III) ethylene satisfying the following conditions (g) and (h):
Copolymer with α-olefin having 3 to 18 carbon atoms 5-89
weight%, (g) Intrinsic viscosity (η ₃ ) 1.2 dl / g or more, less than 9.0 dl / g, (h) Density (d ₃ 0.890-0.960 g / cm ³ , [However, (k) Elution temperature by continuous heating elution fractionation method-Elution
In the amount curve, the area I under the elution temperature of 90 ° C. or more was obtained.
ratio S of the area Ib at an elution temperature of 25 to 90 ° C. to a
(Ib / Ia) is calculated from the following equation._TwoHereinafter, S_Two= 2
0η_Three ^-1exp [−50 (d_Three−0.900)], and (l) 25 ° C.
Orthodichlorobenzene soluble matter W weight% is calculated from the following formula.
W to be calculated_TwoW_Two= 20exp (-η_Three)
And (IV) Ethylene alone which satisfies the following conditions (i) and (j)
Polymer or ethylene and α-olefin having 3 to 18 carbon atoms
5-89% by weight of a copolymer with (i) Intrinsic viscosity (η ₄ ) 0.2-1.6 dl / g, (j) Density (d ₄ ) 0.940-0.980 g / cm ³ And components (I), (II), (III) and (I
V) is 100% by weight and η ₁ , Η ₂ , Η ₃ You
And η ₄ Are different from each other, η ₃ Is η ₄ Greater than
A mixture having a limiting viscosity of 1.0 to 6.0.
0dl / g, Density 0.890-0.970g / cm ³ And the following equation
Echile whose N-value calculated from Equation 1 is 1.7 to 3.5
.Alpha.-olefin copolymer composition. (Equation 1)