JPS60212439A - Polyethylene composition - Google Patents

Abstract

PURPOSE:A polyethylene composition, obtained by incorporating polyethylene having a narrow molecular weight distribution and low balance effect with polyethylene having a relatively wide molecular weight distribution and moderately high balance effect, and having improved physical properties and moldability. CONSTITUTION:A polyethylene composition, consisting of (A) polyethylene prepared by polymerization in the presence of a magnesium compound based Ziegler type catalyst to give 100,000-1,500,000mol.wt., 20-50 MIR at 1g/10min melt index and 20-50g/20cm die swell and (B) polyethylene prepared by polymerization in the presence of a chromium compound supported catalyst to give 50,000- 500,000mol.wt., 40-150 MIR under the same conditions as in the polyethylene (A) and 40-100g/20cm die swell, and obtained by incorporating the polyethylenes (A) with (B) at 1.5-30 molecular weight ratio between the polyethylenes (A) and (B) and 90:10-10:90 compounding weight ratio between the polyethylenes (A) and (B), and having 0.01-0.5g/10min melt index. The polyethylene (A) has a lower density than that of the polyethylene (B).

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a polyethylene composition having excellent physical and chemical properties and moldability, particularly for blow molding,
The present invention relates to a polyethylene composition that has particularly excellent molding processability and impact resistance, and also has good environmental stress cracking resistance (hereinafter referred to as HaOR) for use in extrusion molding, injection-blow molding, etc.

BACKGROUND OF THE INVENTION For polyethylene hollow, extrusion, injection-blow molding applications, etc., polymers with relatively high molecular weights and relatively broad molecular weight distributions are suitable.

Several methods have been proposed as methods for producing polyethylene with a wide molecular weight distribution.

As one method, a method has been proposed in which polyethylene with a cylindrical molecular weight and polyethylene with a low molecular weight are mixed (Japanese Patent Publication No. 45-3215, Japanese Patent Publication No. 45-22007, Japanese Unexamined Patent Publication No. 54-100444, Japanese Unexamined Patent Publication No. 1983-100444, 54-100445,%
Open 1 @ 54-161657, JP 55-60542
, JP-A-55-60543, JP-A-56-57841,
JP 57-133136゜) Also, as another method, 2
A multi-stage polymerization method with more than one stage has been attempted.
11349, Japanese Patent Publication No. 48-42716, Japanese Patent Publication No. 51-4
7079, Japanese Unexamined Patent Publication No. 52-19788).

Polymers produced by these methods have a wide molecular weight distribution and a good E8 (JR).

The present inventor investigated several examples of the above-mentioned method using polyethylene using a Ziegara-based catalyst, and found that the molecular weight distribution was wide and the HaOR was improved, but on the other hand, these polyethylene resin compositions It has a number of drawbacks in terms of practical properties, such as low strength, poor melt viscoelastic properties during molding, prone to uneven thickness in molded products, and inability to mold molded products with complex shapes. fC is solved
,,.

Problems, Means for Solving the Problems, and Structure of the Invention The present invention aims to improve these drawbacks and provide a polyethylene resin composition that has comprehensively excellent physical properties and moldability.

That is, the present invention is a polyethylene composition consisting of (B) two kinds of polyethylene particles selected from the group of single polymers of ethylene and copolymers of ethylene and α-olefins, and (1) polyethylene (4 ) has a molecular weight of 100,000 to 15
00,000, polyethylene (B) has a molecular weight of 50,000 to 500,000, (11) the molecular weight of polyethylene (4)/the molecular weight of polyethylene (B) is 1.5 to 30, (iii) polyethylene (A) ), the blending ratio of (B) is (5) to (B) in a weight ratio of 90:10 to 10:9.
MIR when one of the polyethylene particles (B) has a melt index of 1 t710 min of ethylene homopolymer obtained by one-stage polymerization;
Dice wells are 40-150 and 40-100 respectively
f/20cm, and the other is MIR when the melt index of ethylene homopolymer obtained by one-stage polymerization method is If710min.
.

Dice well is 20 or more and less than 50, 20 or more and 5, respectively.
This relates to a polyethylene composition that is polymerized using a catalyst that results in less than 0t/20cIn.

According to the present invention, it has both physical properties such as excellent impact resistance and E8 (JR, rigidity) and excellent molding processability, which has a wide range of industrial applications, and has hollow, extrusion and injection-blow molding applications, etc. A polyethylene resin composition suitable for use is provided.

The present invention will be explained in detail below.

Polyethylene (A), (B) which is a constituent component of the present invention
) is selected from the group of homopolymers of ethylene and copolymers of ethylene and alpha-olefins.

The α-olefin used for copolymerization has 3 to 14 carbon atoms.
Examples include propylene, butene, pentene, hexene, 4-methylpentene-11 octene, decene, and the like.

The molecular weight (MW) of polyethylene particles ranges from 100,000 to 1.5 million, and those less than 100,000 have a lower ESOR and 150
If it exceeds 1,000,000, the physical properties such as uniform dispersibility and impact resistance of each component will deteriorate. More preferably, it is 150,000 to 800,000. The density is preferably 0.91~o, 977/-,
More preferably, it is 0.91 to 0.955 f/cIn''.

The molecular weight (MWB) of polyethylene (B) is 50,000 to 5.
If it is less than 50,000, the physical properties such as uniform dispersion of each component and impact resistance will deteriorate, and if it exceeds 50,000, it will be classified as ESO.
R decreases, more preferably from 70,000 to 30,000. The density is preferably 0.91 to 0.9817 cm", more preferably 0.94 to 0.9817 cm".

Moreover, MWA/MWB is in the range of 1.5 to 30, and those exceeding 3o have poor uniform dispersibility of each component and have poor processability and physical properties. If it is less than 1.5, BS (JR is low. Preferably 2
~10.

In addition, a more desirable embodiment is that the density of the polyethylene is lower than that of polyethylene (B), for example, O, Ol-0 is more preferable than polyethylene (polyethylene v:/CB at a density of 0.91 to 0.95597 cm3). ,0
If it is lower than 6f/x, the impact resistance, ES (IR, etc.) will be further improved.

Next, the mixing ratio of polyethylene (4) and (B) will be explained. The ratio by weight of the amount of polyethylene to the amount of polyethylene (B) ranges from 90:10 to 10:9, preferably from 70:30 to 30:7. Outside this range, the uniform dispersibility of each component will deteriorate, processability and impact strength will not be improved, ESOR will deteriorate, and the characteristics of the polyethylene resin composition of the present invention will be impaired.

Next, when the melt index is 1 f/10 min, the MIR is 40-150 and the die swell is 40-100.
A method for producing a 2/20 secondary ethylene polymer will be described. In the present invention, a preferred catalyst is a catalyst supported on a chromium compound, and a particularly preferred example is a catalyst supported on a chromium compound in combination with an organic all-pole compound.

The chromium compound-supported catalyst used in the present invention is produced, for example, by supporting a chromium compound on an inorganic oxide carrier.

This will be explained in more detail below.

As the inorganic oxide carrier used in the present invention, silica, alumina, silica-alumina, zirconia, doria, etc. can be used, but silica and silica-alumina are preferable, and commercially available silica for highly active catalysts (high surface area, high pore volume) is particularly preferred.

The supported chromium compound is an oxide of chromium, or a compound that at least partially forms chromium oxide upon calcination, such as halides, oxyhalides, nitrates, acetates, sulfates, oxalates of chromium, Specific examples include chromium trioxide, chromyl chloride, potassium chromate, ammonium chromate, chromium nitrate, chromium acetate, chromium acetylacetonate, and ditertiary chromate.

Chromium trioxide, chromium acetate, and chromium acetylacetonate are particularly preferably used.

The chromium compound can be supported on the carrier by known methods such as impregnation, solvent distillation, and sublimation deposition. Depending on the type of chromium compound, it may be supported using an appropriate method, either aqueous or non-aqueous; for example, when using chromium dioxide, water may be used, and when using chromium acetylacetonate, a non-aqueous solution such as toluene may be used. good. The amount of chromium supported ranges from 0.05 to 5%, preferably from 0.1 to 3%, expressed as a weighted percentage of chromium atoms relative to the support.

Calcination activation is generally carried out in a non-reducing atmosphere, for example in the presence of oxygen, but it can also be carried out in the presence of an inert gas or under reduced pressure. Preferably, air substantially free of moisture is used.

Firing temperature is 300°C or higher, preferably 400-900°C
at a temperature range of several minutes to several tens of hours, preferably 30 minutes to 10
Time is done. During firing, it is recommended to blow in sufficient dry air and activate firing under a fluidized state.

Of course, it is also possible to use a known method for controlling activity, molecular weight, etc. by removing titanates, fluorine-containing salts, etc. during supporting or firing.

Further, examples of the organic metal compound used in combination with the chromium compound supported catalyst include the following.

(a) General formula AtaMgβR, 1pR2qR3rX
8Y.

An inert hydrocarbon soluble organomagnesium complex compound represented by (where α, β (a number larger than rlo, pr Q +
r + S + l is 0 or greater than 0, and 0((S
+1 )/(α+β)≦1.5 and p + q + r
There is a relationship of 10s + t = 3α12β, R1,
R", R" are the same or different and have 1 to 20 carbon atoms
hydrocarbon group, X, Y are the same or different OR, '+
O8iR'R'几7. NIL81 also 9 and UshiIO
represents a group selected from B4. R5, 几6゜B7.
)t8.几9 represents a hydrogen atom or a hydrocarbon group, and BIO represents a hydrocarbon group. ) (b) General formula MgR/uR/'vXxY.

(In the formula, R' and R'' represent a hydrocarbon i group, and B/.

Rj is a secondary or tertiary alkyl group in which at least one of them has 4 to 6 carbon atoms, or R' and R' are alkyl groups having different numbers of carbon atoms, or R', At least one of R" is a hydrocarbon group having 6 or more carbon atoms, and X.

Y is 0. A negative group containing N or S atoms, u
+v+x+Y is Of or a number greater than O, u + v
Inert hydrocarbon soluble organomagnesium compound represented by + x + y = 2 and O (x + y≦1.5 °) (c) General formula MaMgβ几1pR2qR3rX5Y
An inert hydrocarbon soluble M-magnesium complex compound represented by t (wherein α, β are numbers greater than 0, P + Q +
r * S Ht is O or greater than 0, and 0≦(S+
1)/(α+β)≦1.5 and p + q + r +
It has the relationship s + t = mα + 2β, M is an atom selected from zinc, boron, aluminum and lithium, m represents the valence of M, and R1, R", R"
are the same or different hydrocarbon groups having 1 to 20 carbon atoms, X and Y are the same or different OR4, OS group@B"
FLl, represents a group selected from NRRn9° and 5R10, 1lL4. Rj, B8.几1゜BS, B
e represents a hydrogen atom or a hydrocarbon group; BIO represents a hydrocarbon group).

(d) General formula M aM g / R'p R"q
(08t H3R4)r (in the formula, M is aluminum,
Atoms selected from the group consisting of zinc, boron, Bl, Bj.

Bj represents a hydrocarbon group having 1 to 20 carbon atoms, R4 represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and α
, β, r are numbers greater than 0, p, q are 0 or a number greater than 0, p+q+r=mα+2β, m is the valence of M) (e) General formula AtRI, (O8iHR”R8)3
．． −.

(In the formula, Bl and B11 represent a hydrocarbon group having 1 to 20 carbon atoms, R3 represents hydrogen or a hydrocarbon group having 1 to 20 carbon atoms, and n is a number of 1 to 3.) Aluminum compound (f) General formula At几1pHq(OI'L2)! (0
8iHR”R4).

(In the formula, p≧1.1≧q≧O, x≧0.25, Y≧
0.15゜1.5≧x + y≧0.5 and p + q
+ x + y −3, and “)Ll, B2.
Bl, B4 are the same or different and have 1 to 20 carbon atoms
An organoaluminum compound containing both an alkoxy group and a hydroxyl group (representing a hydrocarbon group).

(g) General formula AtRnX5-n (in the formula, 几 is a hydrocarbon group,
R"R' fZ represents a group, Bl, 几Z, R3,
B4 is a hydrocarbon, and n is a number l≦1≦3)
A foreign aluminum compound represented by

(h) An organic compound represented by the general formula ZoRm Zinc compounds.

(i) An organic lithium compound represented by the general formula LIR (in the formula, 几 represents a hydrocarbon group).

(1) General formula BRtX3-1 (In the formula, 几 is a hydrocarbon group, X is a halogen, ORI or 08iR"几8B4
Bl, Bl, 几4 are hydrocarbon groups, RR
is a hydrogen atom, fc is a hydrocarbon group, and t is 1≦t≦3
An organic boron compound represented by

Regarding the chromium compound-supported catalyst combining these organometallic compounds mentioned above, the °C temperature is given in Japanese Patent Application Laid-Open No. 56-79106.
, 56-120713, 56-131607, 5
7-70108, 57-70109, patent application No. 1987-1
93667.

Melt index is 1 r/1 (M when 1 min
IR force 40-150, tie swell force 40-1oof/
The 2ocrn ethylene homopolymer can be produced by C suspension polymerization, solution polymerization, gas phase polymerization, etc. using the above-mentioned chromium compound-supported catalyst.

Next, when the melt index is Is'/10m1n, M
IR is 20 or more and less than 50, Dicewell is 20 or more and less than 50
A manufacturing method for manufacturing an ethylene polymer having a particle diameter of less than t/20 cm will be described. In the present invention, a preferred catalyst is a magnesium compound-based Ziegler type catalyst, which is produced as follows.

As the magnesium compound-based Ziegler catalyst according to the present invention, any system based on organic magnesium or inorganic magnesium can be used.

Particularly preferred catalysts in the present invention include (1) the general formula MaMgβR', R''qXrYs (where α is 0 or a number greater than 0, p+Q+r+s is 0 or a number greater than O, and p + q + r +s
= mα + 2β, where M is all the elements belonging to Groups 1 to 2 of the periodic table, R1 and B2 are hydrocarbon groups having the same or different numbers of carbon atoms, and X and Y are the same or different. halogen, OR'', 08 iR'R
Represents a group 'lR', NR'R', 8R'1.
R3, R4, R5B6. R? , R8 represents a hydrogen atom or a hydrocarbon group, and R9 represents a hydrocarbon group); (11) a titanium or nonodium compound containing at least one halogen atom; and (If) At ,B,8i,Ge,Sn,T
e.

Among the halide compounds Ω(1) to (lii) of sb, (1
) and (11) or (1), (11), and (lii), and a solid catalyst component and an organometallic compound CB.
). Organometallic compound [, B] binding
[ is a compound of Group 1 of the periodic table, and a complex containing an organoaluminum compound and an organomagnesium is particularly preferable.

The reaction between the catalyst component (A) and the organometallic compound [B] acid component is as follows:
It is also possible to add both components into the polymerization system and carry out the reaction under polymerization conditions as the polymerization progresses, or it may be carried out in advance prior to the polymerization. In addition, the reaction ratio of the catalyst components is (
A) component 11 [B] component 1 to 3000 mmot
It is preferable to carry out the test within the range of .

Instead of the catalyst component (A), a TI compound supported on an inorganic Mg compound may be used.

Among these catalyst systems, the JP-B No. 52-3 system is particularly desirable because it can omit the decatalyst step industrially.
6788.52-36790.52-36791.52
-36792.52-50070.52-36794.
52-36795.52-36796.52-3691
5.52-36917.53-6019, JP-A-1973-
21876.50-31835.50-72044.5
There is one numbered 0-78619.53-40696. Using the catalyst, polyethylene (4) is produced by suspension polymerization, m-liquid polymerization, gas phase polymerization, etc.

The reason why the polyethylene resin composition of the present invention exhibits excellent moldability and physical properties is that polyethylene has a narrow molecular weight distribution and low Nonolans effect, and polyethylene has a relatively wide molecular weight distribution and has a moderate Nonolans effect. It is thought that high polyethylene forms an optimal molecular structure by linking and entangling the molecules.

Examples show how excellent the polyethylene resin composition of the present invention is. For example, when one polyethylene is replaced with another polyethylene, the catalyst used has a molecular weight in the same range as that of the other polyethylene. Even if polyethylene is used, it is difficult to obtain a polyethylene composition with excellent properties like the polyethylene resin composition of the present invention.

By using polyethylene (B) having a large MIR and die swell and a high Nonolas effect, a product with better moldability, E80R, and other physical properties can be obtained.

Any method may be used to mix the two components of polyethylene (with N), but for example, in a molten state, usually 15
It is preferable to use a single-screw or twin-screw extruder, a kneader, etc. at a temperature of 0 to 300°C.

The composition thus produced has an MI of 0.001 or more and less than 1O, and a density of 0.91 to 0.97 t/c.
m" preferably 0.935 to 0.96597 cm". Molecular weight distribution is 60 or more in MIR, preferably 7
It is 5 or more.

When used for injection-blow molding, MI is preferably 0.5 or more and 3 or less, and MI is preferably 0.005 or more and 1 or less for hollow or extrusion molding.

The polyethylene resin composition contains a heat stabilizer, an antioxidant,
Substances that can be normally added to or blended with polyolefins, such as ultraviolet absorbers, pigments, antistatic agents, lubricants, fillers, other polyolefins, thermoplastic resins, and rubbers, are used as necessary. Further, foam molding can be carried out by mixing a foaming agent.

Effects The characteristics of the polyethylene resin composition of the present invention are summarized as follows.

(1) Good fluidity and viscoelastic properties when melted, and excellent moldability. In particular, blow molding, extrusion moldability of pipes, sheets, etc., injection molding.
Good blow moldability and small thickness irregularities in molded products.

(2) The molded product has extremely high rigidity and impact resistance, and is E8
0R is also quite excellent, and all these characteristics are well balanced in practical terms.

(3) It has excellent physical properties and processability, making it easy to make thin-walled molded products. Therefore, it is suitable for the era of resource saving and energy saving.

(4) Molded products with good appearance can be obtained.

(5) Easy to manufacture.

(6) It can also be applied to various molding applications such as injection, film, processing, rotary and foam molding.

EXAMPLES AND COMPARATIVE EXAMPLES The present invention will be explained in more detail with reference to Examples below, but the present invention is not limited to these Examples in any way.

Symbols, measurement methods, and measurement conditions shown in Examples and Comparative Examples.

(1) MI: represents melt index, ASTMD
-1238, measured at a temperature of 190°C and a load of 2.16 kg.

(II) MIR; Load 21. under MI measurement conditions.
It refers to the quotient obtained by dividing the value measured with 6# by MI, and is one measure of molecular weight distribution, and the larger this value, the wider the molecular weight distribution.

(iiD molecule i (MW)? Using decalin solution, 13
Intrinsic viscosity (η) measured at 5°C and Journal of
Formula described in Polymer Science Vol. 36, p. 91 (1957), r) = 6.8 X 10-'MW' 61 to M
I hit W. Incidentally, the molecular weight in the present invention is determined entirely by this method.

Oψ density; measured according to ASTM D-1505.

(v) Impact strength i This is the notched Izo impact strength according to ASTM D-256.

(vD E80R; indicates environmental stress fracture resistance.

Using a blow molding machine with a 50 small-diameter screw, the cylinder temperature was 190°C and the mold temperature was 40°C. Fill with 200 d of % aqueous solution and seal tightly.
Put it in the oven at 60℃ 1.! ? ) Measure the time until cracks appear on the wall.

&1) Impact resistance of Certo; cold water (13℃)
) is filled, sealed, and repeatedly dropped from a height of 1.9 m onto a concrete surface, and the number of times until the &) bottle is destroyed is measured.

&l[l Extrusion processability: Using the above blow molding machine, measure the extrusion amount when extruding at a cylinder temperature of 190° C. and a screw rotation speed of 46 rpm.

4 cm Die swell: Expressed as the weight of a 20 cm long A-lino when extruded under the above &i00 conditions using a blow molding die with an outer diameter of 15 cm and an inner diameter of 10 m+.

(Thickness unevenness on the Settle; made at the time of Sakaki mentioned above/) Regarding the wall, we visually observed the thickness of the pinch-off weld at the no.y-dol part, where the thickness tends to become thinner, and found that it was in very good condition. A good condition is indicated by ◎, a very poor condition is indicated by Δ, and a very bad condition is indicated by ×.

Example 1-1 (1) Synthesis of catalyst for polyethylene (4) 2 tons of trichlorosilane (H8i0t3) 1 mol/l hexane solution
was placed in an 8t autoclave and kept at 50°C. This has a composition of AtMg5. o(0*Hs)z, o(n 0iH
s) 2 tons of a 1 mol/l hexane solution of the organoaluminum-magnesium complex of e, 5 (00 nH*) s, s was added dropwise over 2 hours with stirring, and the mixture was further reacted at this temperature for 2 hours. The produced solid component was washed twice with 2 tons of hexane by the sedimentation method. 2 tons of titanium tetrachloride was added to the slurry containing this solid component and reacted at 130° C. for 2 hours. The solid catalyst was isolated and washed with hexane until no free halogen was detected. This solid catalyst is 2.
It contained 1% titanium.

(2) Production of Polyethylene Container Polyethylene was produced by continuous polymerization using a stainless steel polymerization machine with a reaction capacity of 200 tons. Polymerization temperature was 86℃,
The polymerization pressure was 12 kg/cm”G, 8) cf/Hr.
The polymerization was controlled so that the amount produced was . The catalyst was triethylaluminum at a concentration of 0.5 mmo//l,
The solid catalyst was introduced together with 30t/1-1r of hexane so that the amount of polymerization produced was 8 mol/hr. Hydrogen was used as a molecular weight regulator.

Polyethylene (4) is copolymerized with butene-1 and has a density of 0.
95 (1). Polymerization was carried out so that the MWA was 250,000. The hydrogen concentration was about 15%, the butene-1% degree was about 3%, and the catalyst efficiency was 400,000 i polymer/fTi.

(3) Synthesis of catalyst for polyethylene (B) Dissolve 1 (l) of chromium trioxide in 2,000 m of distilled water, and add 500 m of silica (Grade 952 manufactured by Fuji Devin) to this solution.
f was immersed and stirred at room temperature for 1 hour.

This slurry was heated to distill off water, and then dried under reduced pressure at 120°C for 10 hours. This solid was calcined at 700°C for 5 hours under dry air circulation to obtain solid component (a). The obtained solid component (a) contained 1% by weight of chromium and was stored at room temperature under a nitrogen atmosphere.

(4) Production of polyethylene (B) Polyethylene was produced by continuous polymerization using the polymerization machine used in (2). Polymerization temperature: 83°C, polymerization pressure: 11A
The polymerization was controlled so that the production amount was 10.s#, /Hr at il/crn''G.The catalyst was the solid component synthesized in (3) at a concentration of 77~/L, and 401/Hr of hexane. Using hydrogen as a molecular weight regulator, the hydrogen concentration was made approximately 25%, the molecular weight was approximately 120,000, and the MIR
52, polyethylene (B) having a density of 0.967 was produced.

(5) d? ! Preparation of J ethylene resin composition The polyethylenes (4) and (B) produced as described above were mixed in a ratio of 50:500, and then this mixture was heated and treated with an antioxidant, Ctetrakis. Methylene-3
-(3',5'-di-t-butyl-4'-hydroxyphenyl)propione-)) 300 ppm of methane and 300 ppm of dilauryl-3,3'-thiodizolobionic acid ester were cooled and placed in a Henschel mixer. Stir and mix thoroughly. This mixture was mixed with Farrell's FUM for 2 hours.
The mixture was kneaded at a temperature of 20°C, and then this mixture was extruded using a single-screw extruder at a temperature of 200°C and pelletized to produce a polyethylene resin composition. As shown in Table 1, this polyethylene resin composition exhibits excellent moldability and physical properties.

Example 1-2 (1) Synthesis of catalyst for polyethylene (B) (1) Synthesis of solid component (a) Solid component (a) was synthesized in the same manner as in Example 1-1 (3).

(II) Synthesis of organoaluminum component (b) Triethylaluminum 100 mmo4 methylhydropolysiloxane (viscosity at 30°C = 30 centistokes)
50 mmot (8i standard), n-hebutane 1501
! Ll was weighed into a glass pressure-resistant container under a nitrogen atmosphere, and reacted at 100°C for 24 hours with stirring using a magnetic stirrer to form At(OzHs)z, 5(O8i.H-OH3.0
zHi). , a 5-heptane solution was synthesized. Next, 100 mmot (At standard) of this solution was heated for 20 mm in a nitrogen atmosphere.
0m/Weigh into a flask and add 5 ethanol from the dropping funnel.
A mixed solution of 0 mmot and 50 wtl of n-hebutane was added dropwise while stirring under water cooling, and after the dropwise addition, the mixture was allowed to react at room temperature for 1 hour.
t(02H5)2.6(002H5)o,5(O8i
-H・OH3・0鵞Hs) o, s A heptane solution was synthesized.

(2) Production of polyethylene (B) Example 1-1 Polyethylene was produced by continuous polymerization using the polymerization machine used in (2). Polymerization temperature is 83℃
, the polymerization pressure is 11 Jrf/cpn Yuki G, 10.5
The polymerization was controlled so that the production amount was kf/Hr.

The catalyst is the solid component (a) synthesized by +3)-(+) 77
At a concentration of ntg/L, the organoaluminum component molecule b) synthesized in (3)-(41) is 0.075 mmot/L.
was introduced with hexane at a concentration of 40 t/hr.

Polyethylene (B) having a molecular weight of about 120,000 and a MIR60 density of 0.967 was produced by using hydrogen as a molecular weight regulator and adjusting the hydrogen concentration to about 30%.

(3) Production of polyethylene resin composition The polyethylene (4) produced in Example 1-1 and the powder of polyethylene (B) produced by the above method were mixed in a weight ratio of 50:50, and carried out. A polyethylene resin composition was produced using the same additives, mixing, mixing, and extrusion conditions as in Example 1-1,
Table 1 shows the results of evaluating the performance. moldability,
It shows very excellent performance in both physical properties.

Example 1-3.1-4 The polyethylene powder produced in Example 1-1, the polyethylene produced in Example 1-2, and R powder (B) were mixed in the amounts shown in Table 1. A polyethylene resin composition was produced in the same manner as in Example 1-1 except for the additives, mixing, cross-wire, extrusion conditions, etc., and the results of evaluating the performance are shown in Table 1.

Comparative Example 1-1 Example 1-1 A polyethylene prison was produced using the catalyst used in (1).

Copolymerized with butene-1, density 0.955, MWA 18
Polymerization was carried out to give a total of 10,000 ml. Hydrogen concentration is about 17%,
The butene-1 concentration was approximately 2.5X, and the catalyst efficiency was 400,000 t polymer/l Tl.

A polyethylene composition was prepared using the same additives and extrusion conditions as in Example 1-1, and its performance was evaluated. Table 1 shows the results.

Comparative Examples 1 to 2 to 1-4 The polyethylene powder produced in Example 1-1 and the polyethylene powder produced in Example 1-2 were mixed in the amounts shown in Table 1. Other than mixing,
A polyethylene resin composition was produced in the same manner as in Example 1-1 using additives, mixing, cross-wire, extrusion conditions, etc., and the results of evaluating its performance are shown in Table 1.

Comparative Example 1-5 (1) Production of ethylene (B) Polyethylene (B) was polymerized using the catalyst and production method used to polymerize polyethylene (4) in Example 1-1.

Polyethylene (B) with a hydrogen concentration of 25%, a molecular weight of about 120,000, and a density of 0.966 was produced.

(2) Manufacture of polyethylene resin composition The polyethylene (G) manufactured in Example 1-1 and the polyethylene (B) powder manufactured above were mixed in a weight ratio of 50:50, and Example The pellets were made into pellets in the same manner as in 1-1, and their performance was evaluated.

The results are shown in Table 1.

Below is the blank space Example 2-1 (1) Synthesis of catalyst for polyethylene (5))・-n-
Butylmagnesium 138f and triethylaluminum 199 were fed into a stirring tank with a capacity of 4t together with 2t of 0-hebutane and allowed to react at 80°C for 2 hours. An aluminum-magnesium complex was synthesized. This complex 4
n-hebutane solution containing 00 mmot (549) 800
A solution of n-hebutane containing 400 mmot of titanium tetrachloride and 800 mmol of titanium tetrachloride was heated to 800 °C by purging with dry nitrogen.
Moisture and oxygen were removed, and the mixture was allowed to react at -20°C for 4 hours with stirring. The resulting hydrocarbon-insoluble solid is isolated and 0-
Washing with hebutane gave 1062 solid.

(2) Production of polyethylene powder Using the above-mentioned catalyst, low molecular weight polyethylene powder was produced by the method and conditions described below, and was used as a raw material for a polyethylene resin composition.

One polymerization was carried out using the same polymerization machine as in Example 1-1 and at the same polymerization temperature and pressure as in Example 1-1. The catalyst used was triethylaluminum at a concentration of 0.5 mmot/Z, and the solid catalyst was used at a concentration of 301/Hr so that the amount of polymerization product was 8 kf/Hr.
It was introduced with hexane and n. Hydrogen was used as the molecular IT regulator. Butene-1 was used as the comonomer. Polyethylene (4) has an MWA of 240,000.

The gas phase composition was adjusted so that the density was 0.950. The hydrogen concentration was about 18%, the butene-1 concentration was about 7%, and the catalyst efficiency was 300,000 V polymer/VHi.

(3) During the synthesis of catalyst for polyethylene (B) Synthesis of solid component (a) Instead of using chromium trioxide 101, chromium acetate (2) 1
Solid component (a) was synthesized and stored in the same manner as in Example 1-1, except that water salt 251 was used and the calcination temperature was 600°C. (11-1) Synthesis of organomagnesium component (b-1) 13.80 t of 1-butylmagnesium and 2.85 t of triethylaluminum were combined with 200 t of n-hesothane.
The composition A7Mga (Os
An organomagnesium complex corresponding to Hs)s(n C14H9)II was synthesized. Subsequently, this solution was cooled to 10° C., and 50 d of n-hebutane solution containing 50 mmot of n-octatool was added dropwise over 1 hour while cooling the reaction mixture to obtain an alkoxy-containing organomagnesium complex solution. Ta. A portion of this solution was taken, oxidized with dry air, and then hydrolyzed to convert all alkyl groups and alkoxy groups into alcohols, which was analyzed using a gas chromatograph. Ethanol, n-butanol, n-
From the analysis value of Octatool, the composition of the above complex is AtMg
4(UtHs)*, to(n(J4)1s)g, *5(
On OgHty)z, og.

(4) Production of polyethylene (B-1) Using the same polymerization machine, polymerization temperature, and pressure as in Example 1-1, the catalyst was (3) -(+
) At a concentration of 73■/l, the solid component (a) synthesized in (3
)-(organoaluminum component synthesized with li-1 (b
-1) At a concentration of 0.075 mmot/l, 40t/l
It was introduced with Hr of hexane. Hydrogen concentration is 5%, butene-1 concentration is approximately 1.5%, molecular weight is 130,000, MIR92,
Polyethylene (B-1) with a density of 0.95917 cm'' was produced.

(5) Production of polyethylene resin composition The polyethylene resin produced as described above and the powder of (B-1) were mixed in a weight ratio of 60:40, and then this mixture was heated, and as an antioxidant, n-octadecyl-β-(4'-
Add 500 ppm of hydroxy-3',5'-dyl-t-butylphenyl) propionate, 200 ppm of tetrakis(2,4-ditardylizotylphenyl)4,4'-hyphenylene diphosphonite and 500 ppm of calcium stearate and mix. The conditions for kneading, extrusion, etc. were the same as in Example 1-1. A polyethylene resin composition was produced. Its performance is shown in Table 2.

Example 2-2 The solid catalyst component (a) used in Example 2-1 was combined with the following organic magnesium component (b-2).

(1) Synthesis of organomagnesium component (b-2)
-Dithylmagnesium 13.802 and diethylzinc 2.
061 with 200 m of n-hebutane in a 500 d flask and reacted at 80'C with stirring for 2 hours to obtain the composition ZnMg5(OzHsls(n04H*
) tz organomagnesium complex heptane solution was obtained.

(2) Production of polyethylene (B-2) Using the same polymerization machine, polymerization temperature, and pressure as in Example 1-1, the catalyst was used at a concentration of 62 ~/l of the isomer component (a) synthesized in Examples 2-1, Organomagnesium component (b-2) 0.065 mmot/l, f
) It was introduced with hexane at 401/Hr. Polyethylene (E) with a molecular cap of 120,000, an MIR of 90, and a density of 0.95917 cm was produced at a hydrogen concentration of 15% and a butene-1 concentration of about 1.5%.

(3) Production of polyethylene resin composition A polyethylene resin composition was produced in the same manner as in Example 2-1 except that polyethylene (5), ((J) and polyethylene (B-2) produced in Example 2-1 were used. The product was manufactured. Its performance is second to none.
Shown in the table.

Comparative Example 2-1 Using the polyethylene (1) produced in Example 2-1, a polyethylene resin composition was produced using the same additives, mixing, kneading and extrusion conditions as in Example 2-1. Its performance is shown in Table 2.

Comparative Example 2-2 Polyethylene (B-a) was produced using the catalyst used to produce the polyethylene prison in Example 2-1.

Polyethylene (4), (B-3) (7) Pa? A polyethylene resin composition was produced in the same manner as in Example 2-1 except that a resin was used. Its performance is shown in Table 2.

The manufacturing conditions for polyethylene (B-3) are as follows.

Hydrogen concentration is about 32%, butene-1 concentration is about 0.3%, catalyst efficiency is 280,000? Polymerization was carried out in the same manner as the polyethylene prison except that the polymer/rTi was used. This polyethylene (B
-3) has a molecular weight of 120,000, an MIR of 37, and a density of 0.960.
It was 17cm".

Example 3 (1) Manufacture of polyethylene sieve Using the catalyst used to produce polyethylene sieve in Example 1-1, polyethylene sieve was polymerized using the polymerization machine, temperature, and pressure as in Example 1-1.

The hydrogen concentration and octene-1 concentration were adjusted so that the polyethylene prison had a molecule f[350,000 and a density of 0.950. The hydrogen concentration was about 10% and the octene-1 concentration was about 2%.

(2) Production of polyethylene (B) Example 1 except that the catalyst used to produce polyethylene (B) in Example 1-2 was used and the hydrogen concentration was approximately 1% so that the molecular weight was 20%. Polyethylene (B) was produced in the same manner as in -1.

(3) Manufacture of polyethylene resin composition A polyethylene resin composition was manufactured by mixing polyethylene powder (B) at the compounding ratio shown in Table 3 and using the same conditions as in Example 1-1 except for the following. Its performance is shown in Table 3.

Comparative Example 3-1 A polyethylene resin composition was produced in the same manner as in Example 1-1 using only polyethylene (4). Its performance is shown in Table 3.

Comparative Example 3-2 Using the catalyst used to produce polyethylene particles in Example 171, polyethylene particles were polymerized using the same polymerization machine, temperature, and pressure as in Example 1-1.

The hydrogen concentration and octene-1 concentration of polyethylene (5) were adjusted to have a molecular weight of 380,000 and a density of 0.950. The hydrogen concentration was about 8% and the octene-1 concentration was about 2%.

Polyethylene (B) was polymerized at a hydrogen concentration of 20% so as to have a molecular weight of 170,000 and a density of 0.967.

Polyethylene (4) and (B) were mixed at the blending ratio shown in Table 3, and the other conditions were the same as in Example 1-1 to produce a polyethylene resin composition. Its performance is shown in Table 3.

As shown in Examples and Comparative Examples 1 to 3 below, the polyethylene resin composition comprising polyethylene (2) and (B) according to the present invention has extremely excellent moldability and physical properties of molded products. and also that they are well balanced. On the other hand, a polyethylene resin composition consisting only of polyethylene (N) has poor molding processability and also has poor physical properties of the molded product.A polyethylene resin composition consisting only of polyethylene (B) has poor molding processability. However, the physical properties of the molded product are considerably lower than the level of the polyethylene resin composition of the present invention.On the other hand, when polyethylene made from the same type of catalyst as the polyethylene prisoner is used instead of (B), Both its moldability and physical properties are at a low level.That is, the present invention was achieved by taking advantage of the properties of the polymers produced by each catalyst, as described above.

Patent applicant: Asahi Kasei Industries, Ltd.

Claims (5)

[Claims] (1) A polyethylene composition consisting of (B) two types of polyethylene particles selected from the group of homopolymers of ethylene and copolymers of ethylene and α-olefins, (i) the polyethylene particles have a molecular weight of 10,000 to 1.5 million, polyethylene (B) has a molecular weight of 50,000 to 500,000, (II) the molecular weight of polyethylene (4)/the molecular weight of polyethylene (B) is 1.5 to 30, and (iiD yW IJ ethylene The blending ratio of (A) and (B) is (5) to (B) from 90 to 10 by weight.
The MIR and die swell are 40 to 150 and 40 to 100y/20yR, respectively, when one of Oφ polyethylene and (B) has a melt index of 19710 mIn of ethylene alone AJi combined by one-stage polymerization method. The other is the MIR and die swell of 20 or more and less than 50 and 20 or more and 50f/20cw when the melt index of ethylene homopolymer is if/10mln, respectively, by one-stage polymerization method.
A polyethylene composition that is polymerized using a catalyst that results in less than I (2) The density of polyethylene (4) is
B) The polyethylene composition according to claim 1 whose density is lower than that of (3) The blending ratio of polyethylene and (B) is
The polyethylene composition according to claim 1 or 2, wherein the weight ratio is in the range of 70:30 to 30:70. (4) The molecular weight of polyethylene (4) is 150,000 to 80
70,000, and the molecular weight of polyethylene (g) is 70,000 to 30,000.
00,000, and the molecular weight ratio (molecular weight of polymer/molecular weight of (B)) is from 2 to 10.
Polyethylene compositions described in section (5) The melt index of the composition is 0.01 or more and 0.01 or more.
Claim 1 in the range of 5r/10m1n or less
．． Polyethylene composition (6) according to item 2.3 or 4. The composition has a melt index of 0.5 or more and 2f/10.
Claim No. 1゜2. m + n or less.
Polyethylene composition (7) according to item 3 or 4. MIR when the melt index of the ethylene homopolymer obtained by the one-stage polymerization method is If/10 m1n. Dice well is 20 or more as polyethylene (4) 5
0 Unfashionable, Polymerized using a catalyst that produces 20 or more and less than 50 f720α, 4 as polyethylene (B)
The polyethylene composition according to any one of claims 1 to 6, which is polymerized using a catalyst such that the number of polyethylene compositions is 0 to 150 and 40 to 1001/20.