JP3372056B2 - Ethylene / α-olefin copolymer composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [0001] BACKGROUND OF THE INVENTION The present invention relates to an extremely wide molecular weight distribution.
And an ethylene / α-olefin copolymer composition.
More specifically, high or medium molecular weight components
Ethylene with very wide short-chain branch distribution between molecules
A first component comprising two types of α-olefin copolymers and
And second component, relatively low molecular weight ethylene homopolymer
And two types of ethylene / α-olefin copolymer
Physical properties such as melt elasticity, flow properties, and mechanical properties
Good balance of high speed moldability and mechanical characteristics at low temperature.
Ethylene-α-olefin copolymer system composition with excellent properties
About. [0002] 2. Description of the Related Art Conventional high pressure method low density polyethylene (HP)
-LDPE), i.e., ethylene in a tubular or autoclaved form.
Radical polymerization at high temperature and pressure using a Reave reactor
Low-density polyethylene is comparable in length to the main chain
Consisting of a long chain branch and an alkyl group having 1 to 6 carbon atoms
Because of the structure having short-chain branches, the crystallinity is low, and
It is soft. For this reason, HP-LDPE is not suitable for environmental stress resistance.
Mechanical properties such as tearability, tensile impact value, dart impact value, and tear strength
Inferior properties, especially high-speed moldability and low-temperature mechanical properties
Having. On the other hand, linear low-density polyethylene (LL)
DPE) includes gas phase, slurry, solution, and high pressure methods.
Various processes of ionic polymerization method, various catalysts, polymerization
Ethylene / α-olefin copolymer produced under conditions
Coalesced, depending on the type of α-olefin used.
Because it has only short-chain branches that are determined uniquely, its mechanical properties are
Superior to HP-LDPE. However, LLDPE is
In general, the melt tension is very narrow due to the very narrow molecular weight distribution.
Melt elasticity and N-values such as, flow parameters, criticality
Poor flow characteristics such as shear rate. Melt elasticity and flow characteristics
Drawbacks mainly appear in the formability, specifically
Decrease in extrusion rate during molding, increase in extrusion pressure, power consumption
Volume, poor high-speed moldability,
Questions such as the formation of soft eyes and thermal degradation due to heat generation in the extruder
There is a point. To improve the flow characteristics of LLDPE,
If the amount is small, mechanical properties such as impact strength and environmental resistance
Excellent cracking properties, especially mechanical properties at low temperatures and melt elasticity
The drawback is that the temperature decreases. Also, the mechanical properties
Even if the density is lowered for improvement, the melt elasticity is almost improved.
Not good. As mentioned above, LLDPE is a machine
Properties, especially mechanical properties, flow properties and melting at low temperatures
It is extremely difficult to improve elasticity at the same time in a well-balanced manner.
It was difficult. Conventionally, in order to improve the flow characteristics, the
To broaden the molecular weight distribution of the α-olefin copolymer
Has been reported (for example, see Japanese Patent Application Laid-Open No. 57-21409).
JP, JP-B-63-47741, etc.)
Simply increasing the molecular weight distribution as described
Where mechanical properties, especially at low temperatures, can be improved
On the contrary, it drops significantly. Also mechanical properties and flow
Regarding the improvement of dynamic characteristics, high molecular weight component and low molecular weight component
Of ethylene / α-olefin copolymer consisting of
To determine the degree of short chain branching of the high molecular weight component
By introducing many short-chain branches into components,
Environmental stress crack resistance (ESCR) as well as fluidity and fluidity
Have also been attempted (Japanese Patent Application Laid-Open No. 54-1004).
No. 44, Japanese Patent Publication No. Sho 64-7096). But,
Mechanical properties, especially at low temperatures, are high molecular weight components
From the above, because it varies greatly depending on the short-chain branch distribution of
Although a slight improvement can be seen in the method,
A satisfactory tool for improving mechanical and flow properties
Not. Balance everything, including melt elasticity.
It is impossible to improve. [0006] SUMMARY OF THE INVENTION The present invention has been made in view of the above points.
Properties, such as heat resistance, ESCR, flexibility, etc., and
Melt elasticity, flow characteristics,
Excellent in properties, especially high-speed moldability and mechanical properties at low temperatures
Provide an ethylene / α-olefin copolymer composition
The purpose is to: [0007] SUMMARY OF THE INVENTION The present inventors have achieved the above object.
As a result of careful study along
And the distribution of short-chain branches between molecules is extremely high.
Two types of wide specific ethylene / α-olefin copolymer
A first component and a second component consisting of
By blending with two types of ethylene polymers,
Melt elasticity, flow properties, mechanical properties, especially at low temperatures
Ethylene / α-ole with excellent properties and excellent processability
Found that fin copolymer composition can be obtained
Ming has been reached. That is, the present invention provides (I)Supported on solid carrier
Polymerized with a high activity Ziegler-type catalyst,following
Ethylene satisfying (a) to (d) and α- having 3 to 18 carbon atoms.
5 to 85% by weight of a copolymer with an olefin, (a) Intrinsic viscosity (η₁) 2.0-9.0 dl / g, (b) Density (d₁0.890-0.935 g / cm^Three, (c) 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 at an elution temperature of 25 to 90 ° C. (Ib / I
a) is calculated from the following equation:₁Less than, S₁= 20η₁ ^-1exp [−50 (d₁−0.900)] (d) Soluble content of orthodichlorobenzene at 25 ° C W wt%
W calculated from the following equation₁that's all, W₁= 20exp (-η₁), (II)High activity Ziegler type supported on solid support
Polymerized with a catalyst,Ethylene satisfying the following (e) to (h):
Copolymer with α-olefin having 3 to 18 carbon atoms 5 to 85
weight%, (e) Intrinsic viscosity (η_Two) 1.6-7.0dl / g, (f) Density (d_Two0.890-0.945 g / cm^Three, (g) 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 at an elution temperature of 25 to 90 ° C. (Ib / I
a) is calculated from the following equation:_TwoLess than, S_Two= 20η_Two ^-1exp [−50 (d_Two−0.900)] (h) Orthodichlorobenzene soluble matter at 25 ° C W wt%
W calculated from the following equation_Twothat's all, W_Two= 20exp (-η_Two) (III) ethylene single weight satisfying the following (i) and (j):
Combined or ethylene and α-olefin having 3 to 18 carbon atoms
5 to 60% by weight of a copolymer with (i) Intrinsic viscosity (η_Three) 0.2 dl / g to 1.5 dl / g, (j) Density (d_Three0.890-0.980g / cm^Three, And (IV) Ethylene homopolymer satisfying the following (k) and (l)
Or ethylene and an α-olefin having 3 to 18 carbon atoms
5 to 60% by weight of a copolymer of (k) Intrinsic viscosity (η_Four) 0.2 dl / g to 1.5 dl / g, (l) Density (d_Four0.890-0.980g / cm^Three And components (I), (II), (III) and
(IV) is 100% by weight in total, and each component (I) to (I
V) are mixtures with different intrinsic viscosities.
The intrinsic viscosity of the mixture is 0.7 to 6.0 dl / g and the density is
0.890-0.950g / cm^ThreeAnd the following equation
Ethylene-α-olefin having an N-value of 1.7 to 3.5
It is intended to provide an epoxy copolymer composition. [0009] (Equation 2) Hereinafter, the contents of the present invention will be described in detail. Of the present invention
High or medium molecular weight components of the first and second components
The component ethylene / α-olefin copolymer is ethylene
And a copolymer of α-olefin having 3 to 18 carbon atoms.
In particular, those having 4 to 10 carbon atoms are preferable in terms of mechanical properties.
Good. Specifically, 1-butene, 1-pentene, 1-
Hexene, 4-methyl-1-pentene, 1-octene,
Examples thereof include 1-nonene and 1-decene. Note that α-
Two or more fins may be used in combination. The first component (I)Is supported on a solid carrier
Polymerized with a highly active Ziegler-type catalystethylene
・ Α-olefin copolymerIs, (A) intrinsic viscosity
(Η₁) Is 2.0 to 9.0 dl / g, preferably 2.0 to 8.5 d / g
l / g, more preferably in the range of 2.0 to 8.0 dl / g,
(b) Density (d₁) Is 0.890-0.935 g / cm^ThreeIn the range
Yes, preferably 0.890 to 0.930 g / cm^ThreeIn the range
is there. The above intrinsic viscosity (η₁) Is less than 2.0 dl / g
Have poor melt elasticity and mechanical properties of the obtained composition.
If it exceeds 9.0 dl / g, the surface roughness and
Moldability is reduced, such as generation of fish eyes. Ma
Density (d₁) Is 0.890 g / cm^ThreeLess than is difficult to manufacture
In addition to being difficult, the resulting composition may cause stickiness.
Therefore, it is not preferable. On the other hand, d₁ Is 0.935 g / cm^ThreeTo
If it exceeds, the melt elasticity and mechanical properties will decrease.
Not preferred. The second component (II)Is supported on a solid carrier
Polymerized with a highly active Ziegler-type catalystethylene
・ Α-olefin copolymerAnd(e) Intrinsic viscosity
(Η_Two) Is 1.6 to 7.0 dl / g, preferably 1.6 to 6.5 d.
l / g, more preferably in the range of 1.6 to 6.0 dl / g,
(f) Density (d_Two) Is 0.890-0.945 g / cm^ThreeRange
, Preferably 0.890 to 0.940 g / cm^ThreeRange
It is. [0014] The highly branched component containing a large amount of short-chain branching 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 can be measured quantitatively. Used in the present invention
Components (I) and (II) are as described in (c) and (g) above, respectively.
The branch distribution is measured from the dissolution temperature in the solvent as shown in
L. Wild et al. (Temperature Ris
ing Elution Fractionation (TREF); Journal of Polyme
rScience: Polymer Physics Edition, Vol. 20, 441-45
5 (1982)).
Area Ia under the curve at a temperature of 90 ° C. or higher and elution temperature 25 to 9
A specific relationship holds between the same area Ib at 0 ° C.
is necessary. That is, the area ratio S shown in the schematic diagram of FIG.
= Ib / Ia in components (I) and (II)
S obtained from the following equation₁And S_TwoMust be
Must. S₁= 20η₁ ^-1 exp [−50 (d₁−0.900)] S_Two= 20η_Two ^-1 exp [−50 (d_Two−0.900)] The value of S is S₁Or S_TwoAbove, the distribution is almost uniform
The melt elasticity and mechanical properties, especially at low temperatures
Are highly effective for the mechanical properties of
On the other hand, it decreases unfavorably. The component (I) (d) used in the present invention and
Ingredient (II) (h) Soluble at 25 ° C orthodichlorobenzene
The elution temperature is too low and the continuous heating elution fractionation method described above
Has a very high degree of branch distribution that cannot be determined
Must be greater than or equal to a specific value.
You. That is, the soluble W content by weight is the same as component (I) and
And (II) are obtained from the following equations.₁And
And W_TwoMust be at least. Preferably each W_Three
And W_FourThat is all. W₁= 20exp [-η₁], W_Two= 20exp [-η_Two] W_Three= 22exp [-η₁], W_Four= 22exp [-η_Two] W value is W₁Or W_TwoLess than melt elastic and mechanical
Properties, especially for mechanical properties at low temperatures
The high branching degree component becomes too small, which is unfavorable as described above.
No. Component (III) which is the low molecular weight component of the present invention
Is ethylene homopolymer or ethylene α-olefin
It is a vinyl copolymer. Uses ethylene and α-olefin
The component (I) and the α-olefin
As in the case of (II), those having 3 to 18 carbon atoms are used.
And preferably have 4 to 10 carbon atoms, and in particular, 1
-Butene, 1-pentene, 1-hexene, 4-methyl
-1-pentene, 1-octene, 1-nonene, 1-de
Sen is preferred in terms of mechanical properties and the like. Note that α-
Two or more fins may be used in combination. The component (III) (i) intrinsic viscosity (η_Three)
Is in the range of 0.2 to 1.5 dl / g, and preferably in the range of 0.2 dl / g.
It is in the range of 3 to 1.4 dl / g. η_ThreeIs less than 0.2 dl / g
Is the mechanical properties of the resulting composition, especially at low temperatures
Inferior properties, on the other hand, if it exceeds 1.5 dl / g, its flow properties
Are not preferred. The (j) density (d) of component (III)_Three) Is 0.
890-0.980g / cm^ThreeIs used, and preferably
0.900-0.975 g / cm^ThreeRange. d_ThreeIs 0.8
90g / cm^ThreeLess than is difficult to manufacture and obtain
This is not preferred because it causes stickiness of the composition. other
0.980g / cm^ThreeIf it exceeds, it is difficult to manufacture
Not only that, the mechanical properties of the resulting composition decrease
Similarly unfavorable. Component (IV) of the present invention, which is a low molecular weight component
Is ethylene homopolymer or ethylene α-olefin
It is a copolymer of ethylene and α-olefin.
The α-olefin used in the reaction includes components (I) to (III)
As in the case, one having 3 to 18 carbon atoms is used.
Or C 4-10, particularly 1-butene as described above,
1-pentene, 1-hexene, 4-methyl-1-pent
Ten, 1-octene, 1-nonene, 1-decene, etc.
It is preferable in terms of mechanical characteristics and the like. Α-olefin is 2
More than one species can be used together. The component (IV) (k) intrinsic viscosity (η_Four) Is
The range of 0.2 to 1.5 dl / g is used, preferably 0.3 to 1.5 dl / g.
1.4 dl / g, more preferably in the range of 0.4 to 1.3 dl / g
is there. η_FourIs less than 0.2 dl / g, the machine
Mechanical properties, especially low temperature mechanical properties, while 1.5 dl
If the amount is more than / g, the flow characteristics are deteriorated.
Not good. The component (IV) (l) density (d_Four) Is 0.8
90-0.980 g / cm^ThreeIs used, and preferably
0.900-0.970 g / cm^ThreeRange. d_FourIs 0.8
90g / cm^ThreeLess than the mechanical properties of the resulting composition
Is low, which is not preferable. 0.980g / cm^ThreeExceeds
Sometimes, it is not preferable because the production is difficult. In the present invention, the components (I), (II) and (II)
The mixing ratio of I) and (IV) is 5 to 85% by weight of the component (I).
%, Component (II) 5 to 85% by weight, component (III) 5 to 60%
% By weight and 5 to 60% by weight of the 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 blending amounts are selected. Component (I) or component (I
If the amount of I) is less than 5% by weight, the melt elasticity and mechanical characteristics
Properties, especially at low temperatures, are not sufficient.
If the amount exceeds%, the flow characteristics will be low.
I can not use it. However, the ultimate viscosity of components (I) to (IV)
It is important that the degrees are different from each other.
If not, one of the objects of the present invention is to
It is difficult to improve the mechanical properties of The ethylene / α-olefin copolymer of the present invention
The combined composition comprises components (I), (II),
Obtained by blending (III) and (IV)
However, the properties of the composition after compounding must be in a specific range.
Absent. That is, ethylene / α-olefin copolymer system
The intrinsic viscosity of the composition is 0.7 to 6.0 dl / g, preferably
Is 1 to 4 dl / g. If the intrinsic viscosity is less than 0.7 dl / g,
Poor melt viscosity and mechanical properties, especially at low temperatures
On the other hand, if it exceeds 6.0 dl / g, flow characteristics
Are unfavorable because of the lowering of In addition, d of the present invention
The density of the Tylene / α-olefin copolymer composition is 0.1.
890-0.950g / cm^ThreeAnd preferably 0.900
~ 0.945g / cm^ThreeIt is. 0.890g / cm density^ThreeLess than
Is difficult to manufacture and the cause of stickiness of the composition
And 0.950g / cm^ThreeIf it exceeds
And low mechanical properties. Furthermore, ethylene-α-ole
The N-value of the fin copolymer composition is 1.7 to 3.5.
Is required, and is preferably from 1.7 to 3.0. N
-If the value is less than 1.7, the high-speed moldability is low, and if the value is 3.5 or more,
Melt fracture is likely to occur. The ethylene / α-olefin copolymer of the present invention
Method for producing body compositionIs each component of the composition
Satisfies certain conditions,There 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
For example, in the case of four-stage polymerization, the first and second stages
The two-stage reactor is used for components (I) and (II), respectively.
High or medium molecular weight ethylene / α-olefin
The polymerization conditions for the third copolymer were maintained, and the third and fourth steps were repeated.
Polymerization of low molecular weight polymers of components (III) and (IV)
While maintaining the conditions, the polymer of the first stage is continuously passed through the second stage.
Through the third and fourth stages to remove ethylene-α-ole
Performing such as producing a fin copolymer composition
be able to. In this case (I), (II), (III) and
Each component of (IV) can be produced in any reactor
The production order and number of stages are not particularly limited.
No. The single-stage or multi-stage polymerization method is particularly limited.
There is no slurry method, gas phase method, solution method, high pressure ion method.
Various methods can be used. These methods
However, all the obtained compositions have the same properties
Things.The reaction temperature and pressure in these methods
Known operating conditions such as force are, for example, chemical engineering, 47,
[5] (1983) Fujita, Ushida, p329 and Komba
-Tech (1990.1) Doi, p77
You. In addition, components used in Examples and Comparative Examples described later.
Preparation of A1 to A11 and B1 to B5 which are minutes (I) or (II)
As can be seen from the example, the comonomer supply
Polymerization reduces the amount of highly branched components and decreases the W value.
And the polymerization temperature and pressure are increased
The S value is large and the W value is small because the distribution of the degree of narrowness is narrow.
Tend to Also polymerizationThe catalyst is, For example, titanium and / or
Or Ziegler type mainly composed of transition metals such as vanadium
CatalystCan be used.In particular, components (I) and (I
The catalyst for producing I)High activity supported on solid carrier
With a Ziegler-type catalystNeed to beYes, below
The details will be described. 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 these inorganic solid carriers such as water silicate
Compounds, sulfur-containing compounds, hydrocarbons, halogen-containing substances
To inorganic solid carriers such as those treated or reacted with
Transition metal compounds such as titanium, vanadium, zirconium
Halides of metals such as chromium and chromium, and alkoxyhalo
Genides, oxides, halogenated oxides, etc.
Is used as a solid component.
Organic compounds, preferably organic gold of zinc or aluminum
Compounds of the genus, or
-Pretreated by contact with an olefin,
Normally 50g-polymer / g-catalyst · hr · kg / cm with catalytic activity^Two-E
Refining pressure or higher, preferably 100 g-polymer / g-touch
Medium ・ hr ・ kg / cm^Two-Olefin pressure. The ethylene / α-olefin copolymer of the present invention
The body composition may have other compositions without departing from the gist of the present invention.
Refining polymer, rubber, antioxidant, UV absorption
Agent, light stabilizer, lubricant, antistatic agent, anti-fog agent, blocky
Anti-aging agent, processing aid, coloring pigment, cross-linking agent, foaming agent, none
Mixing known additives such as organic / organic fillers and flame retardants
Can be. [0029] The present invention will be described below in detail with reference to examples.
However, the present invention is not limited thereto. Destination
The test method used in the present invention is shown below. (1) Intrinsic viscosity The intrinsic viscosity [η] was measured with a decalin solution at 135 ° C. (2) Density Density gradient tube method according to JIS K6760 (23
° C). (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. [Measurement method] 8.5 liter capacity filled with Celite 545
Sample in a stainless steel column of 0.05 wt.
% By heating and melting at 135 ° C.
After injecting 5ml of sodichlorobenzene solution, 4 ℃ / min
Cool the sample to 25 ° C at a cooling rate of
To deposit. Next, orthodichlorobenzene was added to this column.
50 ℃ / hr constant speed while flowing at a constant speed of 1ml / min
And elute the sample sequentially. At this time, in the solvent
Of the asymmetric stretching vibration of methylene
Wave number 2925cm^-1Absorption for is detected by an infrared detector,
The relationship between the elution temperature and the elution amount,
Find the adult distribution. (4) Area ratio S by continuous heating elution fractionation method It was obtained by calculation as described above and FIG. (5) Orthodichlorobenzene soluble matter W at 25 ° C 0.5 g of the sample was placed in 20 ml of orthodichlorobenzene (O
In DCB), heat at 135 ° C for 2 hours
Is completely dissolved and then cooled to 25 ° C. in 2 hours. This
After leaving the solution at room temperature overnight at 25 ° C, filter with Teflon
The filtrate was collected through a filter and collected with an infrared spectrophotometer.
Wave number of asymmetric stretching vibration of 2950cm^-1Measure absorption for
And filter it from the results with a calibration curve created in advance.
Quantify the sample concentration in the liquid. (6) N-value Using a Koka type flow tester (manufactured by Shimadzu Corporation),
Extruded from a 2mmφ × 40mm die at 170 ° C resin temperature
And lower test pressure 20kg / cm^TwoAnd higher test pressure 15
0kg / cm^TwoAnd the apparent shear rate at
It is calculated from: (Equation 3) (7) Melt flow rate (MFR) It was measured according to JIS K6760. (Measurement temperature
190 ° C, load 2.16kg) (8) High load melt flow rate (HLMFR) It was measured in accordance with JIS K6760. (Measurement temperature 1
90 ° 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) It was measured according to JIS K6760. (Pulling speed
50mm / min, specimen thickness 2mm) (11) Tensile impact value (TIS) It was measured in accordance with ASTM D1822. (Specimen thickness
1.5mm) (12) Izod impact value (IIS) According to JIS K7110, at 23 ℃ and -40 ℃
It was 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 this case, a sheet with a thickness of 4 mm was made and the shape of the test piece was No. 2.
A. Sample preparation: 88 hours at 23 ° C and 50% humidity
And measured at 23 ° C. and −40 ° C. Where-
For samples measured at 40 ° C, adjust under the above conditions.
After performing, low temperature adjusted to -40 ° C in advance
The sample was kept in a room for about 3 hours and measured in a low temperature room. Test pieces
Made 5 each, and the average value of 5 measurements was taken as the measured value
Used. (13) Bending stiffness It was measured in accordance with JIS K7106. (Toyo Seiki
(Uses a bending stiffness tester manufactured by Co., Ltd.) (14) Melt tension (MT) Measured with a melt tension tester manufactured by Toyo Seiki Co., Ltd.
did. (Measurement temperature 190 ° C) (15) Critical shear rate (γc) With a capillary rheometer manufactured by INTESCO
Measured. (Measurement temperature 190 ° C) (16) Melting point (Tm) The maximum value measured using a differential scanning calorimeter manufactured by Rigaku Denki Co., Ltd.
Large peak temperatures were used. (Press Sea 0.2mm thick
Test pieces are prepared from (17) Environmental stress crack resistance (ESCR) F of constant strain ESCR according to JIS K6760
₅₀ Was measured. <Example of production by two-stage polymerization> In the multi-stage polymerization process shown in FIG.
Using a stirred type reactor having an internal volume of 30 liters as 1,
Tetrachloride on a solid support containing anhydrous magnesium chloride as a component
A solid catalyst supporting titanium is supplied from line 2;
Triethylaluminum (TEA)
3 and continuously under the polymerization conditions shown in Table 1.
Polymerization of the ren and comonomer was performed. In the figure, reference numeral 4 is
Ethylene supply line, 5 is comonomer supply line, 5
6 indicates a hydrogen supply line, and 7 indicates a solvent supply line.
You. Changing the type of α-olefin and polymerization conditions
By the combination, a polymer of A1 to A11 was produced.A1 to A8 are high
Polymerized with an active Ziegler type catalyst, A9 to A11 are conventional catalysts
Polymerization was carried out using a medium.The polymerization conditions are shown in Tables 1 and 2.
Tables 3 and 4 show the evaluation results of the physical properties. Next, a specific example of the production of the polymer A5 will be described.
Will be described. The polymerization conditions of the first-stage reactor 1 are as follows:
5 ℃, total pressure 8.2kg / cm^TwoG and keep the inside of reactor 1 full
Was. The amount of polymer produced E1 calculated from the heat balance is 1.68 k
g / hr. Partial sampling of polymerization products from the first reactor
Then, the polymer was recovered and physical properties were measured. Then, the first stage
The slurry polymerization product from the reactor is passed via line 8
A differential pressure is applied to the second-stage stirred reactor 9 having an inner volume of 70 liters.
Introduced. Table 1 shows ethylene, 1-butene and hydrogen.
Add as shown, polymerization temperature 60 ° C, total pressure 8.0kg / cm^TwoG,
The polymerization was continued while maintaining the liquid volume at 50 liters. Second step
The polymerization product discharged from the reactor 9 is then transferred to the flushing tank 10
Introduced via line 11. Polymer calculated from heat balance
The production amount E2 was 1.68 kg / hr. Continuous polymerization product
The polymer is extracted from the line 12 and the polymer is recovered.
The sex was evaluated. The finally recovered polymer product amount E is 3.
It was 36 kg / hr, which was in agreement with the calculated value of E1 + E2. Ma
In addition, at the time of average polymerization of the first-stage reactor 1 and the second-stage reactor 9
The intervals were 25 minutes and 40 minutes, respectively. [0032] [Table 1][0033] [Table 2][0034] [Table 3][0035] [Table 4]<Example of production by one-stage polymerization> One-stage polymerization shown in FIG.
In the polymerization process, a 70-liter stirred type reaction
Using anhydrous magnesium chloride as a component.
Catalyst with titanium tetrachloride supported on solid support and triethyl
Polymerization conditions shown in Table 5 using aluminum co-catalyst
To conduct one-stage polymerization continuously to produce low molecular weight component (B1)
Built. In addition, high molecular weight components (B2 ~
B5). The results of evaluating the physical properties of these polymers were
The results are shown in Table 5. [0037] [Table 5]Next, the polymer obtained by the one-stage polymerization is
Use a plastmill to sample samples under a nitrogen atmosphere.
70 g, rotation speed 20 rpm, kneading time 7 minutes, kneading temperature 1
Blend under blending conditions of 60 ° C to prepare blend composition
Made. Table 6 shows the compounding ratio and physical properties. [0039] [Table 6]Examples 1 to 7 are shown in Tables 3 and 4 above.
Polymerization product by two-stage polymerization and one-stage polymerization shown in Table 6
The blend composition consisting of the blended product was prepared in proportions shown in Table 7.
And a composition consisting of four components was prepared. Got
Table 8 shows the results of evaluating the physical properties of the composition. [0041] [Table 7][0042] [Table 8]<Comparative Examples 1 to 6> The results are shown in Tables 3 and 4 above.
Polymerization product by two-stage polymerization and one-stage polymerization shown in Table 6
The blend composition composed of the blended product was prepared in a proportion shown in Table 9.
And a composition consisting of four components was prepared. Of the composition
Table 10 shows the results of the evaluation of the physical properties. [0044] [Table 9][0045] [Table 10]<Comparative Examples 7 to 13> Commercially available linear products of the following brands
Table 11 and Table 11 show the evaluation results for low-density polyethylene.
And Table 12 below. (1) Philips # 10 (manufactured by Philips) (2) NUC G5221 (manufactured by Nippon Unicar) (3) Moretec 0234H (Idemitsu Petrochemical) (4) DSM 1016 (manufactured by DSM) (5) CdF FW1290 (manufactured by CdF) (6) Dow XD6000 8-130 (manufactured by Dow Chemical) (7) Ultzex 2520L (Mitsui Petrochemical Co., Ltd.) [0047] [Table 11][0048] [Table 12]As shown in the comparative examples of Tables 11 and 12,
In addition, all commercially available linear low-density polyethylene
Area ratio S by F and orthodichlorobenzene at 25 ° C
At least one of the soluble components W satisfies the requirements of the present invention.
Can not do it. Therefore, these linear low density poly
Ethylene as component (I) or component (II) of the present invention
Can not be used. 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 same figure, comparing the example with the comparative example,
The composition had a higher molecular weight (about 1
000) and low elution temperature, ie, short chain
Ingredients with a wide variety (soluble in orthodichlorobenzene at 25 ° C)
It can be seen that more is contained. This ingredient originated
Mainly improve the mechanical properties of bright compositions at low temperature
It is speculated that this is a factor. [0051] The ethylene / α-olefin copolymer of the present invention
The coalescing composition has the heat resistance of conventional polyethylene compositions.
In addition to maintaining various physical properties such as properties, ESCR, flexibility, etc.,
It has the features of (1) Mechanical at low temperature, especially at low temperature Izod impact value
Excellent properties and cold resistance. (2) Tensile properties, bending stiffness, environmental stress crack resistance, crack resistance
Good mechanical characteristics such as reap characteristics. (3) Melt elasticity and critical shear such as melt tension
Excellent flow characteristics such as speed, high-speed moldability, etc.
Has good moldability. As a result of the above advantages, various films, sheets, pies
Used for containers, hollow containers, various coating materials, foam materials, etc.
You. In addition, all components such as extrusion molding, hollow molding, injection molding, etc.
A wide range of molded products because it can be suitably used for molding
It became clear that you could get

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 6, (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

Claims (1)

(57) [Claim 1] (I) Having high activity supported on a solid carrier
5 to 85% by weight of a copolymer of ethylene and an α-olefin having 3 to 18 carbon atoms satisfying the following (a) to (d) , polymerized with a Ziegler-type catalyst : (a) intrinsic viscosity (η ₁ ) 2.0-9.0 dl / g, (b) Density (d ₁ ) 0.890-0.935 g / cm ³ , (c) Continuous temperature rising elution temperature The ratio S of the area Ib at an elution temperature of 25 to 90 ° C. to the area Ia under the curve of not less than
a) is calculated from the following equation: S ₁ or less; S ₁ = 20η ₁ ⁻¹ exp [−50 (d ₁ −0.900)] (d) Soluble content of orthodichlorobenzene at 25 ° C. W weight% is calculated from the following equation. W ₁ or more, W ₁ = 20 exp (−η ₁ ), (II) a highly active Ziegler type supported on a solid support
Copolymer of ethylene and α-olefin having 3 to 18 carbon atoms satisfying the following (e) to (h) and polymerized with a catalyst: 5 to 85
(E) Intrinsic viscosity (η ₂ ) 1.6 to 7.0 dl / g, (f) Density (d ₂ ) 0.890 to 0.945 g / cm ³ , (g) Continuous heating elution fractionation method In the elution temperature-elution amount curve, the ratio S (Ib / I) of the area Ib at the elution temperature of 25 to 90 ° C. to the area Ia under the elution temperature of 90 ° C. or more
S ₂ below a) is calculated from the following ^{_{equation, S 2 = 20η 2 -1 exp}} [-50 (d 2 -0.900)] (h) 25 ℃ orthodichlorobenzene soluble content W wt% is calculated from the following equation that W ₂ or _{more, W 2 = 20exp (-η 2} ) (III) below (i) and the ethylene homopolymer satisfies the (j) or a copolymer of ethylene and an α- olefin having from 3 to 18 carbon atoms 5 (I) intrinsic viscosity (η ₃ ) 0.2 dl / g to 1.5 dl / g, (j) density (d ₃ ) 0.890 to 0.980 g / cm ³ , and (IV) 5 to 60% by weight of an ethylene homopolymer or a copolymer of ethylene and an α-olefin having 3 to 18 carbon atoms satisfying (k) and (l), and (k) intrinsic viscosity (η ₄ ) of 0.2 dl / g-1.5 dl / g, (l) density (d ₄ ) 0.890-0.980 g / cm ³ , and the sum of the components (I), (II), (III) and (IV) is 100% by weight. (I) ~
A mixture of (IV) having different intrinsic viscosities, wherein the intrinsic viscosity of the mixture is 0.7 to 6.0 dl / g, the density is 0.890 to 0.950 g / cm ³ and the following equation 1 An ethylene / α-olefin copolymer composition having an N-value of 1.7 to 3.5. (Equation 1)